JP7412530B2 - Curable resin composition, cured film, laminate, method for producing cured film, and semiconductor device - Google Patents

Description

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

Resins such as polyimide, polybenzoxazole, and polyamideimide have excellent heat resistance and insulation properties, and are therefore used in a variety of applications. Although the above-mentioned uses are not particularly limited, examples of semiconductor devices for mounting include use as an insulating film, a sealing material material, or a protective film. It is also used as a base film and coverlay for flexible substrates.

For example, in the above-mentioned applications, the resin such as polyimide, polybenzoxazole, polyamideimide, etc. is a cured resin containing at least one resin selected from the group consisting of a polyimide precursor, a polybenzoxazole precursor, and a polyamideimide precursor. It is used in the form of a synthetic resin composition.
Such a curable resin composition is applied to a substrate by coating, for example, to form a photosensitive film, and then the cured product is applied to the substrate by performing exposure, development, heating, etc. as necessary. can be formed.
The polyimide precursor, polybenzoxazole precursor, and polyamideimide precursor are cyclized, for example, by heating, and become polyimide, polybenzoxazole, and polyamideimide, respectively, in the cured product.
Since the curable resin composition can be applied by known coating methods, for example, there is a high degree of freedom in designing the shape, size, application position, etc. of the curable resin composition when it is applied. It can be said that it has excellent manufacturing adaptability. In addition to the high performance of polyimide, polybenzoxazole, polyamide-imide, etc., industrial applications of the above-mentioned curable resin compositions are increasingly expected from the viewpoint of excellent manufacturing adaptability.

For example, Patent Document 1 describes 100 parts by mass of a polyimide precursor with a specific structure, 1 to 20 parts by mass of a photopolymerization initiator, and 1 part of a functional group selected from the group consisting of a hydroxyl group, an ether group, and an ester group. A negative photosensitive resin composition containing 0.01 to 10 parts by mass of a monocarboxylic acid compound having 2 to 30 carbon atoms or more is described.

Japanese Patent Application Publication No. 2011-191749

In forming patterns made of curable resin compositions, there is a demand for improved resolution.

The present invention provides a curable resin composition with excellent resolution during pattern formation, a cured film obtained by curing the curable resin composition, a laminate containing the cured film, a method for producing the cured film, and It is an object of the present invention to provide a semiconductor device including the cured film or the laminate.

Examples of representative embodiments of the invention are shown below.
<1> At least one resin selected from the group consisting of polyimide precursors, polybenzoxazole precursors, and polyamideimide precursors,
organometallic complexes, and
At least one species selected from the group consisting of a compound represented by the following formula (1-1), a compound represented by the following formula (1-2), and a compound represented by the following formula (1-3) including;
A curable resin composition in which the content of the above compound is 10 to 50,000 ppm based on the total mass of the composition.
In formula (1-1), formula (1-2) or formula (1-3), R ¹¹ and R ¹² each independently represent an unsubstituted aliphatic hydrocarbon group having 1 to 7 carbon atoms or a substituent. At least one member selected from the group consisting of a primary amine salt structure, a secondary amine salt structure, a tertiary amino group, a tertiary amine salt structure, a quaternary ammonium group, and an aliphatic heterocyclic group an aliphatic hydrocarbon group having 1 to 7 carbon atoms having a substituent, or having at least one substituent selected from the group consisting of a hydroxy group, an alkoxy group, a thiol group, and an alkylthio group having 2 carbon atoms -7 aliphatic hydrocarbon group; R ²¹ and R ²² each independently represent an aliphatic hydrocarbon group having 1 to 7 carbon atoms which may have a substituent; R ³¹ and R ³² each Each independently represents an aliphatic hydrocarbon group having 1 to 7 carbon atoms which may have a substituent, and R ³³ represents an aliphatic hydrocarbon group having 1 to 7 carbon atoms which may have a substituent.
<2> The curable resin composition according to <1>, wherein the compound is a compound represented by any one of the following formulas (G-1) to (G-12).

<3> The curable resin composition according to <1> or <2>, further comprising a photopolymerization initiator.
<4> The curable resin composition according to any one of <1> to <3>, further comprising a crosslinking agent.
<5> The curable resin composition according to any one of <1> to <4>, wherein the organometallic complex is a metallocene compound.
<6> The curable property according to any one of <1> to <5>, wherein the metal contained in the organometallic complex is at least one metal selected from the group consisting of titanium, zirconium, and hafnium. Resin composition.
<7> The curable resin composition according to any one of <1> to <6>, wherein the organometallic complex has the ability to initiate radical photopolymerization.
<8> The curable resin composition according to any one of <1> to <7>, which is used for forming a photosensitive film subjected to negative development.
<9> The curable resin composition according to any one of <1> to <8>, which is used for forming an interlayer insulating film for a rewiring layer.
<10> A cured film obtained by curing the curable resin composition according to any one of <1> to <9>.
<11> A laminate comprising two or more cured films according to <10> and a metal layer between any of the cured films.
<12> A method for producing a cured film, comprising a film forming step of applying the curable resin composition according to any one of <1> to <9> to a substrate to form a film.
<13> The method for producing a cured film according to <12>, including an exposure step of exposing the film to light and a development step of developing the film.
<14> The method for producing a cured film according to <13>, wherein the exposure light used for the exposure includes light with a wavelength of 405 nm.
<15> The method for producing a cured film according to <13> or <14>, wherein the exposure is by a laser direct imaging method.
<16> The method for producing a cured film according to any one of <12> to <15>, including a heating step of heating the film at 50 to 450°C.
<17> A semiconductor device comprising the cured film according to <10> or the laminate according to <11>.

According to the present invention, a curable resin composition with excellent resolution during pattern formation, a cured film obtained by curing the curable resin composition, a laminate including the cured film, a method for producing the cured film, And a semiconductor device including the cured film or the laminate is provided.

Main embodiments of the present invention will be described below. However, the invention is not limited to the illustrated embodiments.
In this specification, a numerical range expressed using the symbol "~" means a range that includes the numerical values written before and after "~" as the lower limit and upper limit, respectively.
As used herein, the term "step" includes not only independent steps but also steps that cannot be clearly distinguished from other steps as long as the intended effect of the step can be achieved.
In the description of a group (atomic group) in this specification, the description that does not indicate substitution or unsubstitution includes a group having a substituent (atomic group) as well as a group having no substituent (atomic group). For example, "alkyl group" includes not only an alkyl group without a 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. Examples of the light used for exposure include actinic rays or radiation such as the bright line spectrum of a mercury lamp, far ultraviolet rays typified by excimer lasers, extreme ultraviolet rays (EUV light), X-rays, and electron beams.
As used herein, "(meth)acrylate" means both "acrylate" and "methacrylate", or either "(meth)acrylate", and "(meth)acrylic" means both "acrylic" and "methacrylic", or , and "(meth)acryloyl" means either or both of "acryloyl" and "methacryloyl."
In this specification, Me in the structural formula represents a methyl group, Et represents an ethyl group, Bu represents a butyl group, and Ph represents a phenyl group.
In this specification, the total solid content refers to the total mass of all components of the composition excluding the solvent. Further, in this specification, the solid content concentration is the mass percentage of other components excluding the solvent with respect to the total mass of the composition.
In this specification, unless otherwise stated, weight average molecular weight (Mw) and number average molecular weight (Mn) are defined as polystyrene equivalent values according to gel permeation chromatography (GPC measurement). In this specification, weight average molecular weight (Mw) and number average molecular weight (Mn) are expressed using, for example, HLC-8220GPC (manufactured by Tosoh Corporation) and guard column HZ-L, TSKgel Super HZM-M, TSKgel. It can be determined by using Super HZ4000, TSKgel Super HZ3000, and TSKgel Super HZ2000 (manufactured by Tosoh Corporation). Unless otherwise stated, those molecular weights are measured using THF (tetrahydrofuran) as an eluent. Furthermore, unless otherwise specified, a detector with a wavelength of 254 nm of UV rays (ultraviolet rays) is used for detection in the GPC measurement.
In this specification, when the positional relationship of each layer constituting a laminate is described as "upper" or "lower", there is another layer above or below the reference layer among the plurality of layers of interest. It would be good if there was. That is, a third layer or element may be further interposed between the reference layer and the other layer, and the reference layer and the other layer do not need to be in contact with each other. In addition, unless otherwise specified, the direction in which layers are stacked on the base material is referred to as "top", or if there is a photoresist film, the direction from the base material to the photoresist film is referred to as "top"; The opposite direction is called "down". Note that such a setting in the vertical direction is for convenience in this specification, and in an actual embodiment, the "up" direction in this specification may be different from vertically upward.
In this specification, unless otherwise specified, the composition may contain, as each component contained in the composition, two or more compounds corresponding to that component. Further, unless otherwise specified, the content of each component in the composition means the total content of all compounds corresponding to that component.
In this specification, unless otherwise stated, the temperature is 23° C., the atmospheric pressure is 101,325 Pa (1 atm), and the relative humidity is 50% RH.
In this specification, combinations of preferred aspects are more preferred aspects.

(Curable resin composition)
The curable resin composition of the present invention comprises at least one resin selected from the group consisting of a polyimide precursor, a polybenzoxazole precursor, and a polyamideimide precursor, an organometallic complex, and the formula (1-1 ), a compound represented by formula (1-2), and a compound represented by formula (1-3), and the mass content of the above compound. is 10 to 50,000 ppm based on the total weight of the composition.
Hereinafter, at least one resin selected from the group consisting of a polyimide precursor, a polybenzoxazole precursor, and a polyamideimide precursor is also referred to as a "specific resin", and a compound represented by formula (1-1), The compound represented by formula (1-2) and the compound represented by formula (1-3) are also collectively referred to as a "specific compound."

In formula (1-1), formula (1-2) or formula (1-3), R ¹¹ and R ¹² each independently represent an unsubstituted aliphatic hydrocarbon group having 1 to 7 carbon atoms or a substituent. At least one member selected from the group consisting of a primary amine salt structure, a secondary amine salt structure, a tertiary amino group, a tertiary amine salt structure, a quaternary ammonium group, and an aliphatic heterocyclic group an aliphatic hydrocarbon group having 1 to 7 carbon atoms having a substituent, or having at least one substituent selected from the group consisting of a hydroxy group, an alkoxy group, a thiol group, and an alkylthio group having 2 carbon atoms -7 aliphatic hydrocarbon group; R ²¹ and R ²² each independently represent an aliphatic hydrocarbon group having 1 to 7 carbon atoms which may have a substituent; R ³¹ and R ³² each Each independently represents an aliphatic hydrocarbon group having 1 to 7 carbon atoms which may have a substituent, and R ³³ represents an aliphatic hydrocarbon group having 1 to 7 carbon atoms which may have a substituent.

The curable resin composition of the present invention is preferably used to form a photosensitive film that is subjected to exposure and development, and is preferably used to form a film that is subjected to exposure and development using a developer containing an organic solvent. It is preferable.
Further, the curable resin composition of the present invention is preferably used for forming a photosensitive film to be subjected to negative development.
In the present invention, negative development refers to development in which non-exposed areas are removed by development during exposure and development, and positive development refers to development in which exposed areas are removed by development.
The above-mentioned exposure method, the above-mentioned developer, and the above-mentioned development method include, for example, the exposure method explained in the exposure step in the explanation of the cured film manufacturing method described below, the developer and the development method explained in the development step. is used.

The curable resin composition of the present invention has excellent exposure sensitivity and chemical resistance of the resulting pattern.
Although the mechanism by which the above effect is obtained is unknown, it is presumed as follows.

For example, as described in Patent Document 1, an organic titanium compound or the like is added to a curable resin composition in order to improve chemical resistance.
However, when patterning is performed using a composition containing an organometallic complex, the organometallic complex may aggregate within the film, resulting in a decrease in resolution.
The curable resin composition of the present invention contains a specific compound in a specific content mass.
It is thought that the strong interaction between the specific compound and the organometallic complex causes the organometallic complex contained in the composition to be dispersed in a nearly uniform state within the film. As a result, it is presumed that the resin composition of the present invention has excellent resolution.
If the content of the specific compound is 10 ppm or more based on the total mass of the composition, the dispersibility of the organometallic complex will be sufficiently improved, so it is presumed that the resolution will be excellent.
Furthermore, if the content of the specific compound is 50,000 ppm or less based on the total mass of the composition, it is assumed that the influence of the specific compound on the removability of non-patterned areas by the developer is suppressed, resulting in excellent resolution. be done.

Hereinafter, the components contained in the curable resin composition of the present invention will be explained in detail.

<Specific resin>
The curable resin composition of the present invention contains at least one resin (specific resin) selected from the group consisting of a polyimide precursor, a polybenzoxazole precursor, and a polyamideimide precursor.
The curable resin composition of the present invention preferably contains a polyimide precursor as the specific resin.
Moreover, it is preferable that the specific resin has a radically polymerizable group.
When the specific resin has a radical polymerizable group, the curable resin composition preferably contains a radical photopolymerization initiator described below as a photosensitizer, and contains a radical photopolymerization initiator described below as a photosensitizer, and It is more preferable to include a radical crosslinking agent as described below, and it is still more preferable to include a photoradical polymerization initiator described below as a photosensitizer, a radical crosslinking agent described below, and a sensitizer described below. For example, a negative photosensitive film is formed from such a curable resin composition.
Further, the specific resin may have a polarity converting group such as an acid-decomposable group.
When the specific resin has an acid-decomposable group, the curable resin composition preferably contains a photoacid generator described below as a photosensitizer. From such a curable resin composition, for example, a chemically amplified positive-working photosensitive film or a negative-working photosensitive film is formed.

[Polyimide precursor]
The polyimide precursor used in the present invention is not particularly limited in its type, but preferably contains a repeating unit represented by the following 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 represent 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 preferably an oxygen atom.
R ¹¹¹ in formula (2) represents a divalent organic group. Examples of divalent organic groups include straight-chain or branched aliphatic groups, cyclic aliphatic groups, and aromatic groups, including straight-chain or branched aliphatic groups having 2 to 20 carbon atoms, A group consisting of a cyclic aliphatic group having 6 to 20 carbon atoms, an aromatic group having 6 to 20 carbon atoms, or a combination thereof is preferable, and a group containing an aromatic group having 6 to 20 carbon atoms is more preferable. A particularly preferred embodiment of the present invention is a group represented by -Ar-L-Ar-. 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 -, NHCO-, or a combination of two or more of the above. These preferred ranges are as described above.

Preferably R ¹¹¹ is derived from a diamine. Examples of diamines used in the production of polyimide precursors include linear or branched aliphatic, cyclic aliphatic, and aromatic diamines. One type of diamine may be used, or two or more types may be used.
Specifically, a linear or branched aliphatic group having 2 to 20 carbon atoms, a cyclic aliphatic group having 6 to 20 carbon atoms, an aromatic group having 6 to 20 carbon atoms, or a group consisting of a combination thereof. It is preferable to use a diamine containing an aromatic group having 6 to 20 carbon atoms, and more preferably a diamine containing a group consisting of an aromatic group having 6 to 20 carbon atoms. Examples of aromatic groups include the following.

In the formula, A is a single bond or an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be substituted with a fluorine atom, -O-, -C(=O)-, -S-, -SO _2- , NHCO-, or a combination thereof, and is preferably a group selected from a single bond, an alkylene group having 1 to 3 carbon atoms optionally substituted with a fluorine atom, -O-, -C( A group selected from =O)-, -S-, or -SO ₂ - is more preferable, and -CH ₂ -, -O-, -S-, -SO ₂ -, -C(CF ₃ ) ₂ - or -C(CH ₃ ) ₂ - is more preferable.
In the formula, * represents a bonding site with another structure.

Specifically, the diamines include 1,2-diaminoethane, 1,2-diaminopropane, 1,3-diaminopropane, 1,4-diaminobutane and 1,6-diaminohexane; 1,2- or 1 , 3-diaminocyclopentane, 1,2-, 1,3- or 1,4-diaminocyclohexane, 1,2-, 1,3- or 1,4-bis(aminomethyl)cyclohexane, bis-(4- aminocyclohexyl)methane, bis-(3-aminocyclohexyl)methane, 4,4'-diamino-3,3'-dimethylcyclohexylmethane and isophorone diamine; 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'-diamino Diphenylsulfone, 4,4'- and 3,3'-diaminodiphenylsulfide, 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'-Tetraaminobiphenyl, 3,3',4,4'-tetraaminodiphenyl ether, 1,4-diaminoanthraquinone, 1,5-diaminoanthraquinone, 3,3-dihydroxy-4,4'-diaminobiphenyl , 9,9'-bis(4-aminophenyl)fluorene, 4,4'-dimethyl-3,3'-diaminodiphenylsulfone, 3,3',5,5'-tetramethyl-4,4'-diamino Diphenylmethane, 2,4- and 2,5-diaminocumene, 2,5-dimethyl-p-phenylenediamine, acetoguanamine, 2,3,5,6-tetramethyl-p-phenylenediamine, 2,4,6- Trimethyl-m-phenylenediamine, bis(3-aminopropyl)tetramethyldisiloxane, 2,7-diaminofluorene, 2,5-diaminopyridine, 1,2-bis(4-aminophenyl)ethane, diaminobenzanilide, Esters of diaminobenzoic acid, 1,5-diaminonaphthalene, diaminobenzotrifluoride, 1,3-bis(4-aminophenyl)hexafluoropropane, 1,4-bis(4-aminophenyl)octafluorobutane, 1, 5-bis(4-aminophenyl)decafluoropentane, 1,7-bis(4-aminophenyl)tetradecafluoroheptane, 2,2-bis[4-(3-aminophenoxy)phenyl]hexafluoropropane, 2 ,2-bis[4-(2-aminophenoxy)phenyl]hexafluoropropane, 2,2-bis[4-(4-aminophenoxy)-3,5-dimethylphenyl]hexafluoropropane, 2,2-bis [4-(4-aminophenoxy)-3,5-bis(trifluoromethyl)phenyl]hexafluoropropane, p-bis(4-amino-2-trifluoromethylphenoxy)benzene, 4,4'-bis( 4-Amino-2-trifluoromethylphenoxy)biphenyl, 4,4'-bis(4-amino-3-trifluoromethylphenoxy)biphenyl, 4,4'-bis(4-amino-2-trifluoromethylphenoxy) ) diphenylsulfone, 4,4'-bis(3-amino-5-trifluoromethylphenoxy)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 At least one diamine selected from ',6,6'-hexafluorotridine and 4,4'-diaminoquaterphenyl is mentioned.

Also preferred are the diamines (DA-1) to (DA-18) described in paragraphs 0030 to 0031 of International Publication No. 2017/038598.

Further, diamines having two or more alkylene glycol units in the main chain described in paragraphs 0032 to 0034 of International Publication No. 2017/038598 are also preferably used.

From the viewpoint of flexibility of the resulting organic film, R ¹¹¹ is preferably represented by -Ar-L-Ar-. 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 -, NHCO-, or 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-ray 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-ray transmittance and availability, a divalent organic group represented by formula (61) is more preferable.
Formula (51)

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 trifluoro It is a methyl group.
The monovalent organic groups R ⁵⁰ to R ⁵⁷ include unsubstituted alkyl groups having 1 to 10 carbon atoms (preferably 1 to 6 carbon atoms), and unsubstituted alkyl groups having 1 to 10 carbon atoms (preferably 1 to 6 carbon atoms). Examples include fluorinated alkyl groups.

In formula (61), R ⁵⁸ and R ⁵⁹ are each independently a fluorine atom or a trifluoromethyl group.
Examples of the diamine compound giving the structure of formula (51) or (61) include 2,2'-dimethylbenzidine, 2,2'-bis(trifluoromethyl)-4,4'-diaminobiphenyl, 2,2'- Bis(fluoro)-4,4'-diaminobiphenyl, 4,4'-diaminoctafluorobiphenyl, and the like. These may be used alone or in combination of two or more.

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

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 bonding site with another structure.

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

Specific examples of R ¹¹⁵ include a tetracarboxylic acid residue remaining after removal of an anhydride group from a tetracarboxylic dianhydride. One type of tetracarboxylic dianhydride may be used, or two or more types may be used.
It is preferable that the tetracarboxylic dianhydride is represented by the following formula (O).

In formula (O), R ¹¹⁵ represents a tetravalent organic group. The preferred range of R ¹¹⁵ is the same as 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, 3,3',4,4'- Diphenylsulfidetetracarboxylic dianhydride, 3,3',4,4'-diphenylsulfonetetracarboxylic dianhydride, 3,3',4,4'-benzophenonetetracarboxylic dianhydride, 3,3' , 4,4'-diphenylmethanetetracarboxylic dianhydride, 2,2',3,3'-diphenylmethanetetracarboxylic dianhydride, 2,3,3',4'-biphenyltetracarboxylic dianhydride, 2,3,3',4'-benzophenonetetracarboxylic dianhydride, 4,4'-oxydiphthalic 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 dianhydride, and these Examples include alkyl derivatives having 1 to 6 carbon atoms and alkoxy derivatives having 1 to 6 carbon atoms.

Further, preferred examples include tetracarboxylic dianhydrides (DAA-1) to (DAA-5) described in paragraph 0038 of International Publication No. 2017/038598.

It is also preferable that at least one of R ¹¹¹ and R ¹¹⁵ has an OH group. More specifically, R ¹¹¹ includes a residue of a bisaminophenol derivative.

R ¹¹³ and R ¹¹⁴ each independently represent a hydrogen atom or a monovalent organic group, preferably at least one of R ¹¹³ and R ¹¹⁴ contains a polymerizable group, and more preferably both contain a polymerizable group. preferable. The polymerizable group is a group that can undergo a crosslinking reaction by the action of heat, radicals, etc., and a radically 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 blocked isocyanate group, a methylol group, and an amino group. Examples include groups. The radically polymerizable group contained in the polyimide precursor is preferably a group having an ethylenically unsaturated bond.
Examples of the group having an ethylenically unsaturated bond include a vinyl group, a (meth)allyl group, a group represented by the following formula (III), and the group represented by the following formula (III) is preferred.

In formula (III), R ²⁰⁰ represents a hydrogen atom or a methyl group, preferably a hydrogen atom.
In formula (III), * represents a bonding 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 - or a polyalkyleneoxy group.
Suitable examples of R ²⁰¹ include ethylene group, propylene group, trimethylene group, tetramethylene group, 1,2-butanediyl group, 1,3-butanediyl group, pentamethylene group, hexamethylene group, octamethylene group, dodecamethylene group , -CH ₂ CH (OH) CH ₂ -, polyalkyleneoxy groups, more preferably ethylene group, propylene group, trimethylene group, -CH ₂ CH (OH) CH ₂ -, polyalkyleneoxy groups, polyalkylene More preferred is an oxy group.
In the present invention, a 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 contains multiple types of alkyleneoxy groups with different alkylene groups, the arrangement of the alkyleneoxy groups in the polyalkyleneoxy group may be a random arrangement or an arrangement having blocks. Alternatively, an arrangement having an alternating pattern or the like may be used.
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, and 2 to 6. is more preferable, 2 to 5 is even more preferable, 2 to 4 is even more preferable, 2 or 3 is particularly preferable, and 2 is most preferable.
Further, the alkylene group may have a substituent. Preferred substituents include alkyl groups, aryl groups, halogen atoms, and the like.
Further, the number of alkyleneoxy groups contained in the polyalkyleneoxy group (the number of repeating polyalkyleneoxy groups) is preferably 2 to 20, more preferably 2 to 10, and even more preferably 2 to 6.
From the viewpoint of solvent solubility and solvent resistance, polyalkyleneoxy groups include polyethyleneoxy groups, polypropyleneoxy groups, polytrimethyleneoxy groups, polytetramethyleneoxy groups, or multiple ethyleneoxy groups and multiple propyleneoxy groups. A group bonded to an oxy group is preferable, a polyethyleneoxy group or a polypropyleneoxy group is more preferable, and a polyethyleneoxy group is even more preferable. In the above-mentioned 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, or may be arranged to form blocks. , may be arranged in an alternating pattern. Preferred embodiments of the repeating number of ethyleneoxy groups, etc. in these groups are as described above.

R ¹¹³ and R ¹¹⁴ each independently represent a hydrogen atom or a monovalent organic group. Examples of monovalent organic groups include aromatic groups and aralkyl groups in which an acidic group is bonded to one, two or three, preferably one, of the carbon atoms constituting the aryl group. Specific examples thereof include aromatic groups having 6 to 20 carbon atoms and having an acidic group, and aralkyl groups having 7 to 25 carbon atoms having an acidic group. More specifically, examples thereof include a phenyl group having an acidic group and a benzyl group having an acidic group. The acidic group is preferably an OH group.
It is also more preferable that R ¹¹³ or R ¹¹⁴ is a hydrogen atom, 2-hydroxybenzyl, 3-hydroxybenzyl and 4-hydroxybenzyl.

From the viewpoint of solubility in organic solvents, R ¹¹³ or R ¹¹⁴ is preferably a monovalent organic group. The monovalent organic group preferably includes a linear or branched alkyl group, a cyclic alkyl group, and an aromatic group, and more preferably an alkyl group substituted with an aromatic group.
The alkyl group preferably has 1 to 30 carbon atoms. The alkyl group may be linear, branched, or cyclic. Examples of straight-chain or branched alkyl groups include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, dodecyl group, tetradecyl group, and octadecyl group. , isopropyl group, isobutyl group, sec-butyl group, t-butyl group, 1-ethylpentyl group, 2-ethylhexyl group 2-(2-(2-methoxyethoxy)ethoxy)ethoxy group, 2-(2-(2 -ethoxyethoxy)ethoxy)ethoxy)ethoxy group, 2-(2-(2-(2-methoxyethoxy)ethoxy)ethoxy)ethoxy group, and 2-(2-(2-(2-ethoxyethoxy)ethoxy)ethoxy ) ethoxy group. The cyclic alkyl group may be a monocyclic cyclic alkyl group or a polycyclic cyclic alkyl group. Examples of the monocyclic cyclic alkyl group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a cyclooctyl group. Examples of polycyclic cyclic alkyl groups include adamantyl group, norbornyl group, bornyl group, camphenyl group, decahydronaphthyl group, tricyclodecanyl group, tetracyclodecanyl group, camphoroyl group, dicyclohexyl group, and pinenyl group. can be mentioned. Among these, a cyclohexyl group is most preferred from the viewpoint of achieving both high sensitivity and high sensitivity. Further, as the alkyl group substituted with an aromatic group, a straight-chain alkyl group substituted with an aromatic group described below is preferable.
Specific examples of the aromatic group include substituted or unsubstituted benzene ring, naphthalene ring, pentalene ring, indene ring, azulene ring, heptalene ring, indacene ring, perylene ring, pentacene ring, acenaphthene ring, phenanthrene ring, and anthracene ring. ring, naphthacene ring, chrysene ring, triphenylene ring, fluorene ring, biphenyl ring, pyrrole ring, furan ring, thiophene ring, imidazole ring, oxazole ring, thiazole ring, pyridine ring, pyrazine ring, pyrimidine ring, pyridazine ring, indolizine ring , indole ring, benzofuran ring, benzothiophene ring, isobenzofuran ring, quinolidine ring, quinoline ring, phthalazine ring, naphthyridine ring, quinoxaline ring, quinoxazoline ring, isoquinoline ring, carbazole ring, phenanthridine ring, acridine ring, phenanthroline ring, They are a thianthrene ring, a chromene ring, a xanthene ring, a phenoxathiine ring, a phenothiazine ring, or a phenazine ring. Most preferred is a benzene ring.

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

At least one of R ¹¹³ and R ¹¹⁴ may be a polarity converting group 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 produce an alkali-soluble group such as a phenolic hydroxy group or a carboxy group, but examples include an acetal group, a ketal group, a silyl group, and a silyl ether group. , tertiary alkyl ester groups, etc. are preferable, and from the viewpoint of exposure sensitivity, an acetal 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-butoxycarbonylmethyl group. group, trimethylsilyl ether group, etc. From the viewpoint of exposure sensitivity, ethoxyethyl group or tetrahydrofuranyl group is preferred.

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

Moreover, for the purpose of improving adhesiveness with the substrate, the polyimide precursor may be copolymerized with an aliphatic group having a siloxane structure. Specifically, examples include embodiments in which bis(3-aminopropyl)tetramethyldisiloxane, bis(p-aminophenyl)octamethylpentasiloxane, etc. are used as the diamine component.

The repeating unit represented by formula (2) is preferably a repeating unit represented by formula (2-A). That is, it is preferable that at least one type of polyimide precursor used in the present invention is a precursor having a repeating unit represented by formula (2-A). With such a structure, it is possible to further widen the exposure latitude.
Formula (2-A)

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

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 their preferred ranges are also the same. .
R ¹¹² has the same meaning as R ¹¹² in formula (5), and the preferred ranges are also the same.

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

The polyimide precursor is selected from the group consisting of repeating units represented by any of the following formulas (2-1) to (2-6) as a repeating unit having at least one of a cyclic imide structure and a cyclic isoimide structure. It may also contain at least one type of repeating unit.

In formulas (2-1) to (2-6), R ¹¹¹ , R ¹¹³ , R ¹¹⁴ , R ¹¹⁵ , A ¹ , and A ² are respectively R ¹¹¹ , R ¹¹³ in formula (2) above, It has the same meaning as R ¹¹⁴ , R ¹¹⁵ , A ¹ and A ² , and its preferred embodiments are also the same.

The total content of repeating units represented by any of formulas (2-1) to (2-6) is such that the total molar content of cyclic imide structures and cyclic isoimide structures in 1 g of polyimide precursor is 0. The amount is preferably 08 to 1.68 mmol/g. The total molar content is more preferably 0.10 to 1.00 mmol/g, even more preferably 0.12 to 0.80 mmol/g, and even more preferably 0.15 to 0.60 mmol/g. It is particularly preferable.

An embodiment of the polyimide precursor in the present invention includes an embodiment in which the content of the repeating unit represented by formula (2) is 50 mol% or more of all repeating units. The total content is more preferably 70 mol% or more, still more preferably 90 mol% or more, and particularly preferably more than 90 mol%. The upper limit of the total content is not particularly limited, and all repeating units in the polyimide precursor excluding the terminal are repeating units represented by formula (2), formulas (2-1) to (2-6), etc. It may be any of the repeating units represented by any of the following.

The weight average molecular weight (Mw) of the polyimide precursor is preferably 18,000 to 30,000, more preferably 20,000 to 27,000, and still more preferably 22,000 to 25,000. Further, the number average molecular weight (Mn) is preferably 7,200 to 14,000, more preferably 8,000 to 12,000, and still more preferably 9,200 to 11,200.
The molecular weight dispersity of the polyimide precursor is preferably 2.5 or more, more preferably 2.7 or more, and even more preferably 2.8 or more. The upper limit of the molecular weight dispersity of the polyimide precursor is not particularly determined, but for example, it is preferably 4.5 or less, more preferably 4.0 or less, even more preferably 3.8 or less, and even more preferably 3.2 or less. It is preferably 3.1 or less, even more preferably 3.0 or less, and particularly preferably 2.95 or less.
In this specification, the molecular weight dispersity is a value calculated from weight average molecular weight/number average molecular weight.

[Polybenzoxazole precursor]
Although the structure of the polybenzoxazole precursor used in the present invention is not particularly limited, it preferably contains a repeating unit represented by the following formula (3).

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

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, at least one of them is preferably a polymerizable group.
In formula (3), R ¹²¹ represents a divalent organic group. The divalent organic group is preferably a group containing at least one of an aliphatic group and an aromatic group. As the aliphatic group, a straight chain aliphatic group is preferable. R ¹²¹ is preferably a dicarboxylic acid residue. One type of dicarboxylic acid residue 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.
The dicarboxylic acid containing an aliphatic group is preferably a dicarboxylic acid containing a linear or branched (preferably linear) aliphatic group, and a dicarboxylic acid containing a linear or branched (preferably linear) aliphatic group and two -COOH A dicarboxylic acid consisting of is more preferred. The straight chain or branched (preferably straight chain) aliphatic group preferably has 2 to 30 carbon atoms, more preferably 2 to 25 carbon atoms, even more preferably 3 to 20 carbon atoms, and 4 to 30 carbon atoms. It is more preferably 15, and particularly preferably 5-10. Preferably, the straight chain aliphatic group is an alkylene group.
Examples of dicarboxylic acids containing linear aliphatic groups 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, suberin Acid, dodecafluorosuberic acid, azelaic acid, sebacic acid, hexadecafluorosebacic acid, 1,9-nonanedioic acid, dodecanedioic acid, tridecanedioic acid, tetradecanedioic acid, pentadecanedioic acid, hexadecanedioic acid, heptadecanedioic acid , octadecanedioic acid, nonadecanedioic acid, eicosanedioic acid, heneicosanedioic acid, docosanedioic acid, tricosanedioic acid, tetracosanedioic acid, pentacosanedioic acid, hexacosanedioic acid, heptacosanedioic acid, octacosanedioic acid, nonacosanedioic acid, tria Examples include contanedioic acid, hentriacontanedioic acid, dotriacontanedioic acid, diglycolic acid, and dicarboxylic acids represented by the following formulas.

(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 acid having the following aromatic group is preferable, and the dicarboxylic acid consisting only of the following aromatic group and two -COOH is more preferable.

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 bonding site with another structure.

Specific examples of dicarboxylic acids containing aromatic groups 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 above 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-hydroxyphenyl)methane, 2,2-bis-(4-amino-3-hydroxyphenyl)propane, 4,4'-Diamino-3,3'-dihydroxybenzophenone,3,3'-diamino-4,4'-dihydroxybenzophenone,4,4'-diamino-3,3'-dihydroxydiphenyl ether, 3,3'-diamino-4, Examples include 4'-dihydroxydiphenyl ether, 1,4-diamino-2,5-dihydroxybenzene, 1,3-diamino-2,4-dihydroxybenzene, and 1,3-diamino-4,6-dihydroxybenzene. These bisaminophenols may be used alone or in combination.

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

In the formula, X ₁ represents -O-, -S-, -C(CF ₃ ) ₂ -, -CH ₂ -, -SO ₂ -, -NHCO-, and * and # each represent other structures represents the binding site of R represents a hydrogen atom or a monovalent substituent, preferably a hydrogen atom or a hydrocarbon group, and more preferably a hydrogen atom or an alkyl group. Further, 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 four * and # are bonding sites with the nitrogen atom to which R ¹²² in formula (3) is bonded, and The other two are preferably bonding sites with the oxygen atom to which R ¹²² in formula (3) is bonded, and the two * are bonding sites with the oxygen atom to which R ¹²² in formula (3) is bonded. , and two #s are bonding sites with the nitrogen atom to which R ¹²² in formula (3) is bonded, or two * are bonding sites with the nitrogen atom to which R ¹²² in formula (3) is bonded. and two #s are preferably bonding sites with the oxygen atom to which R ¹²² in formula (3) is bonded, and two * are bonding sites to the oxygen atom to which R ¹²² in formula (3) is bonded. More preferably, it is a bonding site with an atom, and the two #s are bonding sites with a nitrogen atom to which R ¹²² in formula (3) is bonded.

In formula (A-s), R ₁ is a hydrogen atom, alkylene, 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 a hydrogen atom, a linear or branched alkyl group, an alkoxy group, an acyloxy group, or a cyclic alkyl group, and may be the same or different.

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

In the above formula (A-s), having a substituent at the ortho position of the phenolic hydroxy group, that is, at _R3 , is thought to bring the carbonyl carbon of the amide bond closer to the hydroxy group. It is particularly preferred because the effect of achieving a high cyclization rate upon curing is further enhanced.

In addition, in the above formula (A-s), R ₂ is an alkyl group and R ₃ is an alkyl group, which results in high transparency to i-rays and a high cyclization rate when cured at low temperature. It is preferable because the effect can be maintained.

Further, in the above formula (A-s), it is more preferable that R ₁ is alkylene or substituted alkylene. Specific examples of 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 - has a balance of sufficient solubility in solvents while maintaining the effects of high transparency to i-rays and high cyclization rate when cured at low temperatures. This is more preferred in that a polybenzoxazole precursor having excellent properties can be obtained.

For the method for producing the bisaminophenol derivative represented by the above formula (A-s), for example, refer to paragraph numbers 0085 to 0094 and Example 1 (paragraph numbers 0189 to 0190) of JP-A No. 2013-256506. , the contents of which are incorporated herein.

Specific examples of the structure of the bisaminophenol derivative represented by the above formula (A-s) include those described in paragraph numbers 0070 to 0080 of JP-A No. 2013-256506, the contents of which are herein incorporated by reference. be incorporated into. Of course, it goes without saying that it is not limited to these.

In addition to the repeating unit of formula (3) above, the polybenzoxazole precursor may also contain other types of repeating structural units.
The polybenzoxazole precursor includes a repeating unit represented by the following formula (3-1), a repeating unit represented by the following formula (3-2), and the following formula (3) as a repeating unit having a benzoxazole structure. -3) It may contain at least one type of repeating unit selected from the group consisting of repeating units represented by -3).
In formulas (3-1) to (3-3), R ¹²¹ , R ¹²² , R ¹²³ and R ¹²⁴ have the same meanings as R ¹²¹ , R ¹²² , R ¹²³ and R ¹²⁴ in formula (3), respectively. The same applies to preferred embodiments.

The content of the repeating unit represented by formula (3-1), the repeating unit represented by formula (3-2), and the repeating unit represented by formula (3-3) is 1 g of polybenzoxazole. The molar amount of the benzoxazole structure contained in the precursor is preferably 0.22 to 3.97 mmol/g. The molar amount contained above is more preferably 0.25 to 3.00 mmol/g, even more preferably 0.28 to 2.50 mmol/g, and even more preferably 0.30 to 2.00 mmol/g. is particularly preferred.

Further, the polybenzoxazole precursor preferably contains a diamine residue represented by the following formula (SL) as another type of repeating structural unit, since it can suppress the occurrence of warpage due to ring closure.

In formula (SL), Z has an a structure and a b structure, R ^1s is a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, and R ^2s is a hydrocarbon group having 1 to 10 carbon atoms. At least one of R ^3s , R ^4s , R ^5s and R ^6s is an aromatic group, and the rest are hydrogen atoms or organic groups having 1 to 30 carbon atoms, which may be the same or different. The polymerization of the a structure and b structure 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 formula (SL), preferable examples of Z include those in which R ^5s and R ^6s in the b structure are phenyl groups. Further, the molecular weight of the structure represented by formula (SL) is preferably 400 to 4,000, more preferably 500 to 3,000. By setting the molecular weight within the above range, it is possible to more effectively lower the elastic modulus of the polybenzoxazole precursor after dehydration and ring closure, thereby achieving both the effect of suppressing warpage and the effect of improving solvent solubility.

When a diamine residue represented by formula (SL) is included as another type of repeating structural unit, a tetracarboxylic acid residue remaining after the anhydride group is removed from the tetracarboxylic dianhydride is further used as a repeating structural unit. It is also preferable to include. An example of such a tetracarboxylic acid residue is R ¹¹⁵ in formula (2).

The weight average molecular weight (Mw) of the polybenzoxazole precursor, for example, when used in the composition described below, is preferably 18,000 to 30,000, more preferably 20,000 to 29,000, and Preferably it is 22,000 to 28,000. Further, the number average molecular weight (Mn) is preferably 7,200 to 14,000, more preferably 8,000 to 12,000, and still more preferably 9,200 to 11,200.
The molecular weight dispersity of the polybenzoxazole precursor is preferably 1.4 or more, more preferably 1.5 or more, and even more preferably 1.6 or more. The upper limit of the molecular weight dispersity of the polybenzoxazole precursor is not particularly determined, but for example, it is preferably 2.6 or less, more preferably 2.5 or less, even more preferably 2.4 or less, and 2.3 or less. is more preferable, and 2.2 or less is even more preferable.

[Polyamideimide precursor]
The polyamide-imide precursor preferably contains a repeating unit represented by the following formula (PAI-2).

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. represents an organic group.

In formula (PAI-2), R ¹¹⁷ is a linear or branched aliphatic group, a cyclic aliphatic group, an aromatic group, a heteroaromatic group, or a single bond or a linking group that binds these two groups. Examples of the above-linked groups include linear aliphatic groups having 2 to 20 carbon atoms, branched aliphatic groups having 3 to 20 carbon atoms, cyclic aliphatic groups having 3 to 20 carbon atoms, and 6 to 20 carbon atoms. An aromatic group having 6 to 20 carbon atoms, or a group having 6 to 20 carbon atoms combined with a single bond or a connecting group is preferable. A group combining two or more of these is more preferable.
The above-mentioned linking group includes -O-, -S-, -C(=O)-, -S(=O) ₂ -, an alkylene group, a halogenated alkylene group, an arylene group, or a linkage of two or more of these. The group is preferably a group such as -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 together.
The alkylene group is preferably an alkylene group having 1 to 20 carbon atoms, more preferably an alkylene group having 1 to 10 carbon atoms, and even more preferably an alkylene group having 1 to 4 carbon atoms.
The above halogenated alkylene group is preferably a halogenated alkylene group having 1 to 20 carbon atoms, more preferably a halogenated alkylene group having 1 to 10 carbon atoms, and more preferably a halogenated alkylene group having 1 to 4 carbon atoms. Furthermore, examples of the halogen atom in the halogenated alkylene group include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, and the like, with a fluorine atom being preferred. The halogenated alkylene group may have a hydrogen atom or all of the hydrogen atoms may be substituted with a halogen atom, but it is preferable that all of the hydrogen atoms are substituted with a halogen atom. An example of a preferable halogenated alkylene group includes a (ditrifluoromethyl)methylene group.
The arylene group is preferably a phenylene group or a naphthylene group, more preferably a phenylene group, and even more preferably a 1,3-phenylene group or a 1,4-phenylene group.

Further, R ¹¹⁷ is preferably derived from a tricarboxylic acid compound in which at least one carboxy group may be halogenated. The above halogenation is preferably chlorination.
In the present invention, a compound having three carboxy groups is referred to as a tricarboxylic acid compound.
Two of the three carboxy groups of the tricarboxylic acid compound may be converted into acid anhydrides.
Examples of the optionally halogenated tricarboxylic acid compound used in the 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, the tricarboxylic acid compound includes a linear aliphatic group having 2 to 20 carbon atoms, a branched aliphatic group having 3 to 20 carbon atoms, a cyclic aliphatic group having 3 to 20 carbon atoms, and a cyclic aliphatic group having 3 to 20 carbon atoms. A tricarboxylic acid compound containing an aromatic group having 6 to 20 carbon atoms or a combination of two or more of these through a single bond or a connecting group is preferred; A tricarboxylic acid compound containing a combination of two or more aromatic groups of 6 to 20 is more preferred.

Specific examples of tricarboxylic acid compounds include 1,2,3-propanetricarboxylic acid, 1,3,5-pentanetricarboxylic acid, citric acid, trimellitic acid, 2,3,6-naphthalenetricarboxylic acid, and phthalic acid. (or phthalic anhydride) and benzoic acid have a single bond, -O-, -CH ₂ -, -C(CH ₃ ) ₂ -, -C(CF ₃ ) ₂ -, -SO ₂ - or a phenylene group. Examples include linked compounds.
These compounds may be compounds in which two carboxyl groups are anhydrides (for example, trimellitic anhydride), or compounds in which at least one carboxyl group is halogenated (for example, trimellitic anhydride). There may be.

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

The polyamideimide precursor may further include other repeating units.
Other repeating units include the repeating unit represented by formula (2) above, the repeating unit represented by formula (2-1), the repeating unit represented by formula (2-2), and the repeating unit represented by formula (2- Examples include a repeating unit represented by 3), a repeating unit represented by the following formula (PAI-1), and the like.

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 a linear or branched aliphatic group, a cyclic aliphatic group, an aromatic group, a heteroaromatic group, or a single bond or a linking group that connects these two groups. Examples of the above-linked groups include linear aliphatic groups having 2 to 20 carbon atoms, branched aliphatic groups having 3 to 20 carbon atoms, cyclic aliphatic groups having 3 to 20 carbon atoms, and 6 to 20 carbon atoms. An aromatic group having 6 to 20 carbon atoms, or a group having 6 to 20 carbon atoms combined with a single bond or a connecting group is preferable. A group combining two or more of these is more preferable.
The above-mentioned linking group includes -O-, -S-, -C(=O)-, -S(=O) ₂ -, an alkylene group, a halogenated alkylene group, an arylene group, or a linkage of two or more of these. The group is preferably a group such as -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 together.
The alkylene group is preferably an alkylene group having 1 to 20 carbon atoms, more preferably an alkylene group having 1 to 10 carbon atoms, and even more preferably an alkylene group having 1 to 4 carbon atoms.
The above halogenated alkylene group is preferably a halogenated alkylene group having 1 to 20 carbon atoms, more preferably a halogenated alkylene group having 1 to 10 carbon atoms, and more preferably a halogenated alkylene group having 1 to 4 carbon atoms. Furthermore, examples of the halogen atom in the halogenated alkylene group include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, and the like, with a fluorine atom being preferred. The halogenated alkylene group may have a hydrogen atom or all of the hydrogen atoms may be substituted with a halogen atom, but it is preferable that all of the hydrogen atoms are substituted with a halogen atom. An example of a preferable halogenated alkylene group includes a (ditrifluoromethyl)methylene group.
The arylene group is preferably a phenylene group or a naphthylene group, more preferably a phenylene group, and even more preferably a 1,3-phenylene group or a 1,4-phenylene group.

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 carboxyl 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.
The optionally halogenated dicarboxylic acid compound or dicarboxylic acid dihalide compound used in the production of the polyamide-imide precursor includes linear or branched aliphatic, cyclic aliphatic or aromatic dicarboxylic acid compounds or dicarboxylic acid compounds. Examples include acid dihalide compounds.
These dicarboxylic acid compounds or dicarboxylic acid dihalide compounds may be used alone or in combination of two or more.

Specifically, the dicarboxylic acid compound or dicarboxylic acid dihalide compound includes a linear aliphatic group having 2 to 20 carbon atoms, a branched aliphatic group having 3 to 20 carbon atoms, and a cyclic aliphatic group having 3 to 20 carbon atoms. A dicarboxylic acid compound or dicarboxylic acid dihalide compound containing a group group, an aromatic group having 6 to 20 carbon atoms, or a combination of two or more of these through a single bond or a connecting group is preferable, and an aromatic group having 6 to 20 carbon atoms Alternatively, a dicarboxylic acid compound or a dicarboxylic acid dihalide compound containing a group in which two or more aromatic groups having 6 to 20 carbon atoms are combined via a single bond or a connecting group is more preferable.

Specific examples of dicarboxylic acid compounds 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-nonanedioic acid, dodecanedioic acid, tridecanedioic acid, tetradecanedioic acid, pentadecanedioic acid, hexadecanedioic acid, heptadecanedioic acid, octadecane Diacid, nonadecanedioic acid, eicosanedioic acid, heneicosanedioic acid, docosanedioic acid, tricosanedioic acid, tetracosanedioic acid, pentacosanedioic acid, hexacosanedioic acid, heptacosanedioic acid, octacosanedioic acid, nonacosanedioic acid, triacontanedioic acid Acid, hentriacontanedioic acid, dotriacontanedioic acid, diglycolic acid, phthalic acid, isophthalic acid, terephthalic acid, 4,4'-biphenylcarboxylic acid, 4,4'-biphenylcarboxylic acid, 4,4'- Examples include dicarboxydiphenyl ether and benzophenone-4,4'-dicarboxylic acid.
Specific examples of dicarboxylic acid dihalide compounds include compounds having a structure in which two carboxy groups in the above specific examples of dicarboxylic acid compounds are halogenated.

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

The polyamide-imide precursor may include a repeating unit represented by either of the following formulas (PAI-3) and (PAI-4) as a repeating unit having at least one of a cyclic imide structure and a cyclic isoimide structure.

In formula (PAI-3) or formula (PAI-4), R ¹¹¹ and R ¹¹⁷ have the same meanings as R ¹¹¹ and R ¹¹⁷ in formula (PAI-2), respectively, and preferred embodiments are also the same.

The content of the repeating unit represented by either formula (PAI-3) or (PAI-4) is such that the total content of the cyclic imide structure and the cyclic isoimide structure in the polyamide-imide precursor is 0.062 to 1.186 mmol. It is preferable that the amount is /g. The above total content is more preferably 0.070 to 1.000 mmol/g, even more preferably 0.080 to 0.800 mmol/g, and even more preferably 0.090 to 0.700 mmol/g. is particularly preferred.

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

Moreover, for the purpose of improving adhesiveness with the substrate, the polyamideimide precursor may be copolymerized with an aliphatic group having a siloxane structure. Specifically, examples include embodiments in which bis(3-aminopropyl)tetramethyldisiloxane, bis(p-aminophenyl)octamethylpentasiloxane, etc. are used as the diamine component.

As one embodiment of the polyamide-imide precursor in the present invention, a repeating unit represented by formula (PAI-2), a repeating unit represented by formula (PAI-1), a repeating unit represented by formula (PAI-3), Unit, repeating unit represented by formula (PAI-4), repeating unit represented by formula (2), total of repeating units represented by any of formula (2-1) to formula (2-6) An embodiment in which the content is 50 mol% or more of all repeating units is mentioned. The total content is more preferably 70 mol% or more, still more preferably 90 mol% or more, and particularly preferably more than 90 mol%. The upper limit of the above total content is not particularly limited, and all repeating units in the polyamideimide precursor excluding the terminal are represented by the repeating unit represented by the formula (PAI-2) or the formula (PAI-1). Repeating unit, repeating unit represented by either formula (PAI-3) or (PAI-4), repeating unit represented by formula (2), formula (2-1) to formula (2-6) It may be any of the repeating units represented by either.
Further, as another embodiment of the polyamide-imide precursor in the present invention, a repeating unit represented by formula (PAI-2), a repeating unit represented by formula (PAI-1), and a repeating unit represented by formula (PAI-3) are used. ) and (PAI-4), the total content of repeating units represented by either of them is 50 mol% or more of all repeating units. The total content is more preferably 70 mol% or more, still more preferably 90 mol% or more, and particularly preferably more than 90 mol%. The upper limit of the above total content is not particularly limited, and all repeating units in the polyamideimide precursor excluding the terminal are represented by the repeating unit represented by the formula (PAI-2) or the formula (PAI-1). It may be a repeating unit or a repeating unit represented by either formula (PAI-3) or (PAI-4).

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

The degree of molecular weight dispersion of the polyamide-imide precursor is preferably 1.5 to 3.5, more preferably 2 to 3.
In this specification, the degree of dispersion of molecular weight refers to the value obtained by dividing the weight average molecular weight by the number average molecular weight (weight average molecular weight/number average molecular weight).

[Method for producing polyimide precursor, etc.]
Polyimide precursors and the like are obtained by reacting dicarboxylic acids or dicarboxylic acid derivatives with diamines. Preferably, it is obtained by halogenating a dicarboxylic acid or a dicarboxylic acid derivative using a halogenating agent and then reacting it with a diamine.
In the method for producing polyimide precursors, etc., it is preferable to use an organic solvent during the reaction. The number of organic solvents may be one or two or more.
The organic solvent can be appropriately determined depending on the raw material, and examples thereof include pyridine, diethylene glycol dimethyl ether (diglyme), N-methylpyrrolidone, and N-ethylpyrrolidone.

It is also preferable to synthesize using a non-halogen catalyst without using the halogenating agent. As the above-mentioned non-halogen-based catalyst, any known amidation catalyst that does not contain a halogen atom can be used without any particular restriction. For example, boroxine compounds, N-hydroxy compounds, tertiary amines, phosphate esters, amines, Examples include salts, urea compounds, and carbodiimide compounds. Examples of the carbodiimide compound include N,N'-diisopropylcarbodiimide, N,N'-dicyclohexylcarbodiimide, and the like.
In the method for producing polyimide precursors, etc., it is preferable to use an organic solvent during the reaction. The number of organic solvents may be one or two or more.
The organic solvent can be appropriately determined depending on the raw material, and examples thereof include pyridine, diethylene glycol dimethyl ether (diglyme), N-methylpyrrolidone, and N-ethylpyrrolidone.

-Terminal sealing agent-
When manufacturing polyimide precursors, etc., in order to further improve storage stability, the ends of polyimide precursors, etc. are closed with an end-capping agent such as an acid anhydride, monocarboxylic acid, monoacid chloride compound, or monoactive ester compound. Preferably, it is sealed. As the terminal capping agent, it is more preferable to use a monoamine, and preferred compounds of the monoamine include aniline, 2-ethynylaniline, 3-ethynylaniline, 4-ethynylaniline, 5-amino-8-hydroxyquinoline, and 1-ethynylaniline. Hydroxy-7-aminonaphthalene, 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- 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 capping agents.

-Solid precipitation-
The production of the polyimide precursor and the like may include a step of precipitating a solid. Specifically, solid precipitation can be achieved by precipitating the polyimide precursor etc. in the reaction solution in water and dissolving it in a solvent such as tetrahydrofuran in which the polyimide precursor etc. can be dissolved.
Thereafter, the polyimide precursor and the like can be dried to obtain a powdery polyimide precursor and the like.

〔Content〕
The content of the specific resin in the composition of the present invention is preferably 20% by mass or more, more preferably 30% by mass or more, and preferably 40% by mass or more based on the total solid content of the composition. The content is more preferably 50% by mass or more. Further, the content of the resin in the composition of the present invention is preferably 99.5% by mass or less, more preferably 99% by mass or less, and 98% by mass or less based on the total solid content of the composition. It is more preferably 97% by mass or less, even more preferably 95% by mass or less.
The composition of the present invention may contain only one type of specific resin, or may contain two or more types of specific resin. When two or more types are included, it is preferable that the total amount falls within the above range.

Moreover, it is also preferable that the curable resin composition of the present invention contains at least two types of resin.
Specifically, the curable resin composition of the present invention may contain a total of two or more types of specific resin and other resins described below, or may contain two or more types of specific resin, but It is preferable that two or more kinds of resins are included.
When the curable resin composition of the present invention contains two or more specific resins, for example, two or more polyimide precursors having different dianhydride-derived structures (R ¹¹⁵ in the above formula (2)) It is preferable that the polyimide precursor contains a polyimide precursor of

<Specific compound>
The curable resin composition of the present invention is a group consisting of a compound represented by formula (1-1), a compound represented by formula (1-2), and a compound represented by formula (1-3). Contains at least one type (specific compound) selected from.

In formula (1-1), formula (1-2) or formula (1-3), R ¹¹ and R ¹² each independently represent an unsubstituted aliphatic hydrocarbon group having 1 to 7 carbon atoms or a substituent. At least one member selected from the group consisting of a primary amine salt structure, a secondary amine salt structure, a tertiary amino group, a tertiary amine salt structure, a quaternary ammonium group, and an aliphatic heterocyclic group an aliphatic hydrocarbon group having 1 to 7 carbon atoms having a substituent, or an aliphatic hydrocarbon group having 2 to 7 carbon atoms having at least one substituent selected from the group consisting of a hydroxy group, an alkoxy group, a thiol group, and an alkylthio group; 7 represents an aliphatic hydrocarbon group, R ²¹ and R ²² each independently represent an aliphatic hydrocarbon group having 1 to 7 carbon atoms which may have a substituent, and R ³¹ and R ³² each independently represents an aliphatic hydrocarbon group having 1 to 7 carbon atoms which may have a substituent, and R ³³ represents an aliphatic hydrocarbon group having 1 to 7 carbon atoms which may have a substituent.

[R ¹¹ and R ¹² ]
In formula (1-1), R ¹¹ and R ¹² are each independently an unsubstituted aliphatic hydrocarbon group having 1 to 7 carbon atoms, or a primary amine salt structure or a secondary amine salt as a substituent. structure, a tertiary amino group, a tertiary amine salt structure, and an aliphatic hydrocarbon group having 1 to 7 carbon atoms and at least one substituent selected from the group consisting of a quaternary ammonium group. , unsubstituted aliphatic hydrocarbon groups having 1 to 7 carbon atoms are more preferred.
The unsubstituted aliphatic hydrocarbon group having 1 to 7 carbon atoms in R ¹¹ and R ¹² is preferably an unsubstituted saturated aliphatic hydrocarbon group having 1 to 7 carbon atoms; A saturated aliphatic hydrocarbon group is more preferred, and an ethyl group, isopropyl group, t-butyl group or cyclohexyl group is more preferred.

Substituents in R ¹¹ and R ¹² include primary amine salt structure, secondary amine salt structure, tertiary amino group, tertiary amine salt structure, quaternary ammonium group, and aliphatic heterocyclic group. The aliphatic hydrocarbon group having 1 to 7 carbon atoms having at least one substituent selected from the group consisting of the following is preferably a saturated aliphatic hydrocarbon group having 1 to 7 carbon atoms having the above substituent.
Further, the aliphatic hydrocarbon group may have a plurality of the above substituents, but preferably has only one of the above substituents.

The primary amine salt structure in the above substituent refers to a salt structure consisting of a primary amino group (-NH ₂ ) and an acid, preferably a salt structure of a primary amino group and an inorganic acid, and a hydrochloride structure. etc.
The secondary amine salt structure in the above substituent refers to a salt structure consisting of a secondary amino group (-NRH, R represents an organic group) and an acid, and a salt structure of a secondary amino group and an inorganic acid. Preferred structures include hydrochloride structures and the like.
Examples of the secondary amino group constituting the secondary amine salt structure in the substituent include a monoalkylamino group, a monoarylamino group, and a monoalkylamino group having 1 to 4 carbon atoms is preferred.
The tertiary amine salt structure in the above substituent refers to a salt structure consisting of a tertiary amino group (-NR ₂ , R each independently represents an organic group) and an acid; A salt structure with an acid is preferred, and examples include a hydrochloride structure.
The tertiary amino group in the above substituent or the tertiary amino group constituting the tertiary amine is preferably a dialkylamino group, and the two alkyl groups each independently have a carbon number of 1 to 4. A dialkylamino group is more preferred, and a dimethylamino group is even more preferred.
In addition, when one of R ¹¹ and R ¹² has a primary amine salt structure, a secondary amine salt structure, a tertiary amino group, or a tertiary amine salt structure as a substituent, R ¹¹ and R 12 The other of ¹² is preferably the above-mentioned unsubstituted aliphatic hydrocarbon group having 1 to 7 carbon atoms.
Fat having 1 to 7 carbon atoms and having at least one type selected from the group consisting of a primary amine salt structure, a secondary amine salt structure, a tertiary amino group, and a tertiary amine salt structure as a substituent. The group hydrocarbon group is preferably a linear or branched saturated aliphatic hydrocarbon group having 2 to 7 carbon atoms and having these substituents at the end; It is more preferably a linear or branched saturated aliphatic hydrocarbon group with 3 to 5 carbon atoms, and a linear saturated aliphatic hydrocarbon group with 3 to 5 carbon atoms having these substituents at the terminal. It is even more preferable that there be.

The quaternary ammonium group in the above substituent is preferably a group represented by the following formula (A-1).

In formula (A-1), R ^A1 to R ^A3 each independently represent a hydrocarbon group, at least two of R ^A1 to R ^A3 may be combined to form a ring structure, and X is a counter anion. and * represents a bonding site with an aliphatic hydrocarbon group having 1 to 7 carbon atoms.
In formula (A-1), R ^A1 to R ^A3 are each independently more preferably an aromatic hydrocarbon group or an alkyl group, more preferably a phenyl group or an alkyl group having 1 to 4 carbon atoms, and more preferably a phenyl group or an alkyl group having 1 to 4 carbon atoms. An alkyl group is more preferred, and a methyl group is particularly preferred.
An embodiment in which all of R ^A1 to R ^A3 are methyl groups is also one of the preferred embodiments of the present invention.
The ring structure formed by combining at least two of R ^A1 to R ^A3 includes a saturated aliphatic hydrocarbon ring such as a cyclohexane ring, an unsaturated aliphatic hydrocarbon ring such as a cyclohexene ring, and a saturated aliphatic ring such as a morpholino ring. group heterocycles and the like.
In formula (A-1), X represents a counter anion, which may be a monovalent anion or an anion with a valence of two or more, but is preferably a monovalent anion.
Although X is not particularly limited, it is preferably a halide ion or a tosylate anion, and more preferably a halide ion.
Examples of the halide ions include fluoride ions, chloride ions, bromide ions, iodide ions, and the like, with chloride ions being preferred.
Further, when one of R ¹¹ and R ¹² has a quaternary ammonium group as a substituent, the other of R ¹¹ and R ¹² may be the above-mentioned unsubstituted aliphatic hydrocarbon group having 1 to 7 carbon atoms. preferable.
An aliphatic hydrocarbon group having 1 to 7 carbon atoms having a quaternary ammonium group as a substituent is a linear or branched saturated aliphatic hydrocarbon group having 2 to 7 carbon atoms having a quaternary ammonium group at the end. It is preferably a hydrogen group, and more preferably a linear or branched saturated aliphatic hydrocarbon group having 3 to 5 carbon atoms having a quaternary ammonium group at the end. More preferably, it is a linear saturated aliphatic hydrocarbon group having 3 to 5 carbon atoms.

Examples of the heteroatom in the aliphatic heterocyclic group in the above substituent include an oxygen atom, a nitrogen atom, a sulfur atom, and the like, with an oxygen atom being preferred.
The aliphatic heterocyclic group may have only one heteroatom, or may have two or more heteroatoms.
The aliphatic heterocyclic group preferably has a 5-membered ring structure or a 6-membered ring structure, more preferably a 5-membered ring structure.
The aliphatic heterocyclic group may further have a known substituent such as an alkyl group.
The aliphatic heterocyclic group is preferably a 2,2-dimethyl-1,3-dioxolan-4-yl group.
Moreover, when one of R ¹¹ and R ¹² has an aliphatic heterocyclic group as a substituent, it is preferable that the other of R ¹¹ and R ¹² also has an aliphatic heterocyclic group as a substituent.
The aliphatic hydrocarbon group having 1 to 7 carbon atoms having an aliphatic heterocyclic group as a substituent is preferably a saturated aliphatic hydrocarbon group having 1 to 7 carbon atoms having an aliphatic heterocyclic group at the terminal, It is more preferably a linear or branched saturated aliphatic hydrocarbon group having 1 to 4 carbon atoms having an aliphatic heterocyclic group at the end, and more preferably a methyl group having an aliphatic heterocyclic group at the end. preferable.

R ¹¹ and R ¹² are each independently an aliphatic hydrocarbon group having 2 to 7 carbon atoms and having at least one substituent selected from the group consisting of a hydroxy group, an alkoxy group, a thiol group, and an alkylthio group. There may be.
The aliphatic hydrocarbon group having 2 to 7 carbon atoms may have two or more of the above substituents, but an embodiment having only one of the above substituents is also a preferred embodiment of the present invention.
The alkoxy group is preferably an alkoxy group having 1 to 10 carbon atoms, more preferably an alkoxy group having 1 to 4 carbon atoms.
The alkylthio group is preferably an alkylthio group having 1 to 10 carbon atoms, more preferably an alkylthio group having 1 to 4 carbon atoms.
The aliphatic hydrocarbon group having 2 to 7 carbon atoms is preferably a saturated aliphatic hydrocarbon group having 2 to 7 carbon atoms, more preferably a saturated aliphatic hydrocarbon group having 2 to 4 carbon atoms.
Examples of the aliphatic hydrocarbon group having 2 to 7 carbon atoms having at least one substituent selected from the group consisting of a hydroxy group, an alkoxy group, a thiol group, and an alkylthio group include a hydroxyethyl group and a hydroxypropyl group. , methoxyethyl group, ethoxyethyl group, methoxypropyl group, ethoxypropyl group, etc., but are not limited thereto.

[R ²¹ and R ²² ]
R ²¹ and R ²² each independently represent an aliphatic hydrocarbon group having 1 to 7 carbon atoms which may have a substituent.
R ²¹ and R ²² are preferably an unsubstituted aliphatic hydrocarbon group having 1 to 7 carbon atoms, or an aliphatic hydrocarbon group having 1 to 7 carbon atoms having an amino group or a quaternary ammonium group as a substituent. , unsubstituted aliphatic hydrocarbon groups having 1 to 7 carbon atoms are more preferred.
Preferred embodiments of the unsubstituted aliphatic hydrocarbon group having 1 to 7 carbon atoms or the aliphatic hydrocarbon group having 1 to 7 carbon atoms having the above substituent in R ²¹ and R ²² are R 11 and R ²² , respectively. It is the same as that shown in the explanation of ^R12 .

[R ³¹ and R ³² ]
R ³¹ and R ³² each independently represent an aliphatic hydrocarbon group having 1 to 7 carbon atoms which may have a substituent.
R ³¹ and R ³² are preferably an unsubstituted aliphatic hydrocarbon group having 1 to 7 carbon atoms, or an aliphatic hydrocarbon group having 1 to 7 carbon atoms having an amino group or a quaternary ammonium group as a substituent. , unsubstituted aliphatic hydrocarbon groups having 1 to 7 carbon atoms are more preferred.
Preferred embodiments of the unsubstituted aliphatic hydrocarbon group having 1 to 7 carbon atoms in R ³¹ and R ³² or the aliphatic hydrocarbon group having 1 to 7 carbon atoms having the above substituent are R 11 and R ³² , respectively. It is the same as that shown in the explanation of ^R12 .

[ ^R33 ]
R ³³ represents an aliphatic hydrocarbon group having 1 to 7 carbon atoms which may have a substituent, and is preferably an unsubstituted aliphatic hydrocarbon group having 1 to 7 carbon atoms; A saturated aliphatic hydrocarbon group having 1 to 7 carbon atoms is more preferable, and a saturated aliphatic hydrocarbon group having 1 to 4 carbon atoms is more preferable.
R ³³ is preferably a methyl group, ethyl group, propyl group, isopropyl group, butyl group or t-butyl group, and more preferably an ethyl group.

From the viewpoint of resolution, the content of the specific compound is 10 to 50,000 ppm, more preferably 30 to 20,000 ppm, and 70 to 15,000 ppm based on the total mass of the curable resin composition. It is more preferable that
When the curable resin composition contains two or more types of specific compounds, the above-mentioned contained mass is the total mass of all the specific compounds.

Further, the specific compound is preferably a compound that does not contain a radically polymerizable group such as an ethylenically unsaturated group, an epoxy group, an oxetanyl group, an alkoxyalkyl group, a hydroxyalkyl group, an alkoxysilyl group, or a silanol group.

Specific examples of the specific compound include, but are not particularly limited to, compounds represented by formulas (G-1) to (G-27) used in the examples described below.
Among these, from the viewpoint of resolution, compounds represented by any of formulas (G-1) to (G-12) are preferred.

<Organometallic complex>
The curable resin composition of the present invention contains an organometallic complex.
The organometallic complex may be any organic complex compound containing a metal atom, but preferably a complex compound containing a metal atom and an organic group, and a complex compound in which an organic group is coordinated to a metal atom. are more preferred, and metallocene compounds are even more preferred.
In the present invention, the metallocene compound refers to an organometallic complex having two cyclopentadienyl anion derivatives which may have substituents as η5-ligands.
The organic group is not particularly limited, but preferably a hydrocarbon group or a group consisting of a combination of a hydrocarbon group and a heteroatom. As the heteroatom, an oxygen atom, a sulfur atom, and a nitrogen atom are preferable.
In the present invention, at least one of the organic groups is preferably a cyclic group, and more preferably at least two are cyclic groups.
The cyclic group is preferably selected from a 5-membered cyclic group and a 6-membered cyclic group, and more preferably a 5-membered cyclic group.
The above-mentioned cyclic group may be a hydrocarbon ring or a heterocycle, but a hydrocarbon ring is preferable.
As the 5-membered cyclic group, a cyclopentadienyl group is preferred.
Further, the organometallic complex used in the present invention preferably contains 2 to 4 cyclic groups in one molecule.

The metal contained in the organometallic complex is not particularly limited, but is preferably a metal that falls under Group 4 elements, and is preferably at least one metal selected from the group consisting of titanium, zirconium, and hafnium. More preferably, at least one metal selected from the group consisting of titanium and zirconium is more preferable, and titanium is particularly preferable.

The organometallic complex may contain two or more metal atoms or only one metal atom, but preferably contains only one metal atom. When the organometallic complex contains two or more metal atoms, it may contain only one kind of metal atom, or it may contain two or more kinds of metal atoms.

The organometallic complex is preferably a ferrocene compound, a titanocene compound, a zirconocene compound, or a hafnocene compound, more preferably a titanocene compound, a zirconocene compound, or a hafnocene compound, and even more preferably a titanocene compound or a zirconocene compound. , titanocene compounds are particularly preferred.

An embodiment in which the organometallic complex has the ability to initiate photoradical polymerization is also one of the preferred embodiments of the present invention.
According to the present invention, it is thought that by using a specific resin, the organometallic complex is dispersed in a nearly uniform state in the film.
Therefore, when the organometallic complex has the ability to initiate photoradical polymerization, it is considered that local aggregation of the radical polymerization initiator due to aggregation of the organometallic complex is suppressed.
It is thought that by suppressing the aggregation of the radical polymerization initiator, the degree of polymerization of the specific resin or crosslinking agent tends to become nearly uniform within the membrane. Therefore, it is considered that development residues are less likely to occur, pattern breakage, etc. are less likely to occur, and resolution is likely to be improved.
In the present invention, having the ability to initiate photoradical polymerization means being able to generate free radicals that can initiate radical polymerization by irradiation with light. For example, when a composition containing a radical cross-linking agent and an organometallic complex is irradiated with light in a wavelength range in which the organometallic complex absorbs light and in which the radical cross-linker does not absorb light, radicals By checking whether the crosslinking agent disappears, it is possible to check whether the photoradical polymerization initiation ability exists. To confirm the presence or absence of disappearance, an appropriate method can be selected depending on the type of radical crosslinking agent, and for example, it may be confirmed by IR measurement (infrared spectroscopy) or HPLC measurement (high performance liquid chromatography).
When the organometallic complex has the ability to initiate photoradical polymerization, the organometallic complex is preferably a metallocene compound, more preferably a titanocene compound, a zirconocene compound, or a hafnocene compound, and preferably a titanocene compound or a zirconocene compound. are more preferred, and titanocene compounds are particularly preferred.
When the organometallic complex does not have the ability to initiate photoradical polymerization, the organometallic complex contains at least one compound selected from the group consisting of titanocene compounds, tetraalkoxytitanium compounds, titanium acylate compounds, titanium chelate compounds, zirconocene compounds, and hafnocene compounds. It is preferable that the compound is a type of compound, more preferably at least one compound selected from the group consisting of titanocene compounds, zirconocene compounds and hafnocene compounds, and at least one compound selected from the group consisting of titanocene compounds and zirconocene compounds. More preferably, it is a species compound, and particularly preferably a titanocene compound.

The molecular weight of the organometallic complex is preferably 50 to 2,000, more preferably 100 to 1,000.

As the organometallic complex, a compound represented by the following formula (P) is preferably mentioned.

In formula (P), M is a metal atom, and each R is independently a substituent.
Preferably, each R is independently selected from an aromatic group, an alkyl group, a halogen atom, and an alkylsulfonyloxy group.

In formula (P), the metal atom represented by M is preferably an iron atom, a titanium atom, a zirconium atom, or a hafnium atom, more preferably a titanium atom, a zirconium atom, or a hafnium atom, and even more preferably a titanium atom or a zirconium atom. Atoms are particularly preferred.
The aromatic group for R in formula (P) includes an aromatic group having 6 to 20 carbon atoms, preferably an aromatic hydrocarbon group having 6 to 20 carbon atoms, such as a phenyl group, a 1-naphthyl group, or , 2-naphthyl group, etc.
The alkyl group for R in formula (P) is preferably an alkyl group having 1 to 20 carbon atoms, more preferably an alkyl group having 1 to 10 carbon atoms, such as a methyl group, ethyl group, propyl group, octyl group, isopropyl group. , t-butyl group, isopentyl group, 2-ethylhexyl group, 2-methylhexyl group, cyclopentyl group, and the like.
Examples of the halogen atom in R include F, Cl, Br, and I.
The alkyl group constituting the alkylsulfonyloxy group in R above is preferably an alkyl group having 1 to 20 carbon atoms, more preferably an alkyl group having 1 to 10 carbon atoms, such as a methyl group, an ethyl group, a propyl group, an octyl group, Examples include isopropyl group, t-butyl group, isopentyl group, 2-ethylhexyl group, 2-methylhexyl group, and cyclopentyl group.
The above R may further have a substituent. Examples of substituents include halogen atoms (F, Cl, Br, I), hydroxy groups, carboxy groups, amino groups, cyano groups, aryl groups, alkoxy groups, aryloxy groups, acyl groups, alkoxycarbonyl groups, aryloxy Examples include carbonyl group, acyloxy group, monoalkylamino group, dialkylamino group, monoarylamino group, and diarylamino group.

Specific examples of organometallic complexes include, but are not limited to, tetraisopropoxytitanium, tetrakis(2-ethylhexyloxy)titanium, diisopropoxybis(ethyl acetoacetate)titanium, and diisopropoxybis(acetylacetoacetate). titanium, bis(η5-2,4-cyclopentadien-1-yl)bis(2,6-difluoro-3-(1H-pyrrol-1-yl)phenyl)titanium, pentamethylcyclopentadienyltitanium Examples include methoxide, bis(η5-2,4-cyclopentadien-1-yl)bis(2,6-difluorophenyl)titanium, and the following compounds.

In addition, compounds described in paragraphs 0078 to 0088 of International Publication No. 2018/025738 can also be used, but are not limited thereto.

The content of the organometallic complex is preferably 0.1 to 30% by mass based on the total solid content of the curable resin composition of the present invention. The lower limit is more preferably 1.0% by mass or more, still more preferably 1.5% by mass or more, and particularly preferably 3.0% by mass or more. The upper limit is more preferably 25% by mass or less.
One type or two or more types of organometallic complexes can be used. When two or more types are used, the total amount is preferably within the above range.

<Other resins>
The composition of the present invention may contain the above-described specific resin and another resin (hereinafter also simply referred to as "other resin") different from the specific resin.
Other resins include polyamide-imide, polyamide-imide precursors, phenol resins, polyamides, epoxy resins, polysiloxanes, resins containing siloxane structures, acrylic resins, and the like.
For example, by further adding an acrylic resin, a composition with excellent coating properties and an organic film with excellent solvent resistance can be obtained.
For example, instead of or in addition to the crosslinking agent described below, an acrylic resin with a high polymerizable group value and a weight average molecular weight of 20,000 or less may be added to the composition. The coating properties, solvent resistance of the organic film, etc. can be improved.

When the composition of the present invention contains other resins, the content of the other resins is preferably 0.01% by mass or more, and 0.05% by mass or more based on the total solid content of the composition. It is more preferably 1% by mass or more, even more preferably 2% by mass or more, even more preferably 5% by mass or more, and even more preferably 10% by mass or more. .
Further, the content of other resins in the composition of the present invention is preferably 80% by mass or less, more preferably 75% by mass or less, and 70% by mass based on the total solid content of the composition. It is more preferably at most 60% by mass, even more preferably at most 50% by mass.
Further, as a preferable embodiment of the composition of the present invention, the content of other resins can be low. In the above embodiment, the content of the other resin is preferably 20% by mass or less, more preferably 15% by mass or less, and preferably 10% by mass or less based on the total solid content of the composition. The content is more preferably 5% by mass or less, even more preferably 1% by mass or less. The lower limit of the content is not particularly limited, and may be 0% by mass or more.
The composition of the present invention may contain only one type of other resin, or may contain two or more types of other resins. When two or more types are included, it is preferable that the total amount falls within the above range.

<Solvent>
The curable resin composition of the present invention preferably contains a solvent. Any known solvent can be used as the 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.

Examples of esters include ethyl acetate, n-butyl acetate, isobutyl acetate, hexyl acetate, amyl formate, isoamyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, γ-butyrolactone. , ε-caprolactone, δ-valerolactone, alkyloxyacetate (e.g., methyl alkyloxyacetate, ethyl alkyloxyacetate, butyl alkyloxyacetate (e.g., methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, 3-alkyloxypropionate alkyl esters (e.g., methyl 3-alkyloxypropionate, ethyl 3-alkyloxypropionate, etc.), 3-alkyloxypropionate alkyl esters (e.g., methyl 3-methoxypropionate, 3-methoxypropionate), ethyl, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, etc.), 2-alkyloxypropionate alkyl esters (e.g., methyl 2-alkyloxypropionate, ethyl 2-alkyloxypropionate, 2-alkyl 2-alkyloxy- Methyl 2-methylpropionate and ethyl 2-alkyloxy-2-methylpropionate (for example, methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, etc.), methyl pyruvate, pyruvin Preferred examples include ethyl acid, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutanoate, ethyl 2-oxobutanoate, ethyl hexanoate, ethyl heptanoate, dimethyl malonate, diethyl malonate, and the like. .

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

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

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

Suitable examples of sulfoxides include dimethyl sulfoxide.

Amides include N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide, N,N-dimethylisobutyramide, 3-methoxy-N,N- Preferred examples include dimethylpropionamide, 3-butoxy-N,N-dimethylpropionamide, N-formylmorpholine, and N-acetylmorpholine.

Suitable ureas include N,N,N',N'-tetramethylurea, 1,3-dimethyl-2-imidazolidinone, and the like.

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

From the viewpoint of improving the properties of the coated surface, it is also preferable to mix two or more kinds of solvents.

In the present invention, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, methyl 3-methoxypropionate, 2-heptanone, cyclohexanone, cyclopentanone, γ- Consisting of one or more solvents selected from butyrolactone, dimethyl sulfoxide, ethyl carbitol acetate, butyl carbitol acetate, N-methyl-2-pyrrolidone, propylene glycol methyl ether, and propylene glycol methyl ether acetate Mixed solvents are preferred. Particularly preferred is the combination of dimethyl sulfoxide and γ-butyrolactone. Also preferred are combinations of N-methyl-2-pyrrolidone and ethyl lactate, N-methyl-2-pyrrolidone and ethyl lactate, diacetone alcohol and ethyl lactate, and cyclopentanone and γ-butyrolactone.

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

The solvent may contain only one type, or may contain two or more types. When two or more types of solvents are contained, it is preferable that the total amount is within the above range.

<Photosensitizer>
The composition of the present invention preferably contains a photosensitizer.
The photosensitizer does not include the above-mentioned organometallic complex having the ability to initiate photoradical polymerization.
The composition of the present invention preferably contains a photopolymerization initiator.

[Photopolymerization initiator]
The composition of the present invention preferably contains a photopolymerization initiator as a photosensitizer.
The photopolymerization initiator is preferably a radical photopolymerization initiator. The radical photopolymerization initiator is not particularly limited and can be appropriately selected from known radical photopolymerization initiators. For example, a photoradical polymerization initiator that is sensitive to light in the ultraviolet to visible range is preferable. Alternatively, the activator may be an activator that generates active radicals by having some effect with the photoexcited sensitizer.

In the present invention, compounds that correspond to organometallic complexes do not correspond to photosensitizers or radical photopolymerization initiators.

When the organometallic complex has the ability to initiate photoradical polymerization, the composition of the present invention preferably does not substantially contain any radical polymerization initiator other than the organometallic complex. Substantially not containing any radical polymerization initiator other than the above organometallic complex means that in the composition of the present invention, the content of the radical polymerization initiator other than the above organometallic complex is based on the total mass of the above organometallic complex. , 5% by mass or less, preferably 3% by mass or less, more preferably 1% by mass or less, and even more preferably 0.1% by mass.
Moreover, when the composition of the present invention contains an organometallic complex having the ability to initiate radical polymerization, it is also preferable that the composition of the present invention contains the above-mentioned organometallic complex and a photoradical polymerization initiator. According to such an aspect, as described above, generation of development residues, pattern disconnection, etc. can be suppressed, and exposure sensitivity can also be improved.
When the composition of the present invention contains an organometallic complex having no ability to initiate radical photopolymerization, the composition of the present invention preferably contains a radical photopolymerization initiator. Since the composition of the present invention contains a specific resin, it is thought that aggregation of the organometallic complex is suppressed. It is assumed that by suppressing the aggregation of organometallic complexes that do not have the ability to initiate photoradical polymerization, the local increase in plasticity of the film due to aggregation is suppressed, and the local increase in the degree of polymerization at the aggregation site is also suppressed. be done. As a result, it is presumed that variations in sensitivity depending on the region of the film are suppressed and resolution is improved.
When the composition of the present invention contains an organometallic complex and a radical photopolymerization initiator, the content of the organometallic complex with respect to the total content of the organometallic complex and the radical photopolymerization initiator is 20 to 80% by mass. The amount is preferably 30 to 70% by mass, and more preferably 30 to 70% by mass.
Further, as the photoradical polymerization initiator, the oxime compounds described below are preferable.

The photoradical polymerization initiator must contain at least one compound having a molar absorption coefficient of at least about 50 L·mol ⁻¹ ·cm ⁻¹ within the range of about 300 to 800 nm (preferably 330 to 500 nm). is preferred. The molar extinction coefficient of a compound can be measured using a known method. For example, it is preferable to measure at a concentration of 0.01 g/L using an ethyl acetate solvent with an ultraviolet-visible spectrophotometer (Cary-5 spectrophotometer manufactured by Varian).

As the photoradical polymerization initiator, any known compound can be used. For example, halogenated hydrocarbon derivatives (e.g., compounds having a triazine skeleton, compounds having an oxadiazole skeleton, compounds having a trihalomethyl group, etc.), acylphosphine compounds such as acylphosphine oxide, hexaarylbiimidazole, oxime derivatives, etc. Examples include oxime compounds, organic peroxides, thio compounds, ketone compounds, aromatic onium salts, ketoxime ethers, aminoacetophenone compounds, hydroxyacetophenones, azo compounds, azide compounds, and organic boron compounds. For these details, the descriptions in paragraphs 0165 to 0182 of Japanese Patent Application Publication No. 2016-027357 and paragraphs 0138 to 0151 of International Publication No. 2015/199219 can be referred to, and the contents thereof are incorporated herein.

Examples of the ketone compound include compounds described in paragraph 0087 of JP-A-2015-087611, the contents of which are incorporated herein. As a commercially available product, Kayacure DETX (manufactured by Nippon Kayaku Co., Ltd.) is also suitably used.

In one embodiment of the present invention, a hydroxyacetophenone compound, an aminoacetophenone compound, and an acylphosphine compound can be suitably used as the photoradical polymerization initiator. More specifically, for example, the aminoacetophenone initiator described in JP-A-10-291969 and the acylphosphine oxide initiator described in Japanese Patent No. 4225898 can be used.

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

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

As the aminoacetophenone initiator, a compound described in JP-A-2009-191179 whose maximum absorption wavelength is matched to a light source having a wavelength of 365 nm or 405 nm can also be used.

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

More preferred examples of the photoradical polymerization initiator include oxime compounds. By using an oxime compound, it becomes possible to improve exposure latitude more effectively. Oxime compounds are particularly preferred because they have a wide exposure latitude (exposure margin) and also act as photocuring accelerators.

As specific examples of the oxime compound, compounds described in JP-A No. 2001-233842, compounds described in JP-A No. 2000-080068, and compounds described in JP-A No. 2006-342166 can be used.

Preferred oxime compounds include, for example, compounds with the following structures, 3-benzoyloxyiminobutan-2-one, 3-acetoxyiminobutan-2-one, 3-propionyloxyiminobutan-2-one, 2-acetoxy Iminopentan-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 composition of the present invention, it is particularly preferable to use an oxime compound (oxime-based photopolymerization initiator) as a photoradical polymerization initiator. The oxime-based photopolymerization initiator has a >C=N-O-C(=O)- linking group in the molecule.

Commercially available products include IRGACURE OXE 01, IRGACURE OXE 02, IRGACURE OXE 03, IRGACURE OXE 04 (manufactured by BASF), and ADEKA Optomer N-1919 (manufactured by ADEKA Co., Ltd., the light described in JP-A No. 2012-014052). Radical polymerization initiator 2) is also suitably used. Furthermore, TR-PBG-304 (manufactured by Changzhou Strong Electronics New Materials Co., Ltd.), ADEKA ARCLES NCI-831, and ADEKA ARCLES NCI-930 (manufactured by ADEKA Corporation) can also be used. Additionally, DFI-091 (manufactured by Daito Chemix Co., Ltd.) can be used. Moreover, oxime compounds having the following structures can also be used.

As the photopolymerization initiator, an oxime compound having a fluorene ring can also be used. Specific examples of oxime compounds having a fluorene ring include compounds described in JP-A No. 2014-137466 and compounds described in Japanese Patent No. 6,636,081.

As the photopolymerization initiator, it is also possible to use an oxime compound having a skeleton in which at least one benzene ring of a carbazole ring is a naphthalene ring. Specific examples of such oxime compounds include compounds described in International Publication No. 2013/083505.

It is also possible to use an oxime compound containing a fluorine atom. Specific examples of such oxime compounds include compounds described in JP-A No. 2010-262028, compounds 24, 36 to 40 described in paragraph 0345 of Japanese Patent Publication No. 2014-500852, and JP-A No. 2013-2013. Examples include the compound (C-3) described in paragraph 0101 of Publication No. 164471.

The most preferred oxime compounds include oxime compounds having specific substituents as shown in JP-A No. 2007-269779, and oxime compounds having a thioaryl group as shown in JP-A No. 2009-191061.

From the viewpoint of exposure sensitivity, photoradical polymerization initiators include trihalomethyltriazine compounds, benzyl dimethyl ketal compounds, α-hydroxyketone compounds, α-aminoketone compounds, acylphosphine compounds, phosphine oxide compounds, metallocene compounds, oxime compounds, and triaryl compounds. selected from the group consisting of imidazole dimers, onium salt compounds, benzothiazole compounds, benzophenone compounds, acetophenone compounds and derivatives thereof, cyclopentadiene-benzene-iron complexes and salts thereof, halomethyloxadiazole compounds, and 3-aryl substituted coumarin compounds. Compounds such as

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

In addition, photoradical polymerization initiators include benzophenone, N,N'-tetraalkyl-4,4'-diaminobenzophenone such as N,N'-tetramethyl-4,4'-diaminobenzophenone (Michler's ketone), 2-benzyl Aromatic ketones such as -2-dimethylamino-1-(4-morpholinophenyl)-butanone-1,2-methyl-1-[4-(methylthio)phenyl]-2-morpholino-propanone-1, alkylanthraquinone, etc. It is also possible to use quinones condensed with the aromatic ring of , benzoin ether compounds such as benzoin alkyl ether, benzoin compounds such as benzoin and alkylbenzoin, and benzyl derivatives such as benzyl dimethyl ketal. Moreover, a compound represented by the following formula (I) can also be used.

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

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

Further, as the photoradical polymerization initiator, compounds described in paragraphs 0048 to 0055 of International Publication No. 2015/125469 can also be used.

When a photopolymerization initiator is included, its content is preferably 0.1 to 30% by mass, more preferably 0.1 to 20% by mass, based on the total solid content of the composition of the present invention, More preferably, it is 0.5 to 15% by weight, even more preferably 1.0 to 10% by weight. The photopolymerization initiator may contain only one type, or may contain two or more types. When containing two or more types of photopolymerization initiators, it is preferable that the total amount is within the above range.

[Photoacid generator]
Moreover, it is also preferable that the composition of the present invention contains a photoacid generator as a photosensitizer.
By containing a photoacid generator, for example, acid is generated in the exposed area of the photosensitive film, increasing the solubility of the exposed area in a developer (e.g., aqueous alkaline solution), and the exposed area is removed by the developer. A positive pattern can be obtained.
Furthermore, when the composition contains a photoacid generator and a crosslinking agent other than the radical crosslinking agent described below, for example, the acid generated in the exposed area accelerates the crosslinking reaction of the crosslinking agent, and the exposed area It is also possible to adopt an embodiment in which the area is more difficult to be removed by a developer than the non-exposed area. According to this aspect, a negative pattern can be obtained.

Photoacid generators are not particularly limited as long as they generate acid upon exposure to light, but include quinonediazide compounds, onium salt compounds such as diazonium salts, phosphonium salts, sulfonium salts, and iodonium salts, imidosulfonates, and oximes. Examples include sulfonate compounds such as sulfonate, diazodisulfone, disulfone, and o-nitrobenzylsulfonate.

Quinonediazide compounds include those in which the sulfonic acid of quinonediazide is bonded to a polyhydroxy compound through an ester bond, those in which the sulfonic acid of quinonediazide is bonded to a polyamino compound through a sulfonamide bond, and those in which the sulfonic acid of quinonediazide is bonded to a polyhydroxy polyamino compound through an ester bond and a sulfonamide bond. Examples include those bound by at least one of the following. In the present invention, for example, it is preferable that 50 mol% or more of the total functional groups of these polyhydroxy compounds and polyamino compounds are substituted with quinonediazide.

In the present invention, as the quinonediazide, either a 5-naphthoquinonediazide sulfonyl group or a 4-naphthoquinonediazide sulfonyl group is preferably used. The 4-naphthoquinonediazide sulfonyl ester compound has absorption in the i-line region of a mercury lamp and is suitable for i-line exposure. The 5-naphthoquinonediazide sulfonyl ester compound has absorption extending to the G-line region of a mercury lamp, and is suitable for G-line exposure. In the present invention, it is preferable to select a 4-naphthoquinone diazide sulfonyl ester compound or a 5-naphthoquinone diazide sulfonyl ester compound depending on the wavelength of exposure. Further, a naphthoquinonediazide sulfonyl ester compound having a 4-naphthoquinonediazide sulfonyl group or a 5-naphthoquinonediazide sulfonyl group may be contained in the same molecule, or a 4-naphthoquinonediazide sulfonyl ester compound and a 5-naphthoquinonediazide sulfonyl ester compound may be contained in the same molecule. May be contained.

The above naphthoquinonediazide compound can be synthesized by an esterification reaction between a compound having a phenolic hydroxyl group and a quinonediazide sulfonic acid compound, and can be synthesized by a known method. By using these naphthoquinonediazide compounds, resolution, sensitivity, and film retention rate are further improved.
Examples of the naphthoquinone diazide compound include 1,2-naphthoquinone-2-diazide-5-sulfonic acid, 1,2-naphthoquinone-2-diazide-4-sulfonic acid, and salts or ester compounds of these compounds. It will be done.

Examples of the onium salt compound or sulfonate compound include compounds described in paragraphs 0064 to 0122 of JP-A No. 2008-013646.

It is also preferable that the photoacid generator is a compound containing an oxime sulfonate group (hereinafter also simply referred to as "oxime sulfonate compound").
The oxime sulfonate compound is not particularly limited as long as it has an oxime sulfonate group. An oxime sulfonate compound represented by 105) is preferable.

In formula (OS-1), X ³ represents an alkyl group, an alkoxyl group, or a halogen atom. When multiple X ³ 's exist, they may be the same or different. The alkyl group and alkoxyl group in X ³ above may have a substituent. The alkyl group for X ³ above is preferably a linear or branched alkyl group having 1 to 4 carbon atoms. The alkoxyl group for X ³ above is preferably a linear or branched alkoxyl group having 1 to 4 carbon atoms. The halogen atom in X ³ is preferably a chlorine atom or a fluorine atom.
In formula (OS-1), m3 represents an integer of 0 to 3, preferably 0 or 1. When m3 is 2 or 3, multiple X ³ 's may be the same or different.
In formula (OS-1), R ³⁴ represents an alkyl group or an aryl group, an alkyl group having 1 to 10 carbon atoms, an alkoxyl group having 1 to 10 carbon atoms, a halogenated alkyl group having 1 to 5 carbon atoms, a carbon Preferably, it is a halogenated alkoxyl group of numbers 1 to 5, a phenyl group optionally substituted with W, a naphthyl group optionally substituted with W, or an anthranyl group optionally substituted with W. W is a halogen atom, a cyano group, a nitro group, an alkyl group having 1 to 10 carbon atoms, an alkoxyl group having 1 to 10 carbon atoms, a halogenated alkyl group having 1 to 5 carbon atoms, or a halogenated alkoxyl group having 1 to 5 carbon atoms. group, 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 substitution position of X ³ is ortho position, R ³⁴ is a linear alkyl group having 1 to 10 carbon atoms, 7, Particularly preferred are compounds having a 7-dimethyl-2-oxonorbornylmethyl group or a p-tolyl group.

Specific examples of the oxime sulfonate compound represented by formula (OS-1) include those described in paragraph numbers 0064 to 0068 of JP-A No. 2011-209692 and paragraph numbers 0158 to 0167 of JP-A No. 2015-194674. The following compounds are exemplified, the contents of which are incorporated herein.

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 exist in plurality, each independently represents a hydrogen atom, an alkyl group, an aryl group. represents a group or a halogen atom, and R ^s6 , which may exist in plurality, each independently represents a halogen atom, an alkyl group, an alkyloxy group, a sulfonic acid group, an aminosulfonyl group, or an alkoxysulfonyl group, and Xs represents O or S. where 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 6 to 30 carbon atoms) represented by R s1 (preferably number 4 to 30) may have a substituent T.

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). , a hydrogen atom or an alkyl group. Of the two or more R ^s2 that may be present in the compound, one or two are preferably an alkyl group, an aryl group, or a halogen atom, and more preferably one is an alkyl group, an aryl group, or a halogen atom. , it is particularly preferred that one of them is an alkyl group and the others are hydrogen atoms. The alkyl group or aryl group represented by R ^s2 may have a substituent T.
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 ring member is a 5-membered ring or a 6-membered ring.

In formulas (OS-103) to (OS-105), ns represents 1 or 2; when Xs is O, ns is preferably 1; and when Xs is S, ns is It is preferable that it is 2.
In formulas (OS-103) to (OS-105), the alkyl group (preferably having 1 to 30 carbon atoms) and alkyloxy group (preferably having 1 to 30 carbon atoms) represented by R ^s6 have a substituent group. may have.
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, and 0. is particularly preferred.

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

In formulas (OS-106) to (OS-111), R ^t1 represents an alkyl group, aryl group, or heteroaryl group, R ^t7 represents a hydrogen atom or a bromine atom, and R ^t8 represents a hydrogen atom and the number of carbon atoms. 1 to 8 alkyl group, halogen atom, chloromethyl group, bromomethyl group, bromoethyl group, methoxymethyl group, phenyl group or chlorophenyl group, R ^t9 represents a hydrogen atom, halogen atom, methyl group or methoxy group, R ^t2 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 having 1 to 8 carbon atoms, a halogen atom or a phenyl group, more preferably an alkyl group having 1 to 8 carbon atoms, and an alkyl group having 1 to 6 carbon atoms. More preferably, it is a methyl group, and a methyl group is particularly preferred.

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 above-mentioned oxime sulfonate compound, the steric structure (E, Z) of the oxime may be either one or a mixture.
Specific examples of the oxime sulfonate compounds represented by the above formulas (OS-103) to (OS-105) include paragraph numbers 0088 to 0095 of JP-A No. 2011-209692 and paragraph numbers of JP-A No. 2015-194674. The compounds described in numbers 0168 to 0194 are exemplified, the contents of which are incorporated herein.

Other preferred embodiments of the oxime sulfonate compound containing at least one oxime sulfonate group include compounds represented by the following formulas (OS-101) and (OS-102).

In formula (OS-101) or formula (OS-102), R ^u9 is a hydrogen atom, an alkyl group, an alkenyl group, an alkoxyl group, an alkoxycarbonyl group, an acyl group, a carbamoyl group, a sulfamoyl group, a sulfo group, a cyano group, Represents an aryl group or a heteroaryl group. An embodiment in which R ^u9 is a cyano group or an aryl group is more preferred, and an embodiment in which R ^u9 is a cyano group, a phenyl group, or a naphthyl group is even more preferred.
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 each independently represent a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, an alkoxyl 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 rings may be condensed to form a condensed ring together with the benzene ring. R ^u1 to R ^u4 are preferably a hydrogen atom, a halogen atom, or an alkyl group, and an embodiment in which at least two of R ^u1 to R ^u4 bond to each other to form an aryl group is also preferred. Among these, an embodiment in which R ^u1 to R ^u4 are all hydrogen atoms is preferred. All of the above substituents may further have a substituent.

The compound represented by the above formula (OS-101) is more preferably a compound represented by the formula (OS-102).
Further, in the above-mentioned oxime sulfonate compound, the steric structures (E, Z, etc.) of the oxime and benzothiazole rings may be either one or a mixture.
Specific examples of the compound represented by formula (OS-101) include compounds described in paragraph numbers 0102 to 0106 of JP-A No. 2011-209692 and paragraph numbers 0195 to 0207 of JP-A No. 2015-194674. , the contents of which are incorporated herein.
Among the above compounds, the following b-9, b-16, b-31, and b-33 are preferred.

In addition, commercially available products may be used as the photoacid generator. Commercially available products include WPAG-145, WPAG-149, WPAG-170, WPAG-199, WPAG-336, WPAG-367, WPAG-370, WPAG-443, WPAG-469, WPAG-638, WPAG-699 (all Fujifilm Wako Pure Chemical Industries, Ltd.), Omnicat 250, Omnicat 270 (all manufactured by IGM Resins B.V.), Irgacure 250, Irgacure 270, Irgacure 290 (all manufactured by BASF), MBZ-101 ( (manufactured by Midori Kagaku Co., Ltd.), etc.

Further, preferred examples include compounds represented by the following structural formula.

Organic halogenated compounds can also be used as photoacid generators. Examples of organic halogenated compounds include Wakabayashi et al. "Bull Chem. Soc Japan" 42, 2924 (1969), U.S. Pat. 48-36281, JP 55-32070, JP 60-239736, JP 61-169835, JP 61-169837, JP 62-58241, JP 62- No. 212401, JP-A-63-70243, JP-A-63-298339, M. P. Examples include compounds described in Hutt "Journal of Heterocyclic Chemistry" 1 (No. 3), (1970), and in particular, oxazole compounds substituted with trihalomethyl groups: S-triazine compounds.
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(monochloromethyl)- 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-epoxy phenyl)-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-(pi-propyloxystyryl)-4,6-bis(trichloromethyl)-s-triazine, 2-(p-tolyl)-4,6 -bis(trichloromethyl)-s-triazine, 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(tribromomethyl)-s- Examples include triazine, 2-methyl-4,6-bis(tribromomethyl)-s-triazine, and 2-methoxy-4,6-bis(tribromomethyl)-s-triazine.

Organic borate compounds can also be used as photoacid generators. Examples of organic borate compounds include JP-A-62-143044, JP-A-62-150242, JP-A-9-188685, JP-A-9-188686, JP-A-9-188710, and JP-A-2000. -131837, Japanese Unexamined Patent Publication No. 2002-107916, Patent No. 2764769, Japanese Patent Application No. 2000-310808, etc., and described in Kunz, Martin "Rad Tech'98. Proceeding April 19-22, 1998, Chicago", etc. organic borates, organic boron sulfonium complexes or organic boron oxosulfonium complexes described in JP-A-6-157623, JP-A-6-175564, JP-A-6-175561, JP-A-6-175554 organoboron iodonium complexes described in JP-A-6-175553, organoboron-phosphonium complexes described in JP-A-9-188710, JP-A-6-348011, JP-A-7-128785, JP-A-Hei 7-128785; Specific examples include organic boron transition metal coordination complexes such as those disclosed in JP-A No. 7-140589, JP-A-7-306527, and JP-A-7-292014.

Disulfone compounds can also be used as photoacid generators. Examples of the disulfone compound include compounds described in JP-A-61-166544, Japanese Patent Application No. 2001-132318, and diazodisulfone compounds.

Examples of the onium salt compounds include S. I. Schlesinger, Photogr. Sci. Eng. , 18, 387 (1974), T. S. Diazonium salts described in Bal et al, Polymer, 21,423 (1980), ammonium salts described in US Pat. No. 4,069,055, JP-A-4-365049, etc.; 055 and 4,069,056, European Patent Nos. 104 and 143, US Patent Nos. 339,049 and 410,201, and JP-A-2 -150848, iodonium salts described in JP-A-2-296514, European Patent No. 370,693, European Patent No. 390,214, European Patent No. 233,567, European Patent No. 297,443, European Patent No. 297,442, US Pat. No. 4,933,377, No. 161,811, No. 410,201, No. 339,049, No. 4,760,013, No. 4,734,444, No. 2,833,827, The sulfonium salts described in German Patent Nos. 2,904,626, 3,604,580 and 3,604,581; V. Crivello et al, Macromolecules, 10(6), 1307 (1977), J. V. Crivello et al, J. Polymer Sci. , Polymer Chem. Ed. , 17, 1047 (1979); S. Wen et al, Teh, Proc. Conf. Rad. Examples include onium salts such as arsonium salts and pyridinium salts described in Curing ASIA, p478 Tokyo, Oct. (1988).

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

In formula (RI-I), Ar ₁₁ represents an aryl group having 20 or less carbon atoms which may have 1 to 6 substituents, and preferred substituents include an alkyl group having 1 to 12 carbon atoms, and 1 to 6 carbon atoms. ~12 alkenyl group, C1-12 alkynyl group, C1-12 aryl group, C1-12 alkoxy group, C1-12 aryloxy group, halogen atom, C1-12 alkylamino group, dialkylamino group having 1 to 12 carbon atoms, alkylamino group or arylamido group having 1 to 12 carbon atoms, carbonyl group, carboxyl group, cyano group, sulfonyl group, thioalkyl group having 1 to 12 carbon atoms, Examples include thioaryl groups having 1 to 12 carbon atoms. Z11 ^- represents a monovalent anion, which is a halogen ion, perchlorate ion, hexafluorophosphate ion, tetrafluoroborate ion, sulfonate ion, sulfinate ion, thiosulfonate ion, or sulfate ion, and is important in terms of stability. Among them, perchlorate ion, hexafluorophosphate ion, tetrafluoroborate ion, sulfonate ion, and sulfinate ion are preferred. In formula (RI-II), Ar ₂₁ and Ar ₂₂ each independently represent an aryl group having 20 or less carbon atoms which may have 1 to 6 substituents, and preferred substituents include aryl groups having 1 to 12 carbon atoms. Alkyl group, alkenyl group having 1 to 12 carbon atoms, alkynyl group having 1 to 12 carbon atoms, aryl group having 1 to 12 carbon atoms, alkoxy group having 1 to 12 carbon atoms, aryloxy group having 1 to 12 carbon atoms, halogen atom , alkylamino group having 1 to 12 carbon atoms, dialkylamino group having 1 to 12 carbon atoms, alkylamino group or arylamido group having 1 to 12 carbon atoms, carbonyl group, carboxyl group, cyano group, sulfonyl group, 1 carbon number Examples include thioalkyl groups having 1 to 12 carbon atoms and thioaryl groups having 1 to 12 carbon atoms. Z ₂₁ ⁻ represents a monovalent anion, which is a halogen ion, perchlorate ion, hexafluorophosphate ion, tetrafluoroborate ion, sulfonate ion, sulfinate ion, thiosulfonate ion, or sulfate ion, and has stability, From the viewpoint of reactivity, perchlorate ions, hexafluorophosphate ions, tetrafluoroborate ions, sulfonate ions, sulfinate ions, and carboxylate ions are preferred. In formula (RI-III), R ₃₁ , R ₃₂ , and R ₃₃ each independently represent an aryl group having 20 or less carbon atoms, or an alkyl group, an alkenyl group, or an alkynyl group, which may have 1 to 6 substituents. From the viewpoint of reactivity and stability, an aryl group is preferable. Preferred substituents include an alkyl group having 1 to 12 carbon atoms, an alkenyl group having 1 to 12 carbon atoms, an alkynyl group having 1 to 12 carbon atoms, an aryl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, Aryloxy group having 1 to 12 carbon atoms, halogen atom, alkylamino group having 1 to 12 carbon atoms, dialkylamino group having 1 to 12 carbon atoms, alkylamido group or arylamido group having 1 to 12 carbon atoms, carbonyl group, carboxyl 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. Z31 ^- represents a monovalent anion, which is a halogen ion, perchlorate ion, hexafluorophosphate ion, tetrafluoroborate ion, sulfonate ion, sulfinate ion, thiosulfonate ion, or sulfate ion, and has a high stability and reaction From the viewpoint of properties, perchlorate ions, hexafluorophosphate ions, tetrafluoroborate ions, sulfonate ions, sulfinate ions, and carboxylate ions are preferred.

Specific examples include the following.

When a photoacid generator is included, its content is preferably 0.1 to 30% by mass, more preferably 0.1 to 20% by mass, based on the total solid content of the composition of the present invention. , more preferably 2 to 15% by mass. The photoacid generator may contain only one type, or may contain two or more types. When containing two or more types of photoacid generators, it is preferable that the total is within the above range.

[Photobase generator]
The curable resin composition of the present invention may contain a photobase generator as a photosensitizer.
When the curable resin composition contains a photobase generator and a crosslinking agent described below, the crosslinking reaction of the crosslinking agent is promoted, for example, the base generated in the exposed area promotes cyclization of the specific resin. It is also possible to adopt a mode in which exposed areas are more difficult to be removed by a developer than non-exposed areas. According to such an embodiment, a negative relief pattern can be obtained.

The photobase generator is not particularly limited as long as it generates a base upon exposure to light, and any known photobase generator can be used.
For example, M. Shirai, and M. Tsunooka, Prog. Polym. Sci. , 21, 1 (1996); Masahiro Kadooka, Polymer Processing, 46, 2 (1997); C. Kutal, Coord. Chem. Rev. , 211, 353 (2001); Y. Kaneko, A. Sarker, and D. Neckers, Chem. Mater. , 11, 170 (1999); H. Tachi, M. Shirai, and M. Tsunooka, J. Photopolym. Sci. Technol. , 13, 153 (2000); M. Winkle, and K. Graziano, J. Photopolym. Sci. Technol. , 3, 419 (1990); M. Tsunooka, H. Tachi, and S. Yoshitaka, J. Photopolym. Sci. Technol. , 9, 13 (1996); K. Suyama, H. Araki, M. Shirai, J. Photopolym. Sci. Technol. , 19, 81 (2006), those with structures such as transition metal compound complexes and ammonium salts, and those in which the amidine moiety is made latent by forming a salt with a carboxylic acid. Ionic compounds whose base components are neutralized by forming salts, and nonionic compounds whose base components are latent through urethane bonds or oxime bonds such as carbamate derivatives, oxime ester derivatives, and acyl compounds. can be mentioned.
In the present invention, more preferable examples of the photobase generator include carbamate derivatives, amide derivatives, imide derivatives, α-cobalt complexes, imidazole derivatives, cinnamic acid amide derivatives, oxime derivatives, and the like.

The basic substance generated from the photobase generator includes, but is not particularly limited to, compounds having an amino group, particularly monoamines, polyamines such as diamines, and amidine.
From the viewpoint of imidization rate, it is preferable that the basic substance has a large pKa of the conjugate acid in DMSO (dimethyl sulfoxide). The above pKa is preferably 1 or more, more preferably 3 or more. The upper limit of the pKa is not particularly limited, but is preferably 20 or less.
Here, the above pKa represents the logarithm of the reciprocal of the first dissociation constant of the acid, and is based on Determination of Organic Structures by Physical Methods (Authors: Brown, HC, McDaniel, DH, Hafliger, O., Nachod, FC; Edited by: Braude, EA, Nachod, FC; Academic Press, New York, 1955) and Data for Biochemical Research (author: Dawson, RMCet al; Oxford, Clarendon Press, 1959) can be referred to. For compounds that are not described in these documents, a value calculated from the structural formula using ACD/pKa (manufactured by ACD/Labs) software is used as the pKa.

From the viewpoint of storage stability of the curable resin composition, the photobase generator is preferably a photobase generator that does not contain salt in its structure, and the nitrogen atom of the base moiety generated in the photobase generator Preferably there is no charge on it. As a photobase generator, it is preferable that the generated base is made latent using a covalent bond, and the base generation mechanism is such that the covalent bond between the nitrogen atom of the generated base moiety and the adjacent atom is broken. It is preferable that the base be generated by When the photobase generator does not contain salt in its structure, the photobase generator can be made neutral, so that the solvent solubility is better and the pot life is improved. For these reasons, the amine generated from the photobase generator used in the present invention is preferably a primary amine or a secondary amine.
Furthermore, from the viewpoint of chemical resistance of the pattern, the photobase generator is preferably a photobase generator containing a salt in its structure.

Furthermore, for the reasons mentioned above, as a photobase generator, it is preferable that the base generated as described above is made latent using a covalent bond, and the base generated can form an amide bond, a carbamate bond, or an oxime bond. Preferably, it is made latent by using
Examples of the photobase generator according to the present invention include photobase generators having a cinnamic acid amide structure as disclosed in JP2009-080452A and WO2009/123122; A photobase generator having a carbamate structure as disclosed in JP-A No. 2007-249013 and JP-A No. 2008-003581, a carbamoyl Examples include photobase generators having an oxime structure, but the present invention is not limited thereto, and other structures of known photobase generators can also be used.

Other photobase generators include compounds described in paragraph numbers 0185 to 0188, 0199 to 0200, and 0202 of JP2012-093746A, and compounds described in paragraphs 0022 to 0069 of JP2013-194205A. Examples include the compounds described in paragraph numbers 0026 to 0074 of JP 2013-204019 A, and the compounds described in paragraph number 0052 of WO 2010/064631.

In addition, commercially available products may be used as the photobase generator. Commercial products include WPBG-266, WPBG-300, WPGB-345, WPGB-140, WPBG-165, WPBG-027, WPBG-018, WPGB-015, WPBG-041, WPGB-172, WPGB-174, WPBG -166, WPGB-158, WPGB-025, WPGB-168, WPGB-167, WPBG-082 (all manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), A2502, B5085, N0528, N1052, O0396, O0447, O0448 ( (manufactured by Tokyo Kasei Kogyo Co., Ltd.), etc.

When a photobase generator is included, its content is preferably 0.1 to 30% by mass, and preferably 0.1 to 20% by mass, based on the total solid content of the curable resin composition of the present invention. is more preferable, and even more preferably 2 to 15% by mass. The photobase generator may contain only one type, or may contain two or more types. When containing two or more types of photobase generators, it is preferable that the total is within the above range.

<Thermal polymerization initiator>
The composition of the invention may also contain a thermal polymerization initiator, in particular a thermal radical polymerization initiator. A thermal radical polymerization initiator is a compound that generates radicals using thermal energy and initiates or accelerates the polymerization reaction of a compound having polymerizability. By adding a thermal radical polymerization initiator, it is possible to advance the polymerization reaction of the resin and the crosslinking agent in the heating step described below, so that the solvent resistance can be further improved.

Specific examples of the thermal radical polymerization initiator include compounds described in paragraphs 0074 to 0118 of JP-A No. 2008-063554.

When a thermal polymerization initiator is included, its content is preferably 0.1 to 30% by mass, more preferably 0.1 to 20% by mass, based on the total solid content of the composition of the present invention. More preferably, it is 0.5 to 15% by mass. The thermal polymerization initiator may contain only one type, or may contain two or more types. When containing two or more types of thermal polymerization initiators, it is preferable that the total amount is within the above range.

<Thermal acid generator>
Compositions of the invention may also include a thermal acid generator.
The thermal acid generator generates acid by heating and promotes the crosslinking 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. It has the effect of

The thermal decomposition starting temperature of the thermal acid generator is preferably 50°C to 270°C, more preferably 50°C to 250°C. In addition, no acid is generated during drying (prebaking: approximately 70 to 140°C) after applying the composition to the substrate, and during final heating (curing: approximately 100 to 400°C) after patterning by subsequent exposure and development. It is preferable to select a thermal acid generator that generates an acid because it can suppress a decrease in sensitivity during development.
The thermal decomposition initiation temperature is determined as the peak temperature of the lowest exothermic peak when the thermal acid generator is heated to 500° C. at 5° C./min in a pressure-resistant capsule.
Examples of equipment used to measure the thermal decomposition start temperature include Q2000 (manufactured by TA Instruments).

The acid generated from the thermal acid generator is preferably a strong acid, such as arylsulfonic acids such as p-toluenesulfonic acid and benzenesulfonic acid, alkylsulfonic acids such as methanesulfonic acid, ethanesulfonic acid, butanesulfonic acid, or trifluoromethane. Haloalkylsulfonic acids such as sulfonic acids are preferred. Examples of such thermal acid generators include those described in paragraph 0055 of JP-A No. 2013-072935.

Among these, those that generate alkyl sulfonic acids having 1 to 4 carbon atoms or haloalkylsulfonic acids having 1 to 4 carbon atoms are more preferable, from the viewpoint that there is little residual in the organic film and it is difficult to deteriorate the physical properties of the organic film, and methanesulfonic acid is preferable. (4-hydroxyphenyl)dimethylsulfonium, (4-((methoxycarbonyl)oxy)phenyl)dimethylsulfonium methanesulfonate, benzyl(4-hydroxyphenyl)methylsulfonium methanesulfonate, benzyl methanesulfonate (4-((methoxycarbonyl)oxy)phenyl) carbonyl)oxy)phenyl)methylsulfonium, (4-hydroxyphenyl)methyl((2-methylphenyl)methyl)sulfonium methanesulfonate, (4-hydroxyphenyl)dimethylsulfonium trifluoromethanesulfonate, trifluoromethanesulfonic acid (4- ((methoxycarbonyl)oxy)phenyl)dimethylsulfonium, benzyl(4-hydroxyphenyl)methylsulfonium trifluoromethanesulfonate, benzyl(4-((methoxycarbonyl)oxy)phenyl)methylsulfonium trifluoromethanesulfonate, trifluoromethanesulfonic acid (4-hydroxyphenyl)methyl((2-methylphenyl)methyl)sulfonium, 3-(5-(((propylsulfonyl)oxy)imino)thiophene-2(5H)-ylidene)-2-(o-tolyl) Propane nitrile, 2,2-bis(3-(methanesulfonylamino)-4-hydroxyphenyl)hexafluoropropane are preferred as the thermal acid generator.

Further, the compound described in paragraph 0059 of JP-A-2013-167742 is also preferable as a thermal acid generator.

The content of the thermal acid generator is preferably 0.01 parts by mass or more, more preferably 0.1 parts by mass or more, based on 100 parts by mass of the specific resin. By containing 0.01 parts by mass or more, the crosslinking reaction is promoted, so that the mechanical properties and solvent resistance of the organic film can be further improved. Further, from the viewpoint of electrical insulation of the organic film, the content is preferably 20 parts by mass or less, more preferably 15 parts by mass or less, and even more preferably 10 parts by mass or less.

<Onium salt>
The curable resin composition of the present invention may further contain an onium salt.
In particular, when the curable resin composition of the present invention contains a polyimide precursor or a polybenzoxazole precursor as the specific resin, it is preferable to contain an onium salt.
The type of onium salt is not particularly limited, but ammonium salts, iminium salts, sulfonium salts, iodonium salts, and phosphonium salts are preferred.
Among these, ammonium salts or iminium salts are preferred from the viewpoint of high thermal stability, and sulfonium salts, iodonium salts or phosphonium salts are preferred from the viewpoint of compatibility with the polymer.

Furthermore, an onium salt is a salt of a cation and an anion having an onium structure, and the cation and anion may or may not be bonded through a covalent bond. .
That is, the onium salt may be an inner salt having a cation moiety and an anion moiety within the same molecular structure, or an onium salt in which a cation molecule and an anion molecule, which are separate molecules, are ionically bonded. Although it may be an intermolecular salt, it is preferably an intermolecular salt. Furthermore, in the curable resin composition of the present invention, the cation moiety or cation molecule and the anion moiety or anion molecule may be bonded to each other by an ionic bond or may be dissociated.
The cation in the onium salt is preferably an ammonium cation, a pyridinium cation, a sulfonium cation, an iodonium cation or a phosphonium cation, and more preferably at least one cation selected from the group consisting of a tetraalkylammonium cation, a sulfonium cation and an iodonium cation.

The onium salt used in the present invention may be a thermal base generator described below.
The thermal base generator refers to a compound that generates a base when heated, and includes, for example, a compound that generates a base when heated to 40° C. or higher.
Examples of onium salts include onium salts described in paragraphs 0122 to 0138 of International Publication No. 2018/043262. In addition, onium salts used in the field of polyimide precursors can be used without particular limitation.

When the curable resin composition of the present invention contains an onium salt, the content of the onium salt is preferably 0.1 to 50% by mass based on the total solid content of the curable resin composition of the present invention. The lower limit is more preferably 0.5% by mass or more, even more preferably 0.85% by mass or more, and even more preferably 1% by mass or more. The upper limit is more preferably 30% by mass or less, further preferably 20% by mass or less, even more preferably 10% by mass or less, may be 5% by mass or less, and may be 4% by mass or less.
One type or two or more types of onium salts can be used. When two or more types are used, the total amount is preferably within the above range.

<Thermal base generator>
The curable resin composition of the present invention may further contain a thermal base generator.
In particular, when the curable resin composition of the present invention contains a polyimide precursor or a polybenzoxazole precursor as the specific resin, it preferably contains a thermal base generator.
The other thermal base generator may be a compound corresponding to the above-mentioned onium salt, or may be a thermal base generator other than the above-mentioned onium salt.
Examples of thermal base generators other than the above-mentioned onium salts include nonionic thermal base generators.
Examples of the nonionic thermal base generator include compounds represented by formula (B1) or formula (B2).

In formulas (B1) and (B2), Rb ¹ , Rb ² and Rb ³ are each independently an organic group having no tertiary amine structure, a halogen atom or a hydrogen atom. However, Rb ¹ and Rb ² do not become hydrogen atoms at the same time. Further, none of Rb ¹ , Rb ² and Rb ³ has a carboxy group. In 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, this does not apply when the bonded carbon atom forms a carbonyl group, that is, when it forms an amide group together with a nitrogen atom.

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

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

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

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

In the formula, Rb ¹¹ and Rb ¹² and Rb ³¹ and Rb ³² are the same as Rb ¹ and Rb ² in Formula (B1), respectively.
Rb ¹³ is an alkyl group (preferably 1 to 24 carbon atoms, more preferably 2 to 18 carbon atoms, even more preferably 3 to 12 carbon atoms), an alkenyl group (preferably 2 to 24 carbon atoms, more preferably 2 to 18 carbon atoms, 3 to 12 carbon atoms) is more preferable), an aryl group (preferably has 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, even more preferably 6 to 12 carbon atoms), an arylalkyl group (preferably has 7 to 23 carbon atoms, more preferably 7 to 19 carbon atoms), 7 to 12 are more preferable), and may have a substituent within the range that produces the effects of the present invention. Among these, Rb ¹³ is preferably an arylalkyl group.

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

Rb ³⁵ is an alkyl group (preferably 1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms, even more preferably 3 to 8 carbon atoms), an alkenyl group (preferably 2 to 12 carbon atoms, more preferably 2 to 10 carbon atoms, 3 to 8 carbon atoms) 8 is more preferable), an aryl group (preferably 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, even more preferably 6 to 12 carbon atoms), an arylalkyl group (preferably 7 to 23 carbon atoms, more preferably 7 to 19 carbon atoms) , 7 to 12 are more preferred), and an aryl group is preferred.

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

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

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

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

The content of the other thermal base generator is preferably 0.1 to 50% by mass based on the total solid content of the curable resin composition of the present invention. The lower limit is more preferably 0.5% by mass or more, and even more preferably 1% by mass or more. The upper limit is more preferably 30% by mass or less, and even more preferably 20% by mass or less. One type or two or more types of thermal base generators can be used. When two or more types are used, the total amount is preferably within the above range.

<Crosslinking agent>
The curable resin composition of the present invention preferably contains a crosslinking agent.
Examples of crosslinking agents include radical crosslinking agents and other crosslinking agents.

<Radical crosslinking agent>
It is preferable that the curable resin composition of the present invention further contains a radical crosslinking agent.
A radical crosslinking agent is a compound having a radically polymerizable group. As the radically 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, and a (meth)acryloyl group.
Among these, as the group containing an ethylenically unsaturated bond, a (meth)acryloyl group is preferable, and a (meth)acryloxy group is more preferable from the viewpoint of reactivity.

The radical crosslinking agent may be any compound having one or more ethylenically unsaturated bonds, but it is more preferably a compound having two or more ethylenically unsaturated bonds.
The compound having two ethylenically unsaturated bonds is preferably a compound having two groups containing the above ethylenically unsaturated bonds.
Moreover, from the viewpoint of the film strength of the resulting pattern, the curable resin composition of the present invention preferably contains a compound having three or more ethylenically unsaturated bonds as a radical crosslinking agent. The compound having three or more ethylenically unsaturated bonds is preferably a compound having 3 to 15 ethylenically unsaturated bonds, more preferably a compound having 3 to 10 ethylenically unsaturated bonds, and more preferably a compound having 3 to 6 ethylenically unsaturated bonds. More preferred are compounds having the following.
Further, the compound having three or more ethylenically unsaturated bonds is preferably a compound having three or more groups containing the above ethylenically unsaturated bond, more preferably a compound having 3 to 15 groups, A compound having 3 to 10 is more preferable, and a compound having 3 to 6 is particularly preferable.
In addition, from the viewpoint of the film strength of the resulting pattern, the curable resin composition of the present invention contains a compound having two ethylenically unsaturated bonds and a compound having three or more ethylenically unsaturated bonds. It is also preferable.

The molecular weight of the radical crosslinking agent is preferably 2,000 or less, more preferably 1,500 or less, and even more preferably 900 or less. The lower limit of the molecular weight of the radical crosslinking agent is preferably 100 or more.

Specific examples of radical crosslinking agents include unsaturated carboxylic acids (for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.), their esters, and amides. These are esters of saturated carboxylic acids and polyhydric alcohol compounds, and amides of unsaturated carboxylic acids and polyhydric amine compounds. In addition, addition reaction products of unsaturated carboxylic acid esters or amides having nucleophilic substituents such as hydroxy groups, amino groups, and sulfanyl groups with monofunctional or polyfunctional isocyanates or epoxies, and monofunctional or polyfunctional A dehydration condensation reaction product with a functional carboxylic acid is also preferably used. In addition, addition reaction products of unsaturated carboxylic acid esters or amides having electrophilic substituents such as isocyanate groups and epoxy groups with monofunctional or polyfunctional alcohols, amines, and thiols, and furthermore, halogen groups Substitution reaction products of unsaturated carboxylic acid esters or amides having a leaving substituent such as or tosyloxy group and monofunctional or polyfunctional alcohols, amines, and thiols are also suitable. Further, as another example, it is also possible to use a group of compounds in which the unsaturated carboxylic acid mentioned above is replaced with an unsaturated phosphonic acid, a vinylbenzene derivative such as styrene, vinyl ether, allyl ether, or the like. As a specific example, the descriptions in paragraphs 0113 to 0122 of JP-A No. 2016-027357 can be referred to, and the contents thereof are incorporated into the present specification.

Further, the radical crosslinking agent is preferably a compound having a boiling point of 100° C. or higher under normal pressure. Examples include polyethylene glycol di(meth)acrylate, trimethylolethane tri(meth)acrylate, neopentyl glycol di(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol Penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, hexanediol(meth)acrylate, trimethylolpropane tri(acryloyloxypropyl)ether, tri(acryloyloxyethyl)isocyanurate, glycerin, trimethylolethane, etc. A compound obtained by adding ethylene oxide or propylene oxide to a functional alcohol and then converting it into (meth)acrylate, which is described in Japanese Patent Publication No. 48-041708, Japanese Patent Publication No. 50-006034, and Japanese Patent Publication No. 51-037193. Urethane (meth)acrylates, polyester acrylates, epoxy resins and (meth)acrylics described in JP-A-48-064183, JP-B-49-043191, and JP-B-52-030490. Examples include polyfunctional acrylates and methacrylates such as epoxy acrylates, which are reaction products with acids, and mixtures thereof. Also suitable are the compounds described in paragraphs 0254 to 0257 of JP-A-2008-292970. Also included are polyfunctional (meth)acrylates obtained by reacting a polyfunctional carboxylic acid with a compound having a cyclic ether group and an ethylenically unsaturated bond, such as glycidyl (meth)acrylate.

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

Furthermore, other examples include specific unsaturated compounds described in Japanese Patent Publication No. 46-043946, Japanese Patent Publication No. 01-040337, and Japanese Patent Publication No. 01-040336, and those described in Japanese Patent Publication No. 02-025493. Vinylphosphonic acid compounds and the like can also be mentioned. Further, compounds containing perfluoroalkyl groups described in JP-A-61-022048 can also be used. Furthermore, Japan Adhesive Association Journal vol. 20, No. 7, pp. 300-308 (1984) as photopolymerizable monomers and oligomers can also be used.

In addition to the above, compounds described in paragraphs 0048 to 0051 of JP2015-034964A and compounds described in paragraphs 0087 to 0131 of International Publication No. 2015/199219 can also be preferably used, and the contents of these are herein incorporated by reference. incorporated into the book.

In addition, compounds obtained by adding ethylene oxide or propylene oxide to a polyfunctional alcohol and then converting it into (meth)acrylate, which are described in JP-A No. 10-062986 as formulas (1) and (2) together with specific examples thereof, can also be used. It can be used as a radical crosslinking agent.

Furthermore, the compounds described in paragraphs 0104 to 0131 of JP-A No. 2015-187211 can also be used as a radical crosslinking agent, and the contents thereof are incorporated herein.

Examples of radical crosslinking agents include dipentaerythritol triacrylate (commercially available product: KAYARAD D-330; manufactured by Nippon Kayaku Co., Ltd.) and dipentaerythritol tetraacrylate (commercially available product: KAYARAD D-320; manufactured by Nippon Kayaku Co., Ltd.). ), A-TMMT: manufactured by Shin Nakamura Chemical Co., Ltd.), dipentaerythritol penta(meth)acrylate (commercially available product is KAYARAD D-310; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol hexa(meth) ) acrylate (commercially available products are KAYARAD DPHA; manufactured by Nippon Kayaku Co., Ltd.; A-DPH; manufactured by Shin-Nakamura Chemical Industry Co., Ltd.), and their (meth)acryloyl groups via ethylene glycol residues or propylene glycol residues. A structure in which both are bonded together is preferred. These oligomeric types can also be used.

Commercially available radical crosslinking agents include, for example, SR-494, a tetrafunctional acrylate having four ethyleneoxy chains, manufactured by Sartomer; SR-209, manufactured by Sartomer, a difunctional methacrylate having four ethyleneoxy chains; 231, 239, DPCA-60, a hexafunctional acrylate with 6 pentyleneoxy chains manufactured by Nippon Kayaku Co., Ltd., TPA-330, a trifunctional acrylate with 3 isobutyleneoxy chains, urethane oligomer UAS-10 , UAB-140 (manufactured by Nippon Paper Industries), NK Ester M-40G, NK Ester 4G, NK Ester M-9300, NK Ester A-9300, UA-7200 (manufactured by Shin-Nakamura Chemical Industry Co., Ltd.), DPHA-40H (Japan Kayaku Co., Ltd.), UA-306H, UA-306T, UA-306I, AH-600, T-600, AI-600 (Kyoeisha Chemical Co., Ltd.), Blenmar PME400 (NOF Corporation), etc. Can be mentioned.

As the radical crosslinking agent, urethane acrylates as described in Japanese Patent Publication No. 48-041708, Japanese Patent Application Publication No. 51-037193, Japanese Patent Publication No. 02-032293, and Japanese Patent Publication No. 02-016765, Urethane compounds having an ethylene oxide skeleton described in Japanese Patent Publication No. 58-049860, Japanese Patent Publication No. 56-017654, Japanese Patent Publication No. 62-039417, and Japanese Patent Publication No. 62-039418 are also suitable. Furthermore, as a radical crosslinking agent, compounds having an amino structure or a sulfide structure in the molecule, which are described in JP-A-63-277653, JP-A-63-260909, and JP-A-01-105238, are used. You can also do that.

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 the unreacted hydroxy group of the aliphatic polyhydroxy compound is reacted with a non-aromatic carboxylic acid anhydride to form an acid group. A radical crosslinking agent having the following is more preferable. Particularly preferably, in the radical crosslinking agent in which an unreacted hydroxy group of an aliphatic polyhydroxy compound is reacted with a non-aromatic carboxylic acid anhydride to have an acid group, the aliphatic polyhydroxy compound is pentaerythritol or dipentaerythritol. It is a compound that is Commercially available products include, for example, polybasic acid-modified acrylic oligomers manufactured by Toagosei Co., Ltd., such as M-510 and M-520.

The preferred acid value of the radical crosslinking agent having an acid group is 0.1 to 40 mgKOH/g, particularly preferably 5 to 30 mgKOH/g. If the acid value of the radical crosslinking agent is within the above range, it will be excellent in handling during production and furthermore, it will be excellent in developability. Moreover, it has good polymerizability. On the other hand, from the viewpoint of development speed in alkali development, 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. The above acid value is measured according to the description in JIS K 0070:1992.

The curable resin composition of the present invention preferably uses bifunctional methacrylate or acrylate from the viewpoint of pattern resolution and film stretchability. Specific compounds include triethylene glycol diacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, tetraethylene glycol diacrylate, PEG200 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, dimethylol-tricyclodecane diacrylate, dimethylol-tricyclodecane dimethacrylate, EO adduct diacrylate of bisphenol A, EO adduct dimethacrylate of bisphenol A, PO adduct diacrylate of bisphenol A, PO adduct of bisphenol A Adduct dimethacrylate, 2-hydroxy-3-acryloyloxypropyl methacrylate, isocyanuric acid EO-modified diacrylate, isocyanuric acid-modified dimethacrylate, other bifunctional acrylates having a urethane bond, and bifunctional methacrylates having a urethane bond can be used. can. These can be used as a mixture of two or more types, if necessary. Note that, for example, PEG200 diacrylate refers to polyethylene glycol diacrylate in which the formula weight of polyethylene glycol chains is about 200.
Furthermore, from the viewpoint of suppressing warpage due to control of the elastic modulus of the pattern, a monofunctional radical crosslinking agent can be preferably used as the radical crosslinking agent. Examples of monofunctional radical crosslinking agents include n-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, butoxyethyl (meth)acrylate, carbitol (meth)acrylate, and cyclohexyl (meth)acrylate. ) acrylate, benzyl (meth)acrylate, phenoxyethyl (meth)acrylate, N-methylol (meth)acrylamide, glycidyl (meth)acrylate, polyethylene glycol mono(meth)acrylate, polypropylene glycol mono(meth)acrylate, etc. Preferably used are acrylic acid derivatives, N-vinyl compounds such as N-vinylpyrrolidone and N-vinylcaprolactam, and allyl compounds such as allyl glycidyl ether, diallyl phthalate and triallyl trimellitate. As the monofunctional radical crosslinking agent, a compound having a boiling point of 100° C. or higher at normal pressure is also preferred in order to suppress volatilization before exposure.

When containing a radical crosslinking agent, its content is preferably more than 0% by mass and 60% by mass or less based on the total solid content of the curable resin composition of the present invention. The lower limit is more preferably 5% by mass or more. The upper limit is more preferably 50% by mass or less, and even more preferably 30% by mass or less.

One type of radical crosslinking agent may be used alone, or two or more types may be used in combination. When two or more types are used together, it is preferable that the total amount falls within the above range.

<Other crosslinking agents>
The curable resin composition of the present invention preferably contains another crosslinking agent different from the above-mentioned radical crosslinking agent.
In the present invention, other crosslinking agents refer to crosslinking agents other than the above-mentioned radical crosslinking agents, which form covalent bonds with other compounds in the composition or their reaction products through the sensitization of the above-mentioned photosensitizers. It is preferable that the compound has a plurality of groups in its molecule that promote the formation reaction, and the reaction that forms a covalent bond with other compounds in the composition or the reaction product thereof is facilitated by the action of an acid or base. Compounds having a plurality of groups promoted by in the molecule are preferred.
The acid or base is preferably an acid or base generated from a photoacid generator or a photobase generator, which is a photosensitizer, in the exposure step.
The other crosslinking agent is preferably a compound having at least one group selected from the group consisting of a methylol group and an alkoxymethyl group; A compound having a structure directly bonded to a nitrogen atom is more preferred.
Other crosslinking agents include, for example, reacting an amino group-containing compound such as melamine, glycoluril, urea, alkylene urea, or benzoguanamine with formaldehyde or formaldehyde and alcohol to convert the hydrogen atom of the amino group into a methylol group or an alkoxymethyl group. Examples include compounds having a substituted structure. The method for producing these compounds is not particularly limited, and any compound having the same structure as the compound produced by the above method may be used. Moreover, an oligomer formed by self-condensation of the methylol groups of these compounds may also be used.
As the above amino group-containing compound, a crosslinking agent using melamine is a melamine crosslinking agent, a crosslinking agent using glycoluril, urea or alkylene urea is a urea crosslinking agent, and a crosslinking agent using alkylene urea is an alkylene urea crosslinking agent. A crosslinking agent using benzoguanamine is called a benzoguanamine-based crosslinking agent.
Among these, the curable 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 a glycoluril-based crosslinking agent and melamine, which will be described later. It is more preferable to include at least one compound selected from the group consisting of crosslinking agents.

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

Specific examples of urea-based crosslinking agents include monohydroxymethylated glycoluril, dihydroxymethylated glycoluril, trihydroxymethylated glycoluril, tetrahydroxymethylated glycoluril, monomethoxymethylated glycoluril, and dimethoxymethylated glycoluril. , trimethoxymethylated glycoluril, tetramethoxymethylated glycoluril, monomethoxymethylated glycoluril, dimethoxymethylated glycoluril, trimethoxymethylated glycoluril, tetraethoxymethylated glycoluril, monopropoxymethylated glycoluril, Propoxymethylated glycoluril, triproxymethylated glycoluril, tetrapropoxymethylated glycoluril, monobutoxymethylated glycoluril, dibutoxymethylated glycoluril, tributoxymethylated glycoluril, or tetrabutoxymethylated glycoluril, etc. glycoluril crosslinking agent;
Urea-based crosslinking agents such as bismethoxymethylurea, bisethoxymethylurea, bispropoxymethylurea, bisbutoxymethylurea,
Monohydroxymethylated ethyleneurea or dihydroxymethylated ethyleneurea, monomethoxymethylated ethyleneurea, dimethoxymethylated ethyleneurea, monoethoxymethylated ethyleneurea, diethoxymethylated ethyleneurea, monopropoxymethylated ethyleneurea, dipropoxymethyl ethylene urea-based crosslinking agents such as ethylene urea, monobutoxymethyl ethylene urea, or dibutoxy methyl ethylene urea,
Monohydroxymethylated propylene urea, dihydroxymethylated propylene urea, monomethoxymethylated propylene urea, dimethoxymethylated propylene urea, monodiethoxymethylated propylene urea, diethoxymethylated propylene urea, monopropoxymethylated propylene urea, dipropoxy Propylene urea-based crosslinking agents such as methylated propylene urea, monobutoxymethylated propylene urea, or dibutoxymethylated propylene urea,
Examples include 1,3-di(methoxymethyl)4,5-dihydroxy-2-imidazolidinone and 1,3-di(methoxymethyl)-4,5-dimethoxy-2-imidazolidinone.

Specific examples of benzoguanamine-based crosslinking agents include monohydroxymethylated benzoguanamine, dihydroxymethylated benzoguanamine, trihydroxymethylated benzoguanamine, tetrahydroxymethylated benzoguanamine, monomethoxymethylated benzoguanamine, dimethoxymethylated benzoguanamine, and trimethoxymethylated benzoguanamine. , tetramethoxymethylated benzoguanamine, monomethoxymethylated benzoguanamine, dimethoxymethylated benzoguanamine, trimethoxymethylated benzoguanamine, tetraethoxymethylated benzoguanamine, monopropoxymethylated benzoguanamine, dipropoxymethylated benzoguanamine, tripropoxymethylated benzoguanamine, tetrapropoxy Examples include methylated benzoguanamine, monobutoxymethylated benzoguanamine, dibutoxymethylated benzoguanamine, tributoxymethylated benzoguanamine, and tetrabutoxymethylated benzoguanamine.

In addition, as a compound having at least one group selected from the group consisting of a methylol group and an alkoxymethyl group, at least one group selected from the group consisting of a methylol group and an alkoxymethyl group is added to an aromatic ring (preferably a benzene ring). Compounds to which species groups are directly bonded are also preferably used.
Specific examples of such compounds include benzenedimethanol, bis(hydroxymethyl)cresol, bis(hydroxymethyl)dimethoxybenzene, bis(hydroxymethyl)diphenyl ether, bis(hydroxymethyl)benzophenone, hydroxymethylphenyl hydroxymethylbenzoate. , bis(hydroxymethyl)biphenyl, dimethylbis(hydroxymethyl)biphenyl, bis(methoxymethyl)benzene, bis(methoxymethyl)cresol, bis(methoxymethyl)dimethoxybenzene, bis(methoxymethyl)diphenyl ether, bis(methoxymethyl) Benzophenone, methoxymethylphenyl methoxymethylbenzoate, bis(methoxymethyl)biphenyl, dimethylbis(methoxymethyl)biphenyl, 4,4',4''-ethylidene tris[2,6-bis(methoxymethyl)phenol], 5 , 5'-[2,2,2-trifluoro-1-(trifluoromethyl)ethylidene]bis[2-hydroxy-1,3-benzenedimethanol], 3,3',5,5'-tetrakis( (methoxymethyl)-1,1'-biphenyl-4,4'-diol and the like.

Commercial products may be used as other crosslinking agents, and suitable commercial products include 46DMOC, 46DMOEP (manufactured by Asahi Yokuzai Kogyo Co., Ltd.), DML-PC, DML-PEP, DML-OC, and 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 (the above, Honshu (manufactured by Kagaku Kogyo Co., Ltd.), Nikalak (registered trademark, hereinafter the same) MX-290, Nikalak MX-280, Nikalak MX-270, Nikalak MX-279, Nikalak MW-100LM, Nikalak MX-750LM (all manufactured by Sanwa Chemical Co., Ltd.) ), etc.

Further, the curable resin composition of the present invention preferably contains at least one compound selected from the group consisting of an epoxy compound, an oxetane compound, and a benzoxazine compound as another crosslinking agent.

[Epoxy compound (compound with epoxy group)]
The epoxy compound is preferably a compound having two or more epoxy groups in one molecule. Epoxy groups undergo a crosslinking reaction at temperatures below 200° C., and no dehydration reaction due to crosslinking occurs, so membrane shrinkage is less likely to occur. Therefore, containing an epoxy compound is effective for low-temperature curing of the curable resin composition and for suppressing warping.

Preferably, the epoxy compound contains a polyethylene oxide group. This further reduces the elastic modulus and suppresses warping. The polyethylene oxide group means one in which the number of ethylene oxide repeating units is 2 or more, and the number of repeating units is preferably 2 to 15.

Examples of epoxy compounds include bisphenol A type epoxy resin; bisphenol F type epoxy resin; propylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, ethylene glycol diglycidyl ether, butylene glycol diglycidyl ether, and hexamethylene glycol diglycidyl ether. , alkylene glycol type epoxy resin or polyhydric alcohol hydrocarbon type epoxy resin such as trimethylolpropane triglycidyl ether; polyalkylene glycol type epoxy resin such as polypropylene glycol diglycidyl ether; epoxy group such as polymethyl (glycidyloxypropyl) siloxane Examples include, but are not limited to, silicone containing silicone. Specifically, Epiclon (registered trademark) 850-S, Epiclon (registered trademark) HP-4032, Epiclon (registered trademark) HP-7200, Epiclon (registered trademark) HP-820, Epiclon (registered trademark) HP-4700, Epiclon (registered trademark) EXA-4710, Epiclon (registered trademark) HP-4770, Epiclon (registered trademark) EXA-859CRP, Epiclon (registered trademark) EXA-1514, Epiclon (registered trademark) EXA-4880, Epiclon (registered trademark) EXA-4850-150, Epiclon EXA-4850-1000, Epiclon (registered trademark) EXA-4816, Epiclon (registered trademark) EXA-4822, Epiclon (registered trademark) EXA-830LVP, Epiclon (registered trademark) EXA-8183, Epiclon (registered trademark) EXA-8169, Epiclon (registered trademark) N-660, Epiclon (registered trademark) N-665-EXP-S, Epiclon (registered trademark) N-740, Recare Resin (registered trademark) BEO-20E (or more products) name, manufactured by DIC Corporation), RICARE RESIN (registered trademark) BEO-60E, RICARE RESIN (registered trademark) HBE-100, RICARE RESIN (registered trademark) DME-100, RICARE RESIN (registered trademark) L-200 (product name, New Japan Rika Co., Ltd.), EP-4003S, EP-4000S, EP-4088S, EP-3950S (all product names, manufactured by ADEKA Co., Ltd.), Celoxide 2021P, 2081, 2000, 3000, EHPE3150, Epolead GT400, Cerbinase B0134, B0177 (all product names, manufactured by Daicel Corporation), NC-3000, NC-3000-L, NC-3000-H, NC-3000-FH-75M, NC-3100, CER-3000-L, NC-2000 -L, , BREN-S, BREN-10S (all trade names, manufactured by Nippon Kayaku Co., Ltd.).

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

[Benzoxazine compound (compound having a benzoxazolyl group)]
A benzoxazine compound is preferable because it does not generate outgassing during curing due to a crosslinking reaction derived from a ring-opening addition reaction, and furthermore, it reduces thermal shrinkage and suppresses the occurrence of warpage.

Preferred examples of benzoxazine compounds include Ba-type benzoxazine, B-m-type benzoxazine, Pd-type benzoxazine, Fa-type benzoxazine (all trade names, manufactured by Shikoku Kasei Kogyo Co., Ltd.), and Polymer. Examples include benzoxazine adducts of hydroxystyrene resins and phenol novolac type dihydrobenzoxazine compounds. These may be used alone or in combination of two or more.

The content of other crosslinking agents is preferably 0.1 to 30% by mass, more preferably 0.1 to 20% by mass, based on the total solid content of the curable resin composition of the present invention. It is more preferably 0.5 to 15% by weight, and particularly preferably 1.0 to 10% by weight. Only one type of other crosslinking agent may be contained, or two or more types thereof may be contained. When two or more types of other crosslinking agents are contained, it is preferable that the total amount is within the above range.

<Compounds with sulfonamide structure, compounds with thiourea structure>
From the viewpoint of improving the adhesion of the resulting pattern to the substrate, the curable resin composition of the present invention contains at least one compound selected from the group consisting of compounds having a sulfonamide structure and compounds having a thiourea structure. Preferably, it further contains a compound.

[Compound with sulfonamide structure]
The sulfonamide structure is a structure represented by the following formula (S-1).

In formula (S-1), R represents a hydrogen atom or an organic group, R may be combined with another structure to form a ring structure, and * each independently represents a bonding site with another structure. represent.
The above R is preferably the same group as R ² in the following formula (S-2).
The compound having a sulfonamide structure may be a compound having two or more sulfonamide structures, but is preferably a compound having one sulfonamide structure.

The compound having a sulfonamide structure is preferably a compound represented by the following formula (S-2).

In formula (S-2), R ¹ , R ² and R ³ each independently represent a hydrogen atom or a monovalent organic group, and two or more of R ¹ , R ² and R ³ are bonded to each other. It may form a ring structure.
It is preferable that R ¹ , R ² and R ³ are each independently a monovalent organic group.
Examples of R ¹ , R ² and R ³ include a hydrogen atom, 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 carboxy group, Examples include a carbonyl group, an allyl group, a vinyl group, a heterocyclic group, and a combination of two or more thereof.
The alkyl group mentioned above is preferably an alkyl group having 1 to 10 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms. Examples of the alkyl group include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, isopropyl group, and 2-ethylhexyl group.
The above-mentioned cycloalkyl group is preferably a cycloalkyl group having 5 to 10 carbon atoms, more preferably a cycloalkyl group having 6 to 10 carbon atoms. Examples of the cycloalkyl group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, and a cyclohexyl group.
The alkoxy group is preferably an alkoxy group having 1 to 10 carbon atoms, more preferably an alkoxy group having 1 to 5 carbon atoms. Examples of the alkoxy group include methoxy group, ethoxy group, propoxy group, butoxy group, and pentoxy group.
The alkoxysilyl group is preferably an alkoxysilyl group having 1 to 10 carbon atoms, more preferably an alkoxysilyl group having 1 to 4 carbon atoms. Examples of the alkoxysilyl group include a methoxysilyl group, an ethoxysilyl group, a propoxysilyl group, and a butoxysilyl group.
The above aryl group is preferably an aryl group having 6 to 20 carbon atoms, more preferably an aryl group having 6 to 12 carbon atoms. The above aryl group may have a substituent such as an alkyl group. Examples of the aryl group include a phenyl group, tolyl group, xylyl group, and naphthyl group.
The above heterocyclic groups include triazole ring, pyrrole ring, furan ring, thiophene ring, imidazole ring, oxazole ring, thiazole ring, pyrazole ring, isoxazole ring, isothiazole ring, tetrazole ring, pyridine ring, pyridazine ring, and pyrimididine ring. , pyrazine ring, piperidine ring, piperidine, piperazine ring, morpholine ring, dihydropyran ring, tetrahydropyran group, triazine ring, and other groups in which one hydrogen atom is removed from a heterocyclic structure.

Among these, compounds in which R ¹ is an aryl group, and R ² and R ³ are each independently a hydrogen atom or an alkyl group are preferred.

Examples of compounds having a sulfonamide structure include benzenesulfonamide, dimethylbenzenesulfonamide, N-butylbenzenesulfonamide, sulfanilamide, o-toluenesulfonamide, p-toluenesulfonamide, hydroxynaphthalenesulfonamide, naphthalene-1 -Sulfonamide, naphthalene-2-sulfonamide, m-nitrobenzenesulfonamide, p-chlorobenzenesulfonamide, methanesulfonamide, N,N-dimethylmethanesulfonamide, N,N-dimethylethanesulfonamide, N,N-diethyl Examples include methanesulfonamide, N-methoxymethanesulfonamide, N-dodecylmethanesulfonamide, N-cyclohexyl-1-butanesulfonamide, and 2-aminoethanesulfonamide.

[Compound with thiourea structure]
The thiourea structure is a structure represented by the following formula (T-1).

In formula (T-1), R ⁴ and R ⁵ each independently represent a hydrogen atom or a monovalent organic group, R ⁴ and R ⁵ may be combined to form a ring structure, and R ⁴ is * may be bonded to another structure to which R 5 is bonded to form a ring structure; R ⁵ may be bonded to another structure to which * is bonded to form a ring structure; represents the binding site with the structure of

It is preferable that R ⁴ and R ⁵ are each independently a hydrogen atom.
Examples of R ⁴ and R ⁵ include a hydrogen atom, 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 carboxy group, a carbonyl group, Examples include an allyl group, a vinyl group, a heterocyclic group, and a combination of two or more of these groups.
The alkyl group mentioned above is preferably an alkyl group having 1 to 10 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms. Examples of the alkyl group include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, isopropyl group, and 2-ethylhexyl group.
The above-mentioned cycloalkyl group is preferably a cycloalkyl group having 5 to 10 carbon atoms, more preferably a cycloalkyl group having 6 to 10 carbon atoms. Examples of the cycloalkyl group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, and a cyclohexyl group.
The alkoxy group is preferably an alkoxy group having 1 to 10 carbon atoms, more preferably an alkoxy group having 1 to 5 carbon atoms. Examples of the alkoxy group include methoxy group, ethoxy group, propoxy group, butoxy group, and pentoxy group.
The alkoxysilyl group is preferably an alkoxysilyl group having 1 to 10 carbon atoms, more preferably an alkoxysilyl group having 1 to 4 carbon atoms. Examples of the alkoxysilyl group include a methoxysilyl group, an ethoxysilyl group, a propoxysilyl group, and a butoxysilyl group.
The above aryl group is preferably an aryl group having 6 to 20 carbon atoms, more preferably 6 to 12 carbon atoms. The above aryl group may have a substituent such as an alkyl group. Examples of the aryl group include a phenyl group, tolyl group, xylyl group, and naphthyl group.
The above heterocyclic groups include triazole ring, pyrrole ring, furan ring, thiophene ring, imidazole ring, oxazole ring, thiazole ring, pyrazole ring, isoxazole ring, isothiazole ring, tetrazole ring, pyridine ring, pyridazine ring, and pyrimididine ring. , pyrazine ring, piperidine ring, piperidine, piperazine ring, morpholine ring, dihydropyran ring, tetrahydropyran group, triazine ring, and other groups in which one hydrogen atom is removed from a heterocyclic structure.
The compound having a thiourea structure may be a compound having two or more thiourea structures, but is preferably a compound having one thiourea structure.

The compound having a thiourea structure is preferably a compound represented by the following formula (T-2).

In formula (T-2), R ⁴ to R ⁷ each independently represent a hydrogen atom or a monovalent organic group, and at least two of R ⁴ to R ⁷ are bonded to each other to form a ring structure. You can.

In formula (T-2), R ⁴ and R ⁵ have the same meanings as R ⁴ and R ⁵ in formula (T-1), and preferred embodiments are also the same.
In formula (T-2), R ⁶ and R ⁷ are preferably each independently a monovalent organic group.
In formula (T-2), the preferred embodiments of the monovalent organic group in R ⁶ and R ⁷ are the same as the preferred embodiments of the monovalent organic group in R ⁴ and R ⁵ in formula (T-1). .

Examples of compounds having a thiourea structure include N-acetylthiourea, N-allylthiourea, N-allyl-N'-(2-hydroxyethyl)thiourea, 1-adamantylthiourea, N-benzoylthiourea, N,N'- Diphenylthiourea, 1-benzyl-phenylthiourea, 1,3-dibutylthiourea, 1,3-diisopropylthiourea, 1,3-dicyclohexylthiourea, 1-(3-(trimethoxysilyl)propyl)-3-methylthiourea, trimethyl Examples include thiourea, tetramethylthiourea, N,N-diphenylthiourea, ethylenethiourea (2-imidazolinthione), carbimazole, and 1,3-dimethyl-2-thiohydantoin.

〔Content〕
The total content of the compound having a sulfonamide structure and the compound having a thiourea structure with respect to the total mass of the curable resin composition of the present invention is preferably 0.05 to 10% by mass, and 0.1 to 5% by mass. %, and even more preferably 0.2 to 3% by mass.
The curable resin composition of the present invention may contain only one kind of compound selected from the group consisting of a compound having a sulfonamide structure and a compound having a thiourea structure, or may contain two or more kinds. When only one type of compound is included, the content of the compound is preferably within the above range, and when two or more types are included, the total amount thereof is preferably within the above range.

<Migration inhibitor>
It is preferable that the curable resin composition of the present invention further contains a migration inhibitor. By including a migration inhibitor, it is possible to effectively suppress metal ions originating from the metal layer (metal wiring) from moving into the photoresist film.

Migration inhibitors are not particularly limited, but include heterocycles (pyrrole ring, furan ring, thiophene ring, imidazole ring, triazole ring, oxazole ring, thiazole ring, pyrazole ring, isoxazole ring, isothiazole ring, tetrazole ring, pyridine ring, pyridazine ring, pyrimidine ring, pyrazine ring, piperidine ring, piperazine ring, morpholine ring, 2H-pyran ring and 6H-pyran ring, triazine ring), thioureas and sulfanyl group-containing compounds, hindered Examples include phenolic compounds, salicylic acid derivative compounds, and hydrazide derivative compounds. In particular, triazole compounds such as 1,2,4-triazole and benzotriazole, and tetrazole compounds such as 1H-tetrazole and 5-phenyltetrazole can be preferably used.

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

Other migration inhibitors include the rust inhibitors described in paragraph 0094 of JP-A-2013-015701, the compounds described in paragraphs 0073 to 0076 of JP-A-2009-283711, and the compounds described in JP-A-2011-059656. Compounds described in paragraph 0052, compounds described in paragraphs 0114, 0116, and 0118 of JP2012-194520A, compounds described in paragraph 0166 of International Publication No. 2015/199219, etc. can be used.

Specific examples of migration inhibitors include the following compounds.

When the curable resin composition has a migration inhibitor, the content of the migration inhibitor is preferably 0.01 to 5.0% by mass, based on the total solid content of the curable resin composition, and 0. The amount is more preferably .05 to 2.0% by weight, and even more preferably 0.1 to 1.0% by weight.

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

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

Examples of the polymerization inhibitor include hydroquinone, o-methoxyphenol, methoxyhydroquinone, p-methoxyphenol, di-tert-butyl-p-cresol, pyrogallol, p-tert-butylcatechol (t-butylcatechol), 1, 4-benzoquinone, diphenyl-p-benzoquinone, 4,4'-thiobis(3-methyl-6-tert-butylphenol), 2,2'-methylenebis(4-methyl-6-tert-butylphenol), N-nitroso- N-phenylhydroxyamine aluminum salt, phenothiazine, N-nitrosodiphenylamine, N-phenylnaphthylamine, ethylenediaminetetraacetic acid, 1,2-cyclohexanediaminetetraacetic acid, glycol etherdiaminetetraacetic 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- Nitrosophenylhydroxyamine cerous salt, N-nitroso-N-(1-naphthyl)hydroxyamine ammonium salt, bis(4-hydroxy-3,5-tert-butyl)phenylmethane, 1,3,5-tris( 4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 4-hydroxy-2,2, 6,6-tetramethylpiperidine 1-oxyl free radical, phenothiazine, 1,1-diphenyl-2-picrylhydrazyl, dibutyldithiocarbanate copper(II), nitrobenzene, N-nitroso-N-phenylhydroxylamine aluminum salt , N-nitroso-N-phenylhydroxylamine ammonium salt, N,N'-diphenyl-p-phenylenediamine, 2,4-di-tert-butylphenol, di-t-butylhydroxytoluene, 1,4-naphthoquinone, etc. Suitably used. Further, the polymerization inhibitor described in paragraph 0060 of JP 2015-127817A and the compound described in paragraphs 0031 to 0046 of WO 2015/125469 can also be used.

Additionally, the following compounds can be used.

When the curable resin composition of the present invention contains a polymerization inhibitor, the content of the polymerization inhibitor is 0.01 to 20.0% by mass based on the total solid content of the curable resin composition of the present invention. The amount is preferably 0.01 to 5% by weight, more preferably 0.02 to 3% by weight, and even more preferably 0.05 to 2.5% by weight.

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

<Metal adhesion improver>

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

Examples of silane coupling agents include compounds described in paragraph 0167 of WO 2015/199219, compounds described in paragraphs 0062 to 0073 of JP2014-191002, and paragraphs of WO 2011/080992. Compounds described in paragraphs 0063 to 0071, compounds described in paragraphs 0060 to 0061 of JP 2014-191252, compounds described in paragraphs 0045 to 0052 of JP 2014-041264, and compounds described in WO 2014/097594. Examples include the compounds described in paragraph 0055. Furthermore, it is also preferable to use two or more different silane coupling agents as described in paragraphs 0050 to 0058 of JP-A-2011-128358. Moreover, it is also preferable to use the following compounds as the silane coupling agent. In the following formula, Et represents an ethyl group.

Examples of other silane coupling agents include vinyltrimethoxysilane, vinyltriethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, and 3-glycidoxypropylmethyldimethoxysilane. Xypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, p-styryltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane Silane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane, N-2 -(aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N-(1,3-dimethyl-butylidene)propylamine, N-phenyl-3-aminopropyltrimethoxysilane, tris-(trimethoxysilylpropyl)isocyanurate, 3-ureidopropyltrialkoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-isocyanatepropyl Examples include triethoxysilane and 3-trimethoxysilylpropylsuccinic anhydride. These can be used alone or in combination of two or more.

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

As the metal adhesion improver, compounds described in paragraphs 0046 to 0049 of JP2014-186186A and sulfide compounds described in paragraphs 0032 to 0043 of JP2013-072935A can also be used.

The content of the metal adhesion improver is preferably 0.1 to 30 parts by mass, more preferably 0.5 to 15 parts by mass, and even more preferably 0.5 to 15 parts by mass, based on 100 parts by mass of the specific resin. It is in the range of 5 to 5 parts by mass. By setting it above the above-mentioned lower limit, the adhesion between the pattern and the metal layer becomes good, and by setting it below the above-mentioned upper limit, the heat resistance and mechanical properties of the pattern become good. There may be only one type of metal adhesion improver, or two or more types may be used. When two or more types are used, it is preferable that the total is within the above range.

<Metal adhesion improver>
The curable resin composition of the present invention preferably contains a metal adhesion improver for improving adhesion to metal materials used for electrodes, wiring, etc. As the metal adhesion improver, compounds described in paragraphs 0046 to 0049 of JP2014-186186A and sulfide compounds described in paragraphs 0032 to 0043 of JP2013-072935A can also be used.

The content of the metal adhesion improver is preferably in the range of 0.1 to 30 parts by mass, more preferably in the range of 0.5 to 15 parts by mass, based on 100 parts by mass of the heterocyclic polymer precursor. It is preferably in the range of 0.5 to 5 parts by mass. By setting it above the above-mentioned lower limit, the adhesion between the pattern and the metal layer after the heating process will be good, and by setting it below the above-mentioned upper limit, the heat resistance and mechanical properties of the cured product after the heating process will be good. There may be only one type of metal adhesion improver, or two or more types may be used. When two or more types are used, it is preferable that the total is within the above range.

<Other additives>
The curable resin composition of the present invention may optionally contain various additives, such as sensitizers, chain transfer agents, surfactants, higher fatty acid derivatives, and inorganic particles, as long as the effects of the present invention can be obtained. , a curing agent, a curing catalyst, a filler, an antioxidant, an ultraviolet absorber, an anti-aggregation agent, etc. can be added. When blending these additives, the total blending amount is preferably 3% by mass or less based on the solid content of the curable resin composition.

[Sensitizer]
The curable resin composition of the present invention may contain a sensitizer. A sensitizer absorbs specific actinic radiation and becomes electronically excited. The sensitizer in an electronically excited state comes into contact with a thermosetting accelerator, a thermal radical polymerization initiator, a photoradical polymerization initiator, etc., and effects such as electron transfer, energy transfer, and heat generation occur. As a result, the thermal curing accelerator, thermal radical polymerization initiator, and photoradical polymerization initiator undergo chemical changes and are decomposed to generate radicals, acids, or bases.
Examples of the sensitizer include 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-dimethylaminocinnamyl Denindanone, p-dimethylaminobenzylideneindanone, 2-(p-dimethylaminophenylbiphenylene)-benzothiazole, 2-(p-dimethylaminophenylvinylene)benzothiazole, 2-(p-dimethylaminophenylvinylene)iso Naphthothiazole, 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 Coumarin, N-phenyl-N'-ethylethanolamine, N-phenyldiethanolamine, N-p-tolyldiethanolamine, N-phenylethanolamine, 4-morpholinobenzophenone, isoamyl dimethylaminobenzoate, isoamyl diethylaminobenzoate, 2-mercapto Benzimidazole, 1-phenyl-5-mercaptotetrazole, 2-mercaptobenzothiazole, 2-(p-dimethylaminostyryl)benzoxazole, 2-(p-dimethylaminostyryl)benzthiazole, 2-(p-dimethylaminostyryl) ) naphtho(1,2-d)thiazole, 2-(p-dimethylaminobenzoyl)styrene, diphenylacetamide, benzanilide, N-methylacetanilide, 3',4'-dimethylacetanilide and the like.
A sensitizing dye may be used as the sensitizer.
For details of the sensitizing dye, the descriptions in paragraphs 0161 to 0163 of JP 2016-027357A can be referred to, and the contents thereof are incorporated herein.

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

[Chain transfer agent]
The curable resin composition of the present invention may contain a chain transfer agent. Chain transfer agents are defined, for example, in the Polymer Dictionary, 3rd edition (edited by the Society of Polymer Science and Technology, 2005), pages 683-684. As the chain transfer agent, for example, a group of compounds having SH, PH, SiH, and GeH in the molecule are used. These can generate radicals by donating hydrogen to low-activity radicals, or can generate radicals by being oxidized and then deprotonated. In particular, thiol compounds can be preferably used.

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

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

[Surfactant]
A surfactant may be added to the curable resin composition of the present invention from the viewpoint of further improving coating properties. As the surfactant, various types of surfactants can be used, such as fluorine surfactants, nonionic surfactants, cationic surfactants, anionic surfactants, and silicone surfactants. The following surfactants are also preferred. In the following formula, the parentheses indicating the repeating unit of the main chain represent the content (mol %) of each repeating unit, and the parentheses indicating the repeating unit of the side chain represent the number of repeats of each repeating unit.

Further, as the surfactant, compounds described in paragraphs 0159 to 0165 of International Publication No. 2015/199219 can also be used.
As the fluorine-based surfactant, a fluorine-containing polymer having an ethylenically unsaturated group in its side chain can also be used as the fluorine-based surfactant. Specific examples include compounds described in paragraphs 0050 to 0090 and paragraphs 0289 to 0295 of JP-A No. 2010-164965, such as Megafac RS-101, RS-102, and RS-718K manufactured by DIC Corporation. Can be mentioned.

The fluorine content in the fluorosurfactant 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 uniformity of coating film thickness and liquid saving, and has good solubility in the composition.

Examples of silicone surfactants include Toray Silicone DC3PA, Toray Silicone SH7PA, Toray Silicone DC11PA, Toray Silicone SH21PA, Toray Silicone SH28PA, Toray Silicone SH29PA, Toray Silicone SH30PA, and Toray Silicone SH8400 (Toray Silicone SH29PA, Toray Silicone SH30PA, Toray Silicone SH8400) ), TSF-4440, TSF-4300, TSF-4445, TSF-4460, TSF-4452 (manufactured by Momentive Performance Materials), KP341, KF6001, KF6002 (manufactured by Shin-Etsu Silicone Co., Ltd.) ), BYK307, BYK323, BYK330 (manufactured by BYK Chemie Co., Ltd.), and the like.

Examples of the hydrocarbon surfactant include Pionin A-76, Nucalgen FS-3PG, Pionin B-709, Pionin B-811-N, Pionin D-1004, Pionin D-3104, Pionin D-3605, and Pionin D-3605. 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, Examples include Pionin P-4050-T (manufactured by Takemoto Yushi Co., Ltd.).

Examples of nonionic surfactants include glycerol, trimethylolpropane, trimethylolethane, and their ethoxylates and propoxylates (e.g., glycerol propoxylate, glycerol ethoxylate, etc.), 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, 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 (manufactured by Japan Lubrizol Co., Ltd.), NCW-101, NCW-1001, NCW-1002 (manufactured by Wako Pure Chemical Industries, Ltd.), Pionin D-6112, D-6112-W, D-6315 (manufactured by Takemoto Yushi Co., Ltd.), Olfin E1010, Surfynol 104, 400, 440 (manufactured by Nissin Chemical Industries, Ltd.) Co., Ltd.).

Specifically, the cationic surfactants include organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), (meth)acrylic acid-based (co)polymer Polyflow No. 75, No. 77, No. 90, No. 95 (manufactured by Kyoeisha Kagaku Co., Ltd.), W001 (manufactured by Yusho Co., Ltd.), and the like.

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

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

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

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

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

[Inorganic particles]
The resin composition of the present invention may also contain inorganic particles. Specifically, the inorganic particles can 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, even more preferably 0.03 to 1.0 μm, and even more preferably 0.04 to 0.5 μm. Particularly preferred.
By containing a large amount of the average particle diameter of the inorganic particles, the mechanical properties of the cured film may deteriorate. Furthermore, if the average particle diameter of the inorganic particles exceeds 2.0 μm, the resolution may decrease due to scattering of exposure light.

[Ultraviolet absorber]
The composition of the present invention may also contain a UV absorber. As the ultraviolet absorber, salicylate-based, benzophenone-based, benzotriazole-based, substituted acrylonitrile-based, and triazine-based ultraviolet absorbers can be used.
Examples of salicylate UV absorbers include phenyl salicylate, p-octylphenyl salicylate, pt-butylphenyl salicylate, and examples of benzophenone UV absorbers include 2,2'-dihydroxy-4- Methoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2,2',4,4'-tetrahydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2,4-dihydroxybenzophenone, 2- Examples include hydroxy-4-octoxybenzophenone. Furthermore, 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, 2-[2'-hydroxy-5' -(1,1,3,3-tetramethyl)phenyl]benzotriazole and the like.

Examples of substituted acrylonitrile ultraviolet absorbers include ethyl 2-cyano-3,3-diphenylacrylate, 2-ethylhexyl 2-cyano-3,3-diphenylacrylate, and the like. Furthermore, examples of triazine-based ultraviolet absorbers include 2-[4-[(2-hydroxy-3-dodecyloxypropyl)oxy]-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl) )-1,3,5-triazine, 2-[4-[(2-hydroxy-3-tridecyloxypropyl)oxy]-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl) Mono(hydroxyphenyl)triazine compounds such as -1,3,5-triazine, 2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine ;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-(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 Examples include tris(hydroxyphenyl)triazine compounds such as -(3-butoxy-2-hydroxypropyloxy)phenyl]-1,3,5-triazine.

In the present invention, the various ultraviolet absorbers described above may be used alone or in combination of two or more.
The composition of the present invention may or may not contain an ultraviolet absorber, but if it does, the content of the ultraviolet absorber is 0.001% by mass based on the total solid mass of the composition of the present invention. It is preferably 1% by mass or less, and more preferably 0.01% by mass or more and 0.1% by mass or less.

[Organotitanium compound]
The resin composition of this embodiment may contain an organic titanium compound. When the resin composition contains an organic titanium compound, a resin layer having excellent chemical resistance can be formed even when cured at a low temperature.

Examples of organic titanium compounds that can be used include those in which an organic group is bonded to a titanium atom via a covalent bond or an ionic bond.
Specific examples of organic titanium compounds are shown in I) to VII) below:
I) Titanium chelate compound: Among these, a titanium chelate compound having two or more alkoxy groups is more preferable because the storage stability of the negative photosensitive resin composition is good and a good curing pattern can be obtained. Specific examples include titanium bis(triethanolamine) diisopropoxide, titanium di(n-butoxide) bis(2,4-pentanedionate), titanium diisopropoxide bis(2,4-pentanedionate) , titanium diisopropoxide bis(tetramethylheptanedionate), titanium diisopropoxide bis(ethyl acetoacetate), 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 tetramethyl phenoxide, titanium tetra(n-nonyloxide), titanium tetra(n-propoxide), titanium tetrastearyloxide, titanium tetrakis[bis{2,2-(allyloxymethyl)] butoxide}], etc.
III) Titanocene compounds: for example, pentamethylcyclopentadienyl titanium 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) Monoalkoxytitanium compounds: For example, titanium tris(dioctyl phosphate) isopropoxide, titanium tris(dodecylbenzenesulfonate) isopropoxide, and the like.
V) Titanium oxide compound: For example, titanium oxide bis(pentanedionate), titanium oxide bis(tetramethylheptanedionate), phthalocyanine titanium oxide, etc.
VI) Titanium tetraacetylacetonate compound: For example, titanium tetraacetylacetonate.
VII) Titanate coupling agent: for example, isopropyl tridodecyl benzenesulfonyl titanate.

Among these, as the organic titanium compound, at least one compound selected from the group consisting of the above-mentioned I) titanium chelate compounds, II) tetraalkoxytitanium compounds, and III) titanocene compounds is preferred for better chemical resistance. This is preferable from the viewpoint of performance. In particular, titanium diisopropoxide bis(ethylacetoacetate), titanium tetra(n-butoxide), and bis(η5-2,4-cyclopentadien-1-yl)bis(2,6-difluoro-3-(1H -pyrrol-1-yl)phenyl)titanium is preferred.

When blending an organic titanium compound, the blending 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 cyclized resin precursor. . When the amount is 0.05 parts by mass or more, the resulting cured pattern exhibits good heat resistance and chemical resistance, while when the amount is 10 parts by mass or less, the composition has excellent storage stability.

〔Antioxidant〕
The composition of the invention may also contain an antioxidant. By containing an antioxidant as an additive, the elongation characteristics of the cured film and the adhesion to the metal material can be improved. Examples of antioxidants include phenol compounds, phosphite compounds, thioether compounds, and the like. As the phenol compound, any phenol compound known as a phenolic antioxidant can be used. Preferred phenol compounds include hindered phenol compounds. A compound having a substituent at a site adjacent to the phenolic hydroxy group (ortho position) is preferred. The above-mentioned substituents are preferably substituted or unsubstituted alkyl groups having 1 to 22 carbon atoms. Further, as the antioxidant, a compound having a phenol group and a phosphorous acid ester group in the same molecule is also preferable. Further, as the antioxidant, phosphorus-based antioxidants can also be suitably used. As a 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, ethylbis(2,4-di-tert-butyl-6-methylphenyl) phosphite, and the like. Commercially available antioxidants include, for example, Adekastab AO-20, Adekastab AO-30, Adekastab AO-40, Adekastab AO-50, Adekastab AO-50F, Adekastab AO-60, Adekastab AO-60G, Adekastab AO-80. , ADEKA STAB AO-330 (manufactured by ADEKA Co., Ltd.). Further, as the antioxidant, compounds described in paragraph numbers 0023 to 0048 of Japanese Patent No. 6268967 can also be used. The composition of the present invention may also contain a latent antioxidant, if necessary. A latent antioxidant is a compound whose moiety that functions as an antioxidant is protected with a protecting group, and is heated at 100 to 250°C or heated at 80 to 200°C in the presence of an acid/base catalyst. Examples include compounds that function as antioxidants by removing protective groups. Examples of the latent antioxidant include compounds described in WO 2014/021023, WO 2017/030005, and JP 2017-008219. Commercially available latent antioxidants include Adeka Arcles GPA-5001 (manufactured by ADEKA Co., Ltd.). Examples of preferred antioxidants include 2,2-thiobis(4-methyl-6-t-butylphenol), 2,6-di-t-butylphenol, and compounds represented by general formula (3).

In general formula (3), R ⁵ represents a hydrogen atom or an alkyl group having 2 or more carbon atoms, and R ⁶ represents an alkylene group having 2 or more 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, an O atom, and an N atom. k represents an integer from 1 to 4.

The compound represented by general formula (3) suppresses oxidative deterioration of aliphatic groups and phenolic hydroxyl groups of the resin. Moreover, metal oxidation can be suppressed by the rust-preventing effect on metal materials.

Since k can act on resin and metal materials simultaneously, it is more preferable that k is an integer of 2 to 4. R7 is 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, - Examples include O-, -NH-, -NHNH-, and combinations thereof, and may further have a substituent. Among these, it is preferable to have an alkyl ether or -NH- from the viewpoint of solubility in a developer and metal adhesion, and -NH- is preferable from the viewpoint of metal adhesion due to interaction with the resin and metal complex formation. preferable.

Examples of the compound represented by the following general formula (3) include, but are not limited to, the following structures.

The amount of antioxidant added is preferably 0.1 to 10 parts by weight, more preferably 0.5 to 5 parts by weight, based on the resin. If the amount added is less than 0.1 part by mass, it is difficult to obtain the effect of improving the elongation properties after reliability and the adhesion to metal materials, and if it is more than 10 parts by mass, it may be due to interaction with the photosensitizer. , there is a possibility that the sensitivity of the resin composition may be lowered. Only one type of antioxidant may be used, or two or more types may be used. When two or more types are used, it is preferable that their total amount falls within the above range.

<Restrictions on other contained substances>
The water content of the curable resin composition of the present invention is preferably less than 5% by mass, more preferably less than 1% by mass, and even more preferably less than 0.6% by mass from the viewpoint of coated surface properties. Examples of methods for maintaining the moisture content include adjusting the humidity in storage conditions and reducing the porosity of the storage container.

From the viewpoint of insulation, the metal content of the curable resin composition of the present invention is preferably less than 5 mass ppm (parts per million), more preferably less than 1 mass ppm, and even more preferably less than 0.5 mass ppm. Examples of metals include sodium, potassium, magnesium, calcium, iron, chromium, and nickel. When a plurality of metals are included, the total of these metals is preferably within the above range.

Furthermore, methods for reducing metal impurities unintentionally contained in the curable resin composition of the present invention include selecting raw materials with a low metal content as raw materials constituting the curable resin composition of the present invention. Methods include filtering the raw materials constituting the curable resin composition of the invention, lining the inside of the apparatus with polytetrafluoroethylene, etc., and performing distillation under conditions that suppress contamination as much as possible. be able to.

Considering the use as a semiconductor material, the curable resin composition of the present invention has a halogen atom content of preferably less than 500 mass ppm, more preferably less than 300 mass ppm, and more preferably less than 200 mass ppm, from the viewpoint of wiring corrosion resistance. More preferably less than ppm. Among these, those present in the form of halogen ions are preferably less than 5 ppm by mass, more preferably less than 1 ppm by mass, and even more preferably less than 0.5 ppm by mass. Examples of the halogen atom include a chlorine atom and a bromine atom. It is preferable that the total of chlorine atoms and bromine atoms, or the total of chlorine ions and bromine ions, is each within the above range.
Preferred methods for adjusting the content of halogen atoms include ion exchange treatment.

As a container for storing the curable resin composition of the present invention, a conventionally known container can be used. In addition, in order to suppress the contamination of impurities into raw materials and curable resin compositions, storage containers include multilayer bottles whose inner walls are made of 6 types of 6 layers of resin, and 6 types of resins and 7 layers of resin. It is also preferred to use bottles with a layered structure. Examples of such a container include the container described in JP-A No. 2015-123351.

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

<Preparation of curable resin composition>
The curable resin composition of the present invention can be prepared by mixing the above components. The mixing method is not particularly limited and can be performed by a conventionally known method.

Further, in order to remove foreign substances such as dust and fine particles from the curable resin composition, it is preferable to perform filtration using a filter. The filter pore diameter is preferably 1 μm or less, more preferably 0.5 μm or less, and even more preferably 0.1 μm or less. On the other hand, from the viewpoint of productivity, the thickness is preferably 5 μm or less, more preferably 3 μm or less, and even more preferably 1 μm or less. The material of the filter is preferably polytetrafluoroethylene, polyethylene or nylon. The filter may be washed in advance with an organic solvent. In the filter filtration step, a plurality of types of filters may be connected in series or in parallel. When using multiple types of filters, filters with different pore sizes or materials may be used in combination. Additionally, various materials may be filtered multiple times. When filtration is performed multiple times, circulation filtration may be used. Alternatively, filtration may be performed under pressure. When filtration is performed under pressure, the pressure to be applied is preferably 0.05 MPa or more and 0.3 MPa or less. On the other hand, from the viewpoint of productivity, it is preferably 0.01 MPa or more and 1.0 MPa or less, more preferably 0.03 MPa or more and 0.9 MPa or less, and even more preferably 0.05 MPa or more and 0.7 MPa or less.
In addition to filtration using a filter, 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 include inorganic adsorbents such as silica gel and zeolite, and organic adsorbents such as activated carbon.

(Cured film, laminate, semiconductor device, and manufacturing method thereof)
Next, a cured film, a laminate, a semiconductor device, and a manufacturing method thereof will be explained.

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

The cured film of the present invention may be laminated in two or more layers, and more preferably in 3 to 7 layers to form a laminate. The laminate of the present invention preferably includes two or more cured films and includes a metal layer between any of the cured films. For example, a laminate including at least a layered structure in which three layers, a first cured film, a metal layer, and a second cured film are laminated in this order, is preferred. The first cured film and the second cured film are both cured films of the present invention. For example, both of the first cured film and the second cured film are composed of the resin composition of the present invention. Preferred embodiments include a film formed by curing a material. The resin composition of the present invention used to form the first cured film and the resin composition of the present invention used to form the second cured film may have the same composition. However, compositions having different compositions may be used. The metal layer in the laminate of the present invention is preferably used as metal wiring such as a rewiring layer.

Fields to which the cured film of the present invention can be applied include insulating films for semiconductor devices, interlayer insulating films for rewiring layers, stress buffer films, and the like. Other methods include forming a pattern by etching a sealing film, a substrate material (a base film or coverlay of a flexible printed circuit board, an interlayer insulating film), or an insulating film for mounting purposes as described above. For information on these uses, see, for example, Science & Technology Co., Ltd., "Advanced Functionality and Applied Technology of Polyimide," April 2008, Masaaki Kakimoto/Supervised, CMC Technical Library, "Basics and Development of Polyimide Materials," November 2011. You can refer to "Latest Polyimide Fundamentals and Applications" published by Japan Polyimide and Aromatic Polymer Research Group/editor, NTS, August 2010, etc.

The cured films according to the invention can also be used in the production of printing plates such as offset printing plates or screen printing plates, in the etching of molded parts, in the production of protective lacquers and dielectric layers in electronics, in particular microelectronics, etc.

The method for producing a cured film of the present invention (hereinafter also simply referred to as "the production method of the present invention") includes a film forming step of applying the resin composition of the present invention to a base material to form a film (resin film). It is preferable to include.
The method for producing a cured film of the present invention preferably includes the film forming step, an exposure step of exposing the film, and a development step of developing the film. A pattern of the cured film is obtained by the above exposure step and development step.
Further, the method for producing a cured film of the present invention preferably includes the film forming step and, if necessary, the developing step, and further preferably includes a heating step of heating the film at 50 to 450°C.
Specifically, it is also preferable to include the following steps (a) to (d).
(a) A film forming step in which a resin composition is applied to a substrate to form a film (resin composition layer) (b) An exposure step in which the film is exposed to light after the film forming step (c) The exposed film is Developing step (d) Heating step of heating the developed film at 50 to 450° C. By heating in the heating step, the resin layer hardened by exposure can be further hardened. In this heating step, for example, the above-mentioned thermal base generator is decomposed and sufficient curability is obtained.

A method for producing a laminate according to a preferred embodiment of the present invention includes a method for producing a cured film of the present invention. The method for producing a laminate of this embodiment includes forming a cured film according to the method for producing a cured film described above, and then repeating step (a), or steps (a) to (c), or (a). ) to (d) are performed. In particular, it is preferable to perform each of the above steps in sequence multiple times, for example, 2 to 5 times (ie, 3 to 6 times in total). By stacking the cured films in this manner, a laminate can be obtained. In the present invention, it is particularly preferable to provide a metal layer on the portion provided with the cured film, between the cured films, or both. In addition, in manufacturing the laminate, it is not necessary to repeat all steps (a) to (d), and as described above, at least (a), preferably (a) to (c) or (a) to (d) ) can be performed multiple times to obtain a cured film laminate.

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

The type of base material can be determined as appropriate depending on the application, but includes semiconductor manufacturing base materials such as silicon, silicon nitride, polysilicon, silicon oxide, and amorphous silicon, quartz, glass, optical films, ceramic materials, vapor deposited films, There are no particular restrictions on materials such as magnetic films, reflective films, metal base materials such as Ni, Cu, Cr, and Fe, paper, SOG (Spin On Glass), TFT (Thin Film Transistor) array base materials, and electrode plates of plasma display panels (PDP). Moreover, layers such as an adhesive layer and an oxidized layer may be provided on the surface of these base materials. In the present invention, semiconductor production base materials are particularly preferred, and silicon base materials, Cu base materials, and mold base materials are more preferred.
Furthermore, a layer such as an adhesive layer or an oxidized layer made of hexamethyldisilazane (HMDS) or the like may be provided on the surface of these base materials.
Further, as the base material, for example, a plate-shaped base material (substrate) is used.
The shape of the base material is not particularly limited, and may be circular or rectangular, but preferably rectangular.
As for the size of the base material, if it is circular, the diameter is, for example, 100 to 450 mm, preferably 200 to 450 mm. If it is rectangular, the length of the short side is, for example, 100 to 1000 mm, preferably 200 to 700 mm.

Moreover, when forming a resin composition layer on the surface of a resin layer or the surface of a metal layer, a resin layer or a metal layer serves as a base material.

Coating is preferred as a means for applying the resin composition to the substrate.

Specifically, the methods to be applied include 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, and an inkjet method. From the viewpoint of uniformity of the thickness of the resin composition layer, spin coating, slit coating, spray coating, and inkjet methods are more preferred. A resin layer with a desired thickness can be obtained by adjusting the solid content concentration and coating conditions appropriately depending on the method. In addition, the coating method can be appropriately selected depending on the shape of the substrate; spin coating, spray coating, inkjet, etc. are preferable for circular substrates such as wafers, and slit coating and spray coating are preferable for rectangular substrates. method, inkjet method, etc. are preferred. In the case of spin coating, it can be applied, for example, at a rotation speed of 500 to 2,000 rpm for about 10 seconds to 1 minute.
It is also possible to apply a method in which a coating film that has been previously formed on a temporary support by the above-mentioned application method is transferred onto a base material.
Further, depending on the viscosity of the photosensitive resin composition and the desired film thickness, it is also preferable to apply the coating at a rotation speed of 300 to 3,500 rpm for 10 to 180 seconds. Further, in order to obtain uniformity in film thickness, coating can be performed by combining a plurality of rotation speeds.
Regarding the transfer method, the production method described in paragraphs 0023, 0036 to 0051 of JP-A No. 2006-023696 and paragraphs 0096 to 0108 of JP-A No. 2006-047592 can be suitably used in the present invention.
Further, a step of removing excess film may be performed at the end of the base material. Examples of such processes include edge bead rinsing (EBR), air knife, back rinsing, and the like.
Alternatively, a pre-wet process may be employed in which various solvents are applied to the base material before the resin composition is applied to the base material to improve the wettability of the base material, and then the resin composition is applied.

<Drying process>
The manufacturing method of the present invention may include a step of drying to remove the solvent after the film forming step (layer forming step). The preferred drying temperature is 50 to 150°C, more preferably 70 to 130°C, even more preferably 90 to 110°C. The drying time is exemplified by 30 seconds to 20 minutes, preferably 1 minute to 10 minutes, and more preferably 3 minutes to 7 minutes.

<Exposure process>
The manufacturing method of the present invention may include an exposure step of exposing the film (resin composition layer) to light. The amount of exposure is not particularly determined as long as it can cure the resin composition, but for example, it is preferable to irradiate from 100 to 10,000 mJ/cm ² in terms of exposure energy at a wavelength of 365 nm, and from 200 to 8,000 mJ/cm ² Irradiation is more preferred.

The exposure wavelength can be appropriately determined in the range of 190 to 1,000 nm, preferably 240 to 550 nm.
Moreover, it is preferable that the exposure light includes light with a wavelength of 365 nm or 405 nm, and more preferably includes light with a wavelength of 405 nm.

In relation to the light source, the exposure wavelength is: (1) semiconductor laser (wavelength: 830 nm, 532 nm, 488 nm, 405 nm, etc.), (2) metal halide lamp, (3) high-pressure mercury lamp, g-line (wavelength: 436 nm), h (wavelength 405 nm), i-line (wavelength 365 nm), broad (g, h, i-line wavelengths), (4) excimer laser, KrF excimer laser (wavelength 248 nm), ArF excimer laser (wavelength 193 nm), F2 excimer Laser (wavelength: 157 nm), (5) extreme ultraviolet light; EUV (wavelength: 13.6 nm), (6) electron beam, (7) YAG laser with second harmonic of 532 nm and third harmonic of 355 nm. For the resin composition of the present invention, exposure using a high-pressure mercury lamp is particularly preferable, and exposure using i-line is especially preferable. This makes it possible to obtain particularly high exposure sensitivity.
From the viewpoint of handling and productivity, a broad light source (three wavelengths of g, h, and i-rays) of a high-pressure mercury lamp and a semiconductor laser of 405 nm are also suitable.

The method of exposure is not particularly limited, and may be any method as long as at least a part of the film (photoresist film) made of the curable resin composition is exposed to light, such as exposure using a photomask or laser direct imaging method. Examples include exposure.
In the present invention, it is also one of the preferred embodiments that the exposure in the exposure step is by a laser direct imaging method.

<Developing process>
The manufacturing method of the present invention may include a development step of developing the exposed film (resin composition layer) (developing the film). By performing development, the unexposed portions (non-exposed portions) are removed. The developing method is not particularly limited as long as a desired pattern can be formed, and examples thereof include discharging the developer from a nozzle, spraying, immersing the substrate in the developer, etc., and discharging from the nozzle is preferably used. The development process includes a process in which the developer is continuously supplied to the base material, a process in which the developer is kept in a substantially stationary state on the base material, a process in which the developer is vibrated by ultrasonic waves, etc., and a combination of these processes. Processes etc. can be adopted.

Development is performed using a developer. The developer can be used without any particular restrictions as long as the unexposed area is removed.
As the developer, a developer containing an organic solvent or an alkaline aqueous solution can be used.

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

When the developer is a developer containing an organic solvent, the organic solvent includes esters such as ethyl acetate, n-butyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, and ethyl butyrate. , butyl butyrate, methyl lactate, ethyl lactate, γ-butyrolactone, ε-caprolactone, δ-valerolactone, alkyloxyacetate (e.g., methyl alkyloxyacetate, alkyloxyethyl acetate, butyl alkyloxyacetate (e.g., methoxymethyl acetate) , ethyl methoxy acetate, butyl methoxy acetate, methyl ethoxy acetate, ethyl ethoxy acetate, etc.), alkyl 3-alkyloxypropionate (e.g. methyl 3-alkyloxypropionate, ethyl 3-alkyloxypropionate, etc.) , methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, etc.), 2-alkyloxypropionate alkyl esters (e.g. 2-alkyloxypropionate) Methyl, ethyl 2-alkyloxypropionate, propyl 2-alkyloxypropionate, etc. (for example, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, -ethyloxypropionate)), methyl 2-alkyloxy-2-methylpropionate and ethyl 2-alkyloxy-2-methylpropionate (e.g. methyl 2-methoxy-2-methylpropionate, 2-ethoxy-2-ethylpropionate) - ethyl propionate, 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, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether Ethyl ether acetate, propylene glycol monopropyl ether acetate, etc., ketones such as methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, N-methyl-2-pyrrolidone, etc., and cyclic carbonization Examples of hydrogens include toluene, xylene, anisole, limonene, etc., and examples of sulfoxides include dimethyl sulfoxide, and mixtures of these organic solvents are also preferable.

When the developer contains an organic solvent, in the present invention, cyclopentanone and γ-butyrolactone are particularly preferred, and cyclopentanone is more preferred. Further, when the developer contains an organic solvent, one kind of organic solvent or a mixture of two or more kinds of organic solvents can be used.

When the developer is a developer containing an organic solvent, the developer preferably contains 50% by mass or more of an organic solvent, more preferably 70% by mass or more of an organic solvent, and 90% by mass or more of an organic solvent. More preferably, it is a solvent. Further, the developer may be 100% by mass of an organic solvent.

The developer may further contain other components.
Examples of other components include known surfactants and known antifoaming agents.

When the developer is an alkaline aqueous solution, examples of the basic compound that the alkaline aqueous solution may contain include TMAH (tetramethylammonium hydroxide), KOH (potassium hydroxide), and sodium carbonate, with TMAH being preferred. . For example, when TMAH is used, the content of the basic compound in the developer is preferably 0.01 to 10% by mass, more preferably 0.1 to 5% by mass, and 0.3 to 3% by mass based on the total mass of the developer. is even more preferable.

[Developer supply method]
There are no particular restrictions on the method of supplying the developer as long as the desired pattern can be formed, such as immersing the substrate in the developer, using a nozzle to supply the developer onto the substrate and performing paddle development, or continuously applying the developer. There is a way to supply it. There are no particular restrictions on the type of nozzle, and examples include straight nozzles, shower nozzles, spray nozzles, and the like.
From the viewpoint of permeability of the developer, removability of non-image areas, and production efficiency, it is preferable to supply the developer using a straight nozzle or continuously using a spray nozzle. From the viewpoint of permeability, a method of supplying with a spray nozzle is more preferable.
In addition, after continuously supplying the developer using a straight nozzle, the base material is spun to remove the developer from the base material, and after spin drying, the developer is continuously supplied again using the straight nozzle, then the base material is spun and the developer is applied to the base material. A process of removing from above may be adopted, or this process may be repeated multiple times.
In addition, the developer supply method in the development process includes a process in which the developer is continuously supplied to the base material, a process in which the developer is kept in a substantially stationary state on the base material, and a process in which the developer is kept in a substantially stationary state on the base material, and a process in which the developer is kept in an almost stationary state on the base material. A process of vibrating with a sound wave or the like, a process of combining these, etc. can be adopted.

The development time is preferably 5 seconds to 10 minutes, more preferably 10 seconds to 5 minutes. The temperature of the developer at the time of development is not particularly limited, but it can be usually carried out at 10 to 45°C, preferably 20 to 40°C.

After the processing using the developer, rinsing may be further performed. Preferably, rinsing is performed using a solvent different from the developer. For example, rinsing can be performed using a solvent contained in the resin composition.
When the developer is a developer containing an organic solvent, examples of the rinsing solution include PGMEA (propylene glycol monoethyl ether acetate), IPA (isopropanol), and the like, with PGMEA being preferred. Moreover, water is preferable as a rinsing liquid for development with a developer containing an alkaline aqueous solution.
The rinsing time is preferably 10 seconds to 10 minutes, more preferably 20 seconds to 5 minutes, and even more preferably 5 seconds to 1 minute.
The temperature of the rinsing liquid during rinsing is not particularly limited, but it is preferably 10 to 45°C, more preferably 18 to 30°C.

When the rinsing liquid contains an organic solvent, examples of the organic solvent include esters such as ethyl acetate, n-butyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, and butyl butyrate. , methyl lactate, ethyl lactate, γ-butyrolactone, ε-caprolactone, δ-valerolactone, alkyloxyacetate (e.g., methyl alkyloxyacetate, ethyl alkyloxyacetate, butyl alkyloxyacetate (e.g., methyl methoxyacetate, methoxyacetic acid) ethyl, butyl methoxy acetate, methyl ethoxy acetate, ethyl ethoxy acetate, etc.), 3-alkyloxypropionate alkyl esters (e.g. methyl 3-alkyloxypropionate, ethyl 3-alkyloxypropionate, etc.) Methyl methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, etc.), alkyl 2-alkyloxypropionate esters (e.g. methyl 2-alkyloxypropionate, - Ethyl alkyloxypropionate, propyl 2-alkyloxypropionate, etc. (e.g., methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, 2-ethoxypropionate) methyl 2-alkyloxy-2-methylpropionate (e.g. methyl 2-methoxy-2-methylpropionate, 2-ethoxy-2-methylpropionate) methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutanoate, ethyl 2-oxobutanoate, etc., and ethers such as 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 monomethyl ether acetate (PGMEA), Propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, etc., and ketones such as methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, N-methyl-2-pyrrolidone, etc. Examples of aromatic hydrocarbons include toluene, xylene, anisole, limonene, etc.; examples of sulfoxides include dimethyl sulfoxide; examples of alcohols include methanol, ethanol, propanol, isopropanol, butanol, pentanol, octanol, diethylene glycol, propylene glycol, Preferred examples include methylisobutylcarbinol, triethylene glycol, etc., and amides such as N-methylpyrrolidone, N-ethylpyrrolidone, and dimethylformamide.

When the rinsing liquid contains an organic solvent, one type of organic solvent or a mixture of two or more types can be used. In the present invention, cyclopentanone, γ-butyrolactone, dimethyl sulfoxide, N-methylpyrrolidone, cyclohexanone, PGMEA, and PGME are particularly preferred, cyclopentanone, γ-butyrolactone, dimethyl sulfoxide, PGMEA, and PGME are more preferred, and cyclohexanone and PGMEA are particularly preferred. More preferred.

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 90% by mass or more of an organic solvent. is even more preferable. Moreover, 100% by mass of the rinsing liquid may be an organic solvent.

The rinse solution may further contain other components.
Examples of other components include known surfactants and known antifoaming agents.

[How to supply rinsing liquid]
There are no particular restrictions on the method of supplying the rinse liquid as long as the desired pattern can be formed, and the methods include immersing the substrate in the rinse liquid, developing with a puddle on the substrate, supplying the rinse liquid onto the base material with a shower, and the method of supplying the rinse liquid to the base material. There is also a method of continuously supplying the developer using means such as a straight nozzle.
From the viewpoint of permeability of the rinsing liquid, removability of non-image areas, and manufacturing efficiency, there are methods of supplying the rinsing liquid using a shower nozzle, straight nozzle, spray nozzle, etc., and a continuous supply method using a spray nozzle is preferable. From the viewpoint of permeability of the rinsing liquid into the image area, a method of supplying the rinsing liquid using a spray nozzle is more preferable. There are no particular restrictions on the type of nozzle, and examples include straight nozzles, shower nozzles, spray nozzles, and the like.
That is, the rinsing step is preferably a step in which the rinsing liquid is supplied to the exposed film through a straight nozzle or continuously, and more preferably a step in which the rinsing liquid is supplied through a spray nozzle.
In addition, the rinsing liquid supply method in the rinsing process includes a process in which the rinsing liquid is continuously supplied to the substrate, a process in which the rinsing liquid is kept in a substantially stationary state on the substrate, and a process in which the rinsing liquid is A process of vibrating with a sound wave or the like, a process of combining these, etc. can be adopted.

<Heating process>
The manufacturing method of the present invention preferably includes a step of heating the developed film at 50 to 450° C. (heating step).
The heating step is preferably included after the film forming step (layer forming step), the drying step, and the developing step. In the heating step, for example, the above-mentioned thermal base generator is decomposed to generate a base, and the cyclization reaction of the precursor, which is the specific resin, proceeds. Furthermore, although the resin composition of the present invention may contain a radically polymerizable compound other than the precursor which is the specific resin, curing of the radically polymerizable compound other than the precursor which is the unreacted specific resin may also be carried out in this step. It can be proceeded with. The heating temperature (maximum heating temperature) of the layer in the heating step is preferably 50°C or higher, more preferably 80°C or higher, even more preferably 140°C or higher, and even more preferably 150°C or higher. The temperature is more preferably 160°C or higher, even more preferably 170°C or higher. The upper limit is preferably 500°C or less, more preferably 450°C or less, even more preferably 350°C or less, even more preferably 250°C or less, and even more preferably 220°C or less. Even more preferred.

Heating is preferably carried out at a heating rate of 1 to 12°C/min from the temperature at the start of heating to the maximum heating temperature, more preferably 2 to 10°C/min, and even more preferably 3 to 10°C/min. By setting the heating rate to 1°C/min or more, it is possible to prevent excessive volatilization of the amine while ensuring productivity, and by setting the heating rate to 12°C/min or less, the cured film can be Residual stress can be alleviated. In addition, in the case of an oven capable of rapid heating, it is preferable to raise the temperature from the temperature at the start of heating to the maximum heating temperature at a heating rate of 1 to 8°C/second, more preferably 2 to 7°C/second, and 3 to 6°C. C/sec is more preferred.

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

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

Particularly when forming a multilayer laminate, from the viewpoint of adhesion between the layers of the cured film, the heating temperature is preferably 180°C to 320°C, more preferably 180°C to 260°C. Although the reason for this is not clear, it is thought that at this temperature, the ethynyl groups of the specific resin between the layers undergo a crosslinking reaction with each other.

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

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

The heating step is preferably performed in an atmosphere with a low oxygen concentration, such as by flowing an inert gas such as nitrogen, helium, or argon, in order to prevent decomposition of the specific resin. The oxygen concentration is preferably 50 ppm (volume ratio) or less, more preferably 20 ppm (volume ratio) or less.
Examples of the heating means include, but are not limited to, a hot plate, an infrared oven, an electric oven, a hot air oven, and the like.

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

As the metal layer, existing metal species can be used without particular limitation, and examples include copper, aluminum, nickel, vanadium, titanium, chromium, cobalt, gold, and tungsten. An alloy containing is more preferable, and copper is even more preferable.

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

The thickness of the metal layer at the thickest portion is preferably 0.01 to 100 μm, more preferably 0.1 to 50 μm, and even more preferably 1 to 10 μm.

<Lamination process>
Preferably, the manufacturing method of the present invention further includes a lamination step.

The lamination process means that the surface of the cured film (resin layer) or metal layer is again subjected to (a) film formation process (layer formation process), (b) exposure process, (c) development process, and (d) heating process. , is a series of steps that are performed in this order. However, an embodiment may be adopted in which only the film forming step (a) is repeated. Further, the heating step (d) may be performed all at once at the end or in the middle of lamination. That is, the laminated resin composition layers may be cured all at once by repeating steps (a) to (c) a predetermined number of times and then heating in step (d). In addition, after the (c) development step, (e) a metal layer forming step may be included, and even if the heating in (d) is performed each time at this time, the step (d) is performed at once after laminating the layers a predetermined number of times. Heating may also be performed. It goes without saying that the lamination step may further include the above-mentioned drying step, heating step, etc. as appropriate.

When a lamination step is further performed after the lamination step, a surface activation treatment step may be performed after the heating step, the exposure step, or the metal layer forming step. Plasma treatment is exemplified as the surface activation treatment.

The lamination step is preferably performed 2 to 20 times, more preferably 2 to 5 times, and even more preferably 3 to 5 times.
Further, each layer in the lamination process may be a layer with the same composition, shape, thickness, etc., or may be a layer with different layers.

For example, a configuration in which the number of resin layers is 2 or more and 20 or less, such as resin layer/metal layer/resin layer/metal layer/resin layer/metal layer, is preferable, and a configuration in which the number of resin layers is 3 or more and 7 or less is more preferable. More preferably, the number of layers is 3 or more and 5 or less.

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

(Surface activation treatment process)
The method for producing a laminate of the present invention may include a surface activation treatment step of surface activation treatment of at least a portion of the metal layer and the photosensitive resin composition layer.
The surface activation treatment step is usually performed after the metal layer formation step, but it is also possible to perform the metal layer formation step after performing the surface activation treatment step on the photosensitive resin composition layer after the exposure and development step. good.
The surface activation treatment may be performed on at least a portion of the metal layer, or may be performed on at least a portion of the photosensitive resin composition layer after exposure, or the surface activation treatment may be performed on at least a portion of the metal layer and the photosensitive resin composition layer after exposure. Both composition layers may each be applied at least in part. The surface activation treatment is preferably performed on at least a part of the metal layer, and it is preferable that the surface activation treatment is performed on part or all of the region of the metal layer on which the photosensitive resin composition layer is to be formed. . By performing surface activation treatment on the surface of the metal layer in this way, it is possible to improve the adhesion with the resin layer provided on the surface.
Moreover, it is preferable that the surface activation treatment is also performed on part or all of the photosensitive resin composition layer (resin layer) after exposure. By performing surface activation treatment on the surface of the photosensitive resin composition layer in this way, it is possible to improve the adhesion with the metal layer or resin layer provided on the surface that has been surface activated.
Specifically, the surface activation treatment includes plasma treatment of various raw material gases (oxygen, hydrogen, argon, nitrogen, nitrogen/hydrogen mixed gas, argon/oxygen mixed gas, etc.), corona discharge treatment, CF ₄ /O ₂ , etching treatment with NF ₃ /O ₂ , SF ₆ , NF ₃ , NF ₃ /O ₂ , surface treatment with ultraviolet (UV) ozone method, immersion in hydrochloric acid aqueous solution to remove the oxide film, and then removing amino groups and thiol groups. The surface treatment is selected from immersion treatment in an organic surface treatment agent containing at least one compound, and mechanical surface roughening treatment using a brush, and plasma treatment is preferred, and oxygen plasma treatment using oxygen as the 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 .

The present invention also discloses a semiconductor device comprising the cured film or 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 rewiring layer, the descriptions in paragraphs 0213 to 0218 of JP 2016-027357A and the description in FIG. 1 can be referred to, Their contents are incorporated herein.

The present invention will be explained in more detail with reference to Examples below. The materials, usage amounts, ratios, processing details, processing procedures, etc. shown in the following examples can be changed as appropriate without departing from the spirit of the present invention. Therefore, the scope of the present invention is not limited to the specific examples shown below. "Parts" and "%" are based on mass unless otherwise stated.

<Synthesis Example 1: Synthesis of Polymer A-1>
23.48 g of 4,4'-oxydiphthalic dianhydride (ODPA) and 22.27 g of 4,4'-biphthalic dianhydride (BPDA) were placed in a separable flask, and 2-hydroxyethyl methacrylate (HEMA) 39. 69 g of γ-butyrolactone and 136.83 g of γ-butyrolactone were added and stirred at room temperature, and while stirring, 24.66 g of pyridine was added to obtain a reaction mixture. After the exothermic reaction was completed, the mixture was allowed to cool to room temperature and left at room temperature for 16 hours.
Next, under ice cooling, a solution of 62.46 g of dicyclohexylcarbodiimide (DCC) dissolved in 61.57 g of γ-butyrolactone was added to the reaction mixture over 40 minutes with stirring, followed by 4,4'-diaminodiphenyl ether ( A suspension of 27.42 g of DADPE in 119.73 g of γ-butyrolactone was added over 60 minutes with stirring. After further stirring at room temperature for 2 hours, 7.17 g of ethyl alcohol was added and stirred for 1 hour, and then 136.83 g of γ-butyrolactone was added. A precipitate formed in the reaction mixture was removed by filtration to obtain a reaction solution.
The resulting reaction solution was added to 716.21 g of ethyl alcohol to produce a precipitate consisting of a crude polymer. The produced crude polymer was filtered and dissolved in 403.49 g of tetrahydrofuran to obtain a crude polymer solution. The obtained crude polymer solution was dropped into 8470.26 g of water to precipitate the polymer, and the obtained precipitate was filtered and dried under vacuum to obtain a powdery polymer (polyimide precursor) A-1. Ta. When the molecular weight of Polymer A-1 was measured by gel permeation chromatography (standard polystyrene standard), the weight average molecular weight (Mw) was 20,000.

<Synthesis Example 2: Synthesis of Polymer A-2>
Polymer A-2 was synthesized in the same manner as in Synthesis Example 1, except that 23.48 g of ODPA and 22.27 g of BPDA were changed to 46.96 g of ODPA.

<Synthesis Example 3: Synthesis of Polymer A-3>
By the same method as Synthesis Example 1 except that 23.48 g of ODPA and 22.27 g of BPDA were changed to 46.96 g of ODPA, and 39.69 g of HEMA was changed to 19.85 g of HEMA and 18.32 g of diethylene glycol monomethyl ether. , polymer A-3 was synthesized.

<Synthesis Example 4: Synthesis of Polymer A-4>
10.65 g (50 mmol) of 4,6-dihydroxy-1,3-phenylenediamine dihydrochloride are added with removal of moisture in a dry reactor equipped with a flat-bottomed joint fitted with a stirrer, condenser and internal thermometer. It was dissolved in 85.8 g of N-methylpyrrolidone (NMP). Next, a solution of 9.74 g (48 mmol) of terephthalic acid chloride dissolved in 55.0 g of NMP was added dropwise over 1 hour, and the mixture was stirred at 25° C. for 2 hours.
After stirring, the mixture was precipitated in 2 liters of water/methanol=75/25 (volume ratio) and stirred at a speed of 2,000 rpm for 30 minutes. The precipitated polybenzoxazole precursor resin was removed by filtration and washed with 1.5 liters of water. The obtained resin was dried at 40° C. for 1 day under reduced pressure to obtain A-4.

<Synthesis Example 5: Synthesis of Polymer A-5>
Put 29.08 g of trimellitic anhydride into a separable flask, add 19.85 g of 2-hydroxyethyl methacrylate (HEMA) and 136.83 g of γ-butyrolactone, stir at room temperature, and add 24.66 g of pyridine while stirring. In addition, a reaction mixture was obtained. After the exotherm due to the reaction was completed, the mixture was allowed to cool to room temperature and left at room temperature for 16 hours.
Next, under ice cooling, a solution of 62.46 g of dicyclohexylcarbodiimide (DCC) dissolved in 61.57 g of γ-butyrolactone was added to the reaction mixture over 40 minutes with stirring, followed by 4,4'-diaminodiphenyl ether ( A suspension of 27.42 g of DADPE in 119.73 g of γ-butyrolactone was added over 60 minutes with stirring. After further stirring at room temperature for 2 hours, 7.17 g of ethyl alcohol was added and stirred for 1 hour, and then 136.83 g of γ-butyrolactone was added. A precipitate formed in the reaction mixture was removed by filtration to obtain a reaction solution.
The resulting reaction solution was added to 716.21 g of ethyl alcohol to produce a precipitate consisting of a crude polymer. The produced crude polymer was filtered and dissolved in 403.49 g of tetrahydrofuran to obtain a crude polymer solution. The obtained crude polymer solution was dropped into 8470.26 g of water to precipitate the polymer, and the obtained precipitate was filtered and dried under vacuum to obtain powdered polymer (polyamideimide precursor) A-5. Obtained.

<Synthesis Example 6: Synthesis of Polymer A-6>
Polymer A-6 was synthesized in the same manner as in Synthesis Example 1, except that 23.48 g of ODPA and 22.27 g of BPDA were changed to 44.54 g of BPDA.

<Synthesis Example 7: Synthesis of Polymer A-7>
Synthesis Example 1 except that 23.48 g of ODPA and 22.27 g of BPDA were changed to 46.96 g of ODPA, and 39.69 g of HEMA was changed to 52.52 g of the compound represented by the following formula (7-1). Polymer A-7 was synthesized by a similar method.

<Examples and comparative examples>
In each Example, the components listed in the table below were mixed to obtain each curable resin composition. In each comparative example, the components listed in the table below were mixed to obtain comparative compositions.
Specifically, the content of each component listed in Tables 1 to 7 was the amount (parts by mass) listed in parentheses in each column of Tables 1 to 7.
However, the content of the specific compound was such that the content of the specific compound relative to the total mass of the composition was the value described in the column of "Specific compound content (ppm)".
The obtained curable resin composition and comparative composition were filtered under pressure using a polytetrafluoroethylene filter with a pore width of 0.8 μm.
Furthermore, in Tables 1 to 7, the description "-" indicates that the composition does not contain the corresponding component.

Details of each component listed in Tables 1 to 7 are as follows.

〔resin〕
・A-1 to A-7: Polymers A-1 to A-7 obtained by the above synthesis example

[Photosensitizer (photoradical polymerization initiator)]
・B-1 to B-3: Compounds with the following structure

[Organometallic complex]
・X-1: Bis(η5-2,4-cyclopentadien-1-yl)bis(2,6-difluoro-3-(1H-pyrrol-1-yl)phenyl)titanium ・X-2: Pentamethylcyclo Pentadienyl titanium trimethoxide・X-3: Bis(η5-2,4-cyclopentadien-1-yl)bis(2,6-difluorophenyl)titanium・X-4: Tetraisopropoxytitanium (Matsumoto Fine Chemical Co., Ltd.) made)
・X-5: Diisopropoxybis(acetylacetonato)titanium (manufactured by Matsumoto Fine Chemicals)
-X-6 to X-8: Compounds with the following structure.

The above X-1 and X-3 are compounds having the ability to initiate photoradical polymerization.

[Crosslinking agent (radical crosslinking agent)]
・C-1 to C-2: Compound with the following structure

[Polymerization inhibitor, migration inhibitor]
・D-1 to D-7: Compounds with the following structure

〔Additive〕
・E-1 to E-6: Compounds with the following structure

[Metal adhesion improver]
・F-1 to F-6: Compounds with the following structure

In the above structural formula, Me represents a methyl group, and Et represents an ethyl group.

[Specific compound]
・G-1 to G-27: Compounds with the following structure

[Solvent (solvent)]
・NMP: N-methyl-2-pyrrolidone ・EL: Ethyl lactate ・DMSO: Dimethyl sulfoxide

<Evaluation>
[Resolution evaluation]
In each Example or Comparative Example, the prepared curable resin composition or comparative composition was applied onto a silicon wafer by a spin coating method. The silicon wafer was dried on a hot plate at 100° C. for 5 minutes to form a curable resin composition layer with a uniform thickness of 20 μm on the silicon wafer.
In the example described as "M" in the exposure condition, the curable resin composition layer on the silicon wafer was exposed using a stepper. Exposure was carried out using light of the wavelength described in "Exposure wavelength nm" in the table, using a fuse box photomask with 1 μm increments from 5 μm to 25 μm. The exposure amount was determined to minimize the minimum line width described below.
In the examples where "D" was written as the exposure condition, exposure was performed using a direct exposure device (Adtec DE-6UH III). Exposure was carried out by laser direct imaging exposure at a wavelength of 405 nm such that the exposed area was a line part in a line-and-space pattern from 5 μm to 25 μm in 1 μm increments. The exposure amount was determined to minimize the minimum line width described below.
The exposed curable resin composition layer was developed with cyclopentanone for 60 seconds, and then rinsed with PGMEA (propylene glycol monomethyl ether acetate).
In the pattern obtained after development, the line width of the line pattern with the smallest line width between which the silicon wafer was exposed was defined as the "minimum line width" and evaluated according to the following evaluation criteria. It can be said that the smaller the line width, the better the resolution. For example, this is a preferable result because it indicates that the width of the metal wiring formed in the subsequent plating process can be made finer. The measurement limit is 5 μm. The evaluation results are listed in the "Resolution" column in the table.
-Evaluation criteria-
A: The minimum line width was 5 μm or more and less than 8 μm.
B: The minimum line width was 8 μm or more and less than 10 μm.
C: The minimum line width was 10 μm or more and less than 12 μm.
D: The minimum line width was 12 μm or more.

[Exposure sensitivity evaluation]
A curable resin composition layer with a uniform thickness of 20 μm was formed on a silicon wafer by the same method as in the above resolution evaluation.
In the example in which "M" is written in the exposure condition, the curable resin composition layer on the silicon wafer is coated with a stepper at a mask portion with a diameter of 15.0 μm ("Negative" is written in the development condition column in the table). Exposure was performed using a photomask having a non-mask area (example where "positive" is written in the column of current conditions in the table) or a non-mask area (example where "positive" is written in the column of current conditions in the table). The exposure wavelength is listed in "Exposure wavelength nm" in the table. The exposure amount was varied in the range of 50 to 500 mJ/cm ² in steps of 50 mJ/cm ² .
In the examples described as "D" in the exposure conditions, laser direct imaging exposure was performed using a direct exposure device (Adtech DE-6UH III). The exposure wavelength was 405 nm, and exposure was performed so that an unexposed part with a diameter of 15.0 μm was formed. The exposure amount was varied in the range of 50 to 500 mJ/cm ² in steps of 50 mJ/cm ² .
Sensitivity was evaluated according to the following evaluation criteria from the minimum exposure amount at which a hole pattern with a bottom diameter of 15.0 μm was formed. The smaller the minimum exposure amount (the higher the sensitivity), the more preferable it is, and it can be said that the exposure sensitivity is excellent. The evaluation results are listed in the "Sensitivity" column in the table.
-Evaluation criteria-
A: The above minimum exposure amount was less than 100 mJ/cm ² .
B: The minimum exposure amount was 100 mJ/cm ² or more and less than 150 mJ/cm ² .
C: The minimum exposure amount was 150 mJ/cm ² or more.

From the above results, it can be seen that the curable resin composition of the present invention has excellent resolution.
In the comparative compositions according to Comparative Examples 1 to 6, the content of the specific compound is less than 10 ppm or more than 50,000 ppm based on the total mass of the composition.
It can be seen that such a comparative composition has poor resolution.

<Example 101>
The curable resin composition used in Example 1 was applied in a layered manner by spin coating to the surface of the thin copper layer of the resin base material on which the thin copper layer was formed, and dried at 100° C. for 4 minutes. After forming a photoresist film with a thickness of 20 μm, it was exposed using a stepper (NSR1505 i6, manufactured by Nikon Corporation). Exposure was performed at a wavelength of 365 nm through a mask (a binary mask with a 1:1 line-and-space pattern and a line width of 10 μm). After exposure, it was heated at 100° C. for 4 minutes. After the heating, it was developed with cyclohexanone for 2 minutes and rinsed with PGMEA for 30 seconds to obtain a layer pattern.
Next, the temperature was raised at a rate of 10° C./min in a nitrogen atmosphere, and after reaching 230° C., the temperature was maintained at 230° C. for 120 minutes to form an interlayer insulating film for a rewiring layer. This rewiring layer interlayer insulating film had excellent insulation properties.
Furthermore, when semiconductor devices were manufactured using these interlayer insulating films for rewiring layers, it was confirmed that they operated without problems.

Claims (18)

At least one resin selected from the group consisting of polyimide precursors, polybenzoxazole precursors, and polyamideimide precursors,
organometallic complexes, and
At least one species selected from the group consisting of a compound represented by the following formula (1-1), a compound represented by the following formula (1-2), and a compound represented by the following formula (1-3) including;
The content of the compound is 10 to 100 ppm based on the total mass of the composition,
The content of the resin is 50% by mass or more based on the total solid content of the composition,
The curable resin composition of the present invention contains a solvent and has a total solids concentration of 40 to 70% by mass,
Used to form a photosensitive film that is subjected to negative development.
Curable resin composition.
In formula (1-1), formula (1-2) or formula (1-3), R ¹¹ and R ¹² each independently represent an unsubstituted aliphatic hydrocarbon group having 1 to 7 carbon atoms or a substituent. At least one member selected from the group consisting of a primary amine salt structure, a secondary amine salt structure, a tertiary amino group, a tertiary amine salt structure, a quaternary ammonium group, and an aliphatic heterocyclic group an aliphatic hydrocarbon group having 1 to 7 carbon atoms having a substituent, or having at least one substituent selected from the group consisting of a hydroxy group, an alkoxy group, a thiol group, and an alkylthio group having 2 carbon atoms -7 aliphatic hydrocarbon group; R ²¹ and R ²² each independently represent an aliphatic hydrocarbon group having 1 to 7 carbon atoms which may have a substituent; R ³¹ and R ³² each Each independently represents an aliphatic hydrocarbon group having 1 to 7 carbon atoms which may have a substituent, and R ³³ represents an aliphatic hydrocarbon group having 1 to 7 carbon atoms which may have a substituent. At least one resin selected from the group consisting of polyimide precursors, polybenzoxazole precursors, and polyamideimide precursors,
organometallic complexes, and
Containing at least one selected from the group consisting of a compound represented by the following formula (1-2) and a compound represented by the following formula (1-3),
The content of the compound is 10 to 50,000 ppm based on the total mass of the composition,
The content of the resin is 50% by mass or more based on the total solid content of the composition,
Used to form a photosensitive film for negative development.
Curable resin composition.

In formula (1-2) or formula (1-3), R ²¹ and R ²² each independently represent an aliphatic hydrocarbon group having 1 to 7 carbon atoms which may have a substituent, and R ³¹ and R ³² each independently represents an aliphatic hydrocarbon group having 1 to 7 carbon atoms which may have a substituent, and R ³³ represents an aliphatic hydrocarbon group having 1 to 7 carbon atoms which may have a substituent. represents a group. The curable resin composition according to claim 1, wherein the compound is a compound represented by any one of the following formulas (G-1) to (G-12).
The curable compound according to claim 2, wherein the compound is a compound represented by any of the following formulas (G-1) to (G-4) and formulas (G-9) to (G-12). Resin composition.
The curable resin composition according to any one of claims 1 to 4, further comprising a photopolymerization initiator. The curable resin composition according to any one of claims 1 to 5, further comprising a crosslinking agent. The curable resin composition according to any one of claims 1 to 6, wherein the organometallic complex is a metallocene compound. The curable resin composition according to any one of claims 1 to 7, wherein the metal contained in the organometallic complex is at least one metal selected from the group consisting of titanium, zirconium, and hafnium. The curable resin composition according to any one of claims 1 to 8, wherein the organometallic complex has the ability to initiate radical photopolymerization. The curable resin composition according to any one of claims 1 to 9, which is used for forming an interlayer insulating film for a rewiring layer. A cured film obtained by curing the curable resin composition according to any one of claims 1 to 10. A laminate comprising two or more layers of the cured film according to claim 11, and a metal layer between any of the cured films. A method for producing a cured film, comprising a film forming step of applying the curable resin composition according to any one of claims 1 to 10 to a substrate to form a film. The method for producing a cured film according to claim 13, comprising an exposure step of exposing the film and a development step of developing the film. The method for producing a cured film according to claim 14, wherein the exposure light used for the exposure includes light with a wavelength of 405 nm. The method for producing a cured film according to claim 14 or 15, wherein the exposure is by a laser direct imaging method. The method for producing a cured film according to any one of claims 13 to 16, comprising a heating step of heating the film at 50 to 450°C. A semiconductor device comprising the cured film according to claim 11 or the laminate according to claim 12.