WO2022044998A1

WO2022044998A1 - Curable resin composition, cured object, layered product, method for producing cured object, semiconductor device, and polyimide precursor and production method therefor

Info

Publication number: WO2022044998A1
Application number: PCT/JP2021/030587
Authority: WO
Inventors: 大輔浅川
Original assignee: 富士フイルム株式会社
Priority date: 2020-08-25
Filing date: 2021-08-20
Publication date: 2022-03-03
Also published as: JPWO2022044998A1; TW202219080A

Abstract

A curable resin composition including a polyimide precursor having a total content of a cyclic imide structure and a cyclic isoimide structure of 0.28-1.68 mmol/g and an acid value of 5.6-22.5 mgKOH/g; a cured object obtained by curing the curable resin composition; a layered product including the cured object; a method for producing the cured object; a semiconductor device including the cured object or the layered product; and the polyimide precursor and a method for producing the polyimide precursor.

Description

Curable resin composition, cured product, laminate, method for producing cured product, semiconductor device, polyimide precursor and method for producing the same.

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

Polyimide is applied to various applications because it has excellent heat resistance and insulating properties. The application is not particularly limited, and examples thereof include a semiconductor device for mounting as a material for an insulating film or a sealing 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, polyimide is used in the form of a curable resin composition containing a polyimide precursor.
Such a curable resin composition is applied to a base material by, for example, coating to form a photosensitive film, and then exposed, developed, heated or the like as necessary to apply the cured product onto the base material. Can be formed.
The polyimide precursor is, for example, cyclized by heating to become polyimide in a cured product.
Since the curable resin composition can be applied by a known coating method or the like, for example, there is a high degree of freedom in designing the shape, size, application position, etc. of the applied curable resin composition at the time of application. It can be said that it has excellent manufacturing adaptability. In addition to the high performance of polyimide, from the viewpoint of excellent manufacturing adaptability, the above-mentioned curable resin composition is expected to be increasingly applied in industry.

For example, Patent Document 1 describes a negative photosensitive resin composition containing (A1) a first resin, (A2) a second resin, (C) a photopolymerization initiator, and (D) a colorant. The first resin (A1) is (A1-1) polyimide and / or (A1-2) polybenzoxazole.
The (A2) second resin is selected from (A2-2) polybenzoxazole precursor, (A2-3) polysiloxane, (A2-4) cardo-based resin, and (A2-5) acrylic resin. The content ratio of the first resin (A1) to the total of 100% by mass of the above (A1) first resin and the above (A2) second resin is 25 to 90% by mass. A negative photosensitive resin composition characterized by being within the range is described.

Japanese Unexamined Patent Publication No. 2019-023728

Improvement of chemical resistance is required for a cured product made of a curable resin composition.

The present invention relates to a curable resin composition having excellent chemical resistance of the obtained cured product, a cured product obtained by curing the curable resin composition, a laminate containing the cured product, a method for producing the cured product, and a method for producing the cured product. , It is an object of the present invention to provide a semiconductor device containing the cured product or the laminated body.
Another object of the present invention is to provide a novel polyimide precursor and a method for producing the same.

Examples of typical embodiments of the present invention are shown below.
<1> Curable resin composition containing a polyimide precursor having a total content of a cyclic imide structure and a cyclic isoimide structure of 0.28 to 1.68 mmol / g and an acid value of 5.6 to 22.5 mgKOH / g. thing.
<2> The curable resin composition according to <1>, wherein the content of the carboxy group in the polyimide precursor is 5.6 to 22.5 mgKOH / g.
<3> The polyimide precursor contains a repeating unit represented by the following formula (3), and the monovalent organic groups R ¹¹³ and R ¹¹⁴ with respect to all R ¹¹³ and R ¹¹⁴ contained in the polyimide precursor. The curable resin composition according to <1> or <2>, wherein the ratio is 10 to 97 mol%.

In formula (3), R ¹¹¹ represents a divalent organic group, R ¹¹⁵ represents a tetravalent organic group, and R ¹¹³ and R ¹¹⁴ independently represent a hydrogen atom or a monovalent organic group. show.
<4> The curable resin composition according to any one of <1> to <3>, which further contains a photopolymerization initiator.
<5> The curable resin composition according to <4>, wherein the photopolymerization initiator is an oxime compound.
<6> The curable resin composition according to any one of <1> to <5>, which further contains a polymerizable compound.
<7> The curable resin composition according to any one of <1> to <6>, which further contains an organometallic complex.
<8> The curable resin composition according to <7>, wherein the organometallic complex is a metallocene compound.
<9> The curable resin composition according to <7> or <8>, wherein the metal contained in the organic metal complex is at least one metal selected from the group consisting of titanium, zirconium, and hafnium.
<10> The curable resin composition according to any one of <1> to <9>, which is used for forming a photosensitive film to be subjected to negative development.
<11> The curable resin composition according to any one of <1> to <10>, which is used for forming an interlayer insulating film for a rewiring layer.
<12> A cured product obtained by curing the curable resin composition according to any one of <1> to <11>.
<13> A laminated body containing two or more layers made of the cured product according to <12> and containing a metal layer between any of the layers made of the cured product.
<14> A method for producing a cured product, which comprises a film forming step of applying the curable resin composition according to any one of <1> to <11> onto a substrate to form a film.
<15> The method for producing a cured product according to <14>, which comprises an exposure step of selectively exposing the film and a developing step of developing the film with a developer to form a pattern.
<16> The method for producing a cured product according to <15>, wherein the exposure light used for the above exposure includes light having a wavelength of 405 nm.
<17> The method for producing a cured product according to <15> or <16>, wherein the exposure is an exposure by a laser direct imaging method.
<18> The method for producing a cured product according to any one of <14> to <17>, which comprises a heating step of heating the film at 50 to 450 ° C.
<19> A semiconductor device comprising the cured product according to <12> or the laminate according to <13>.
<20> A polyimide precursor having a total content of a cyclic imide structure and a cyclic isoimide structure of 0.28 to 1.68 mmol / g and an acid value of 5.6 to 22.5 mgKOH / g.
<21> The method for producing the polyimide precursor according to <20>.
An amidation step of reacting a dicarboxylic acid compound with a diamine compound to obtain an amide compound,
A method for producing a polyimide precursor, which comprises a partial imidization step of partially imidizing the amide compound.
<22> The method for producing the polyimide precursor according to <20>.
A method for producing a polyimide precursor, which comprises an amidation step of reacting a dicarboxylic acid compound with a diamine compound in the presence of a basic catalyst to obtain an amide compound.

According to the present invention, a curable resin composition having excellent chemical resistance of the obtained cured product, a cured product obtained by curing the curable resin composition, a laminate containing the cured product, and a method for producing the cured product. , And a semiconductor device containing the cured product or the laminate is provided.
Further, according to the present invention, a novel polyimide precursor and a method for producing the same are provided.

Hereinafter, the main embodiments of the present invention will be described. However, the present invention is not limited to the specified embodiments.
In the present specification, the numerical range represented by the symbol "-" means a range including the numerical values before and after "-" as the lower limit value and the upper limit value, respectively.
As used herein, the term "process" means not only an independent process but also a process that cannot be clearly distinguished from other processes as long as the intended action of the process can be achieved.
In the notation of a group (atomic group) in the present specification, the notation not describing substitution and non-substitution also includes a group having a substituent (atomic group) as well as a group having no substituent (atomic group). For example, the "alkyl group" includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).
As used herein, the term "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 emission line spectra of mercury lamps, far ultraviolet rays typified by excimer lasers, extreme ultraviolet rays (EUV light), X-rays, active rays such as electron beams, or radiation.
As used herein, "(meth) acrylate" means both "acrylate" and "methacrylate", or either, and "(meth) acrylic" means both "acrylic" and "methacrylic", or. , Any, and "(meth) acryloyl" means both "acryloyl" and "methacrylic", or either.
In the present specification, Me in the structural formula represents a methyl group, Et represents an ethyl group, Bu represents a butyl group, and Ph represents a phenyl group.
As used herein, the total solid content means the total mass of all the components of the composition excluding the solvent. Further, in the present specification, the solid content concentration is the mass percentage of other components excluding the solvent with respect to the total mass of the composition.
In the present specification, the weight average molecular weight (Mw) and the number average molecular weight (Mn) are values measured by gel permeation chromatography (GPC) method and are defined as polystyrene-equivalent values unless otherwise specified. In the present specification, for the weight average molecular weight (Mw) and the number average molecular weight (Mn), for example, HLC-8220GPC (manufactured by Tosoh Corporation) is used, and guard columns HZ-L, TSKgel Super HZM-M, and TSKgel are used as columns. It can be obtained by connecting and using Super HZ4000, TSKgel Super HZ3000, and TSKgel Super HZ2000 (all manufactured by Tosoh Corporation) in series. Unless otherwise specified, their molecular weights shall be measured using THF (tetrahydrofuran) as an eluent. However, NMP (N-methyl-2-pyrrolidone) can also be used when THF is not suitable as the eluent, such as when the solubility is low. Further, unless otherwise specified, the detection in the GPC measurement shall be performed by using a detector having a wavelength of 254 nm of UV rays (ultraviolet rays).
In the present specification, when the positional relationship of each layer constituting the laminated body is described as "upper" or "lower", the other layer is on the upper side or the lower side of the reference layer among the plurality of layers of interest. All you need is. That is, a third layer or element may be further interposed between the reference layer and the other layer, and the reference layer and the other layer need not be in contact with each other. Unless otherwise specified, the direction in which the layers are stacked on the base material is referred to as "upper", or if there is a resin composition layer, the direction from the base material to the resin composition layer is referred to as "upper". And the opposite direction is called "down". It should be noted that such a vertical setting is for convenience in the present specification, and in an actual embodiment, the "up" direction in the present specification may be different from the vertical upward direction.
Unless otherwise specified in the present specification, the composition may contain, as each component contained in the composition, two or more compounds corresponding to the component. Further, unless otherwise specified, the content of each component in the composition means the total content of all the compounds corresponding to the component.
In the present specification, unless otherwise specified, the temperature is 23 ° C., the atmospheric pressure is 101,325 Pa (1 atmospheric pressure), and the relative humidity is 50% RH.
As used herein, a combination of preferred embodiments is a more preferred embodiment.

(Curable resin composition)
The curable resin composition of the present invention (hereinafter, also simply referred to as “resin composition”) has a total content of the cyclic imide structure and the cyclic isoimide structure of 0.28 to 1.68 mmol / g, and has an acid value of 0.28 to 1.68 mmol / g. It contains a polyimide precursor (hereinafter, also referred to as “specific resin”) having a value of 5.6 to 22.5 mgKOH / g.

The curable resin composition of the present invention is preferably used for forming a photosensitive film to be exposed and developed, and is used for forming a film to be subjected to exposure and development using a developing solution containing an organic solvent. Is preferable.
Further, the curable resin composition of the present invention is preferably used for forming a photosensitive film to be subjected to negative type development.
In the present invention, negative-type development refers to development in which a non-exposed portion is removed by development in exposure and development, and positive-type development refers to development in which an exposed portion is removed by development.
The exposure method, the developer, and the developing method include, for example, the exposure method described in the exposure step in the description of the method for producing a cured product described later, the developer and the developing method described in the developing step. Is used.

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

The polyimide precursor used in the present invention has a total content of the cyclic imide structure and the cyclic isoimide structure of 0.28 to 1.68 mmol / g and an acid value of 5.6 to 22.5 mgKOH / g.
It is presumed that when the total content of the cyclic imide structure and the cyclic isoimide structure is within the above range, the content of the cyclic imide structure in the polyimide formed is high, so that the chemical resistance of the cured product is improved. Will be done. The above effect is particularly remarkable when imidization is performed at a low temperature.
Further, when the acid value is within the above range, the obtained cured product becomes hydrophilic, and it is presumed that the chemical resistance of the cured product is improved.
Further, by setting the total content of the cyclic imide structure and the cyclic isoimide structure within the above range and the acid value within the above range, the chemical resistance is specifically improved beyond the chemical resistance expected by these. do. The reason for this is not clear, but it is presumed that the chemical resistance is further improved by the specific interaction between the highly polar cyclic imide structure and the acid group in the cured product.
Since the cured product has excellent chemical resistance, for example, another curable resin composition containing a solvent is further applied and cured on the cured product obtained by curing the curable resin composition of the present invention, and the laminated body is cured. It is considered that the dissolution of the cured product is suppressed even if the cured product comes into contact with the developing solution or other curable resin composition in the case of producing the above.
According to the present invention, for example, a polar solvent such as dimethyl sulfoxide (DMSO) or N-methylpyrrolidone (NMP), an alkaline aqueous solution such as a tetramethylammonium hydroxide (TMAH) aqueous solution, or the polar solvent and the alkaline aqueous solution. It is considered that a cured product having excellent chemical resistance and having suppressed solubility in the mixed solution of the above can be obtained.

Here, Patent Document 1 describes a curable resin composition containing a polyimide precursor in which the total content of the cyclic imide structure and the cyclic isoimide structure is within the above range and the acid value is within the above range. It has not been.

Further, it is presumed that the total content of the cyclic imide structure and the cyclic isoimide structure is within the above range, and that the cured product obtained by the above interaction is also excellent in elongation at break.
Further, when the total content of the cyclic imide structure and the cyclic isoimide structure of the polyimide precursor at the time of development is within the above range, the strength of the pattern itself formed after development is improved, and the rectangularity of the formed pattern is improved. Presumed to be excellent.
In addition, when the polyimide precursor has a polymerizable group, by setting the acid value within the above range, the content of the polymerizable group is relatively reduced, so that the shrinkage rate before and after curing is reduced and the curing is performed. It is presumed that membrane shrinkage in objects is suppressed. Further, even if the amount of the polymerizable group is reduced to reduce the shrinkage rate, the curable resin composition of the present invention has a high content of the cyclic imide structure in the cured product as described above. Further, since the above-mentioned interaction exists, it is presumed that a cured product having excellent elongation at break and chemical resistance can be obtained.

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

<Specific resin>
The curable resin composition of the present invention has a polyimide precursor having a total content of a cyclic imide structure and a cyclic isoimide structure of 0.28 to 1.68 mmol / g and an acid value of 5.6 to 22.5 mgKOH / g. Includes body (specific resin).

[Total content of cyclic imide structure and cyclic isoimide structure]
The total content of the cyclic imide structure and the cyclic isoimide structure in the specific resin is 0.28 to 1.68 mmol / g.
The specific resin may have at least one of a cyclic imide structure and a cyclic isoimide structure in the side chain, but it is preferable to have it in the main chain.
As used herein, the main chain of a resin is the relatively longest molecular chain in a molecule.
The lower limit of the total content is preferably 0.30 mmol / g or more, and more preferably 0.50 mmol / g or more.
The upper limit of the total content is preferably 1.65 mmol / g or less, and more preferably 1.60 mmol / g or less.
The total content is calculated, for example, by the method described in the examples.

[Acid value]
The acid value of the specific resin is 5.6 to 22.5 mgKOH / g.
The lower limit of the acid value is preferably 5.8 mgKOH / g or more, and more preferably 6.3 mgKOH / g or more.
The upper limit of the acid value is preferably 22.5 mgKOH / g or less, and more preferably 21.5 mgKOH / g or less.
The acid value is calculated, for example, by the method described in Examples.

[Content of carboxy group]
The content of the carboxy group in the specific resin is preferably 5.6 to 22.5 mgKOH / g.
The lower limit of the content of the carboxy group is preferably 5.8 mgKOH / g or more, and more preferably 6.3 mgKOH / g or more.
The upper limit of the content of the carboxy group is preferably 22.5 mgKOH / g or less, and more preferably 21.5 mgKOH / g or less.

Further, the specific resin preferably has a radically polymerizable group.
When the specific resin has a radically polymerizable group, the curable resin composition contains at least one selected from the group consisting of an organic metal complex having a radical polymerization initiator described later and a photoradical polymerization initiator described below. It is preferable that it contains at least one selected from the group consisting of an organic metal complex having a radical polymerization initiation ability described later and a photoradical polymerization initiator described below, and more preferably contains a radical cross-linking agent described below. ..
In the above aspect, an aspect further containing a sensitizer described later is also one of the preferred aspects of the present invention.
From such a curable resin composition, for example, a negative photosensitive film is formed.
When the specific resin has a radically polymerizable group, the molar content of the radically polymerizable group in 1 g of the specific resin is preferably 1.30 to 2.20 mmol / g, preferably 1.40 to 2.10 mmol / g. It is more preferably 1.50 to 2.00 mmol / g, and even more preferably 1.50 to 2.00 mmol / g.

Further, the specific resin may have a polar conversion 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 later as a photosensitive agent. From such a curable resin composition, for example, a chemically amplified positive type photosensitive film or a negative type photosensitive film is formed.

[Repeating unit represented by equation (2)]
The specific resin used in the present invention is not particularly specified, such as its type, but preferably contains a repeating unit represented by the following formula (2).

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

A ¹ and A ² in the formula (2) independently represent an oxygen atom or —NH—, and an oxygen atom is preferable.
R ¹¹¹ in the formula (2) represents a divalent organic group. Examples of the divalent organic group include a linear or branched aliphatic group, a cyclic aliphatic group and a group containing an aromatic group, and a linear or branched aliphatic group having 2 to 20 carbon atoms and a carbon number of carbon atoms are exemplified. A cyclic aliphatic group having 3 to 20, an aromatic group having 3 to 20 carbon atoms, or a group consisting of a combination thereof is preferable, and a group containing an aromatic group having 6 to 20 carbon atoms is more preferable. In the linear or branched aliphatic group, the hydrocarbon group in the chain may be substituted with a group containing a heteroatom, and in the cyclic aliphatic group and the aromatic group, the hydrocarbon group of the ring member is a heteroatom. It may be substituted with a group containing. Preferred embodiments of the present invention exemplify the groups represented by -Ar- and -Ar-L-Ar-, and particularly preferably the groups represented by -Ar-L-Ar-. However, Ar is an aromatic group independently, and L is a single bond, an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be substituted with a fluorine atom, -O-, -CO-,. -S-, -SO _2- or -NHCO-, or a group consisting of a combination of two or more of the above. These preferred ranges are as described above.

R ¹¹¹ is preferably derived from diamine. Examples of the diamine used for producing the polyimide precursor include linear or branched aliphatic, cyclic aliphatic or aromatic diamines. Only one kind of diamine may be used, or two or more kinds of diamines may be used.
Specifically, a linear or branched aliphatic group having 2 to 20 carbon atoms, a cyclic aliphatic group having 3 to 20 carbon atoms, an aromatic group having 3 to 20 carbon atoms, or a group consisting of a combination thereof. The diamine containing the above is preferable, and the diamine containing an aromatic group having 6 to 20 carbon atoms is more preferable. In the linear or branched aliphatic group, the hydrocarbon group in the chain may be substituted with a group containing a heteroatom, and in the cyclic aliphatic group and the aromatic group, the hydrocarbon group of the ring member is a heteroatom. It may be substituted with a containing group. Examples of groups containing aromatic groups include:

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

Specific examples of the diamine 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 isophoronediamine; m- or p-phenylenediamine, diaminotoluene, 4,4'- Or 3,3'-diaminobiphenyl, 4,4'-diaminodiphenyl ether, 3,3-diaminodiphenyl ether, 4,4'-and 3,3'-diaminodiphenylmethane, 4,4'-and 3,3'-diamino Diphenyl sulfone, 4,4'-and 3,3'-diaminodiphenyl sulfide, 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'-diaminoparatelphenyl, 4,4'-bis (4-aminophenoxy) biphenyl, bis [4- (4-aminophenoxy) phenyl] sulfone, bis [4- (3-aminophenoxy) ) Phenyl] sulfone, bis [4- (2-aminophenoxy) phenyl] sulfone, 1,4-bis (4-aminophenoxy) benzene, 9,10-bis (4-aminophenyl) anthracene, 3,3'- Dimethyl-4,4'-diaminodiphenyl sulfone, 1,3-bis (4-aminophenoxy) benzene, 1,3-bis (3-aminophenoxy) benzene, 1,3-bis (4-) Aminophenyl) benzene, 3,3'-diethyl-4,4'-diaminodiphenylmethane, 3,3'-dimethyl-4,4'-diaminodiphenylmethane, 4,4'-diaminooctafluorobiphenyl, 2,2-bis [4- (4-Aminophenoxy) phenyl] propane, 2,2-bis [4- (4-aminophenoxy) phenyl] hexafluoropropane, 9,9-bis (4-aminophenyl) -10-hydroanthracene, 3,3', 4,4'-tetraaminobiphenyl, 3,3', 4,4'-tetraaminodiphenyl ether, 1,4-diaminoanthraquinone, 1,5-diaminoanthraquinone, 3,3-dihydroxy-4, 4'-Diaminobiphenyl, 9,9'-bis (4-aminophenyl) fluorene, 4,4'-dimethyl-3,3'-diaminodiphenylsulfone, 3,3', 5,5'-tetramethyl-4 , 4'-diaminodiphenylmethane, 2,4- and 2,5-diaminocumene, 2,5-dimethyl-p-phenylenediamine, acetoguanamine, 2,3,5,6-tetramethyl-p-phenylenediamine, 2, , 4,6-trimethyl-m-phenylenediamine, bis (3-aminopropyl) tetramethyldisiloxane, bis (p-aminophenyl) octamethylpentasiloxane, 2,7-diaminofluorene, 2,5-diaminopyridine, 1,2-Bis (4-aminophenyl) ethane, diaminobenzanilide, ester of diaminobenzoic acid, 1,5-diaminonaphthalene, diaminobenzotrifluoride, 1,3-bis (4-aminophenyl) hexafluoropropane, 1,4-bis (4-aminophenyl) octafluorobutane, 1,5-bis (4-aminophenyl) decafluoropentane, 1,7-bis (4-aminophenyl) tetradecafluoroheptane, 2,2- Bis [4- (3-aminophenoxy) phenyl] hexafluoropropane, 2,2-bis [4- (2-aminophenoxy) phenyl] hexafluoropropane, 2,2-bis [4- (4-aminophenoxy) -3,5-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) diphenyl sulfone, 4,4'-bis (3-Amino-5-trifluoromethylphenoxy) diphenyl sulfone, 2,2-bis [4- (4-amino-3-trifluoromethylphenoxy) phenyl] hexafluoropropane, 3,3', 5,5' -Tetramethyl-4,4'-diaminobiphenyl, 4,4'-diamino-2,2'-bis (trifluoromethyl) biphenyl, 2,2', 5,5', 6,6'-hexafluorotridin And at least one diamine selected from 4,4'-diaminoquaterphenyl.

Further, the diamines (DA-1) to (DA-18) described in paragraphs 0030 to 0031 of International Publication No. 2017/038598 are also preferable.

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

R ¹¹¹ is preferably represented by −Ar—L—Ar— from the viewpoint of the flexibility of the obtained organic film. However, Ar is an aromatic group independently, and L is an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be substituted with a fluorine atom, —O—, —CO—, —S—. , -SO _2- or -NHCO-, or a group consisting of a combination of two or more of the above. Ar is preferably a phenylene group, and L is preferably an aliphatic hydrocarbon group having 1 or 2 carbon atoms which may be substituted with a fluorine atom, —O—, —CO—, —S— or _—SO2- . .. The aliphatic hydrocarbon group here is preferably an alkylene group.

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

In formula (51), R ⁵⁰ to R ⁵⁷ are independently hydrogen atoms, fluorine atoms or monovalent organic groups, and at least one of R ⁵⁰ to R ⁵⁷ is a fluorine atom, a methyl group or trifluoro. It is a methyl group, and * independently represents a bonding site with a nitrogen atom in the formula (2).
The monovalent organic group of R ⁵⁰ to R ⁵⁷ includes an unsubstituted alkyl group having 1 to 10 carbon atoms (preferably 1 to 6 carbon atoms) and 1 to 10 carbon atoms (preferably 1 to 6 carbon atoms). Examples thereof include an alkyl fluoride group.

In formula (61), R ⁵⁸ and R ⁵⁹ are each independently a fluorine atom, a methyl group, or a trifluoromethyl group, and * is an independent binding site with a nitrogen atom in formula (2). show.
Examples of the diamine giving the structure of the formula (51) or (61) include 2,2'-dimethylbenzidine, 2,2'-bis (trifluoromethyl) -4,4'-diaminobiphenyl, and 2,2'-bis. (Fluoro) -4,4'-diaminobiphenyl, 4,4'-diaminooctafluorobiphenyl and the like can be mentioned. These may be used alone or in combination of two or more.

R ¹¹⁵ in the 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), * independently represents a binding site with another structure.

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

Specific examples of R ¹¹⁵ include tetracarboxylic acid residues remaining after removal of the anhydride group from the tetracarboxylic dianhydride. The polyimide precursor may contain only one type of tetracarboxylic dianhydride residue or two or more types as a structure corresponding to R ¹¹⁵ .
The tetracarboxylic dianhydride is preferably represented by the following formula (O).

In formula (O), R ¹¹⁵ represents a tetravalent organic group. The preferred range of R ¹¹⁵ is synonymous with R ¹¹⁵ in the formula (2), and the preferred range is also the same.

Specific examples of the tetracarboxylic acid dianhydride include pyromellitic acid dianhydride (PMDA), 3,3', 4,4'-biphenyltetracarboxylic acid dianhydride, 3,3', 4,4'-. Diphenylsulfide tetracarboxylic acid dianhydride, 3,3', 4,4'-diphenylsulfone tetracarboxylic acid dianhydride, 3,3', 4,4'-benzophenone tetracarboxylic acid dianhydride, 3,3' , 4,4'-Diphenylmethanetetracarboxylic acid dianhydride, 2,2', 3,3'-diphenylmethanetetracarboxylic acid dianhydride, 2,3,3', 4'-biphenyltetracarboxylic acid dianhydride, 2,3,3', 4'-benzophenone tetracarboxylic acid dianhydride, 4,4'-oxydiphthalic acid dianhydride, 2,3,6,7-naphthalenetetracarboxylic acid dianhydride, 1,4,5 , 7-Naphthalenetetracarboxylic acid dianhydride, 2,2-bis (3,4-dicarboxyphenyl) propane dianhydride, 2,2-bis (2,3-dicarboxyphenyl) propane dianhydride, 2 , 2-bis (3,4-dicarboxyphenyl) hexafluoropropane dianhydride, 1,3-diphenylhexafluoropropane-3,3,4,4-tetracarboxylic acid dianhydride, 1,4,5, 6-naphthalenetetracarboxylic acid dianhydride, 2,2', 3,3'-diphenyltetracarboxylic acid dianhydride, 3,4,9,10-perylenetetracarboxylic acid dianhydride, 1,2,4 5-Naphthalenetetracarboxylic acid dianhydride, 1,4,5,8-naphthalenetetracarboxylic acid dianhydride, 1,8,9,10-phenanthrentetracarboxylic acid dianhydride, 1,1-bis (2, 3-Dicarboxyphenyl) ethane dianhydride, 1,1-bis (3,4-dicarboxyphenyl) ethane dianhydride, 1,2,3,4-benzenetetracarboxylic acid dianhydride, and these. Examples thereof include alkyl having 1 to 6 carbon atoms and an alkoxy derivative having 1 to 6 carbon atoms.

Further, the tetracarboxylic dianhydrides (DAA-1) to (DAA-5) described in paragraph 0038 of International Publication No. 2017/038598 are also mentioned as preferable examples.

In formula (2), it is also possible that at least one of R ¹¹¹ and R ¹¹⁵ has an OH group. More specifically, as R ¹¹¹ , a residue of a bisaminophenol derivative can be mentioned.

R ¹¹³ and R ¹¹⁴ in the formula (2) independently represent a hydrogen atom or a monovalent organic group, respectively. The monovalent organic group preferably contains a linear or branched alkyl group, a cyclic alkyl group, an aromatic group, or a polyalkyleneoxy group. Further, it is preferable that at least one of R ¹¹³ and R ¹¹⁴ contains a polymerizable group, and it is more preferable that both contain a polymerizable group. It is also preferred that at least one of R ¹¹³ and R ¹¹⁴ contains two or more polymerizable groups. As the polymerizable group, a radically polymerizable group is preferable because it is a group capable of undergoing a cross-linking reaction by the action of heat, radicals and the like. 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 and an amino group. Be done. As the radically polymerizable group of the polyimide precursor, a group having an ethylenically unsaturated bond is preferable.
Examples of the group having an ethylenically unsaturated bond include a vinyl group, an allyl group, an isoallyl group, a 2-methylallyl group, a group having an aromatic ring directly bonded to the vinyl group (for example, a vinylphenyl group), and a (meth) acrylamide group. , (Meta) acryloyloxy group, a group represented by the following formula (III) and the like, and a group represented by the following formula (III) is preferable.

In formula (III), ^R200 represents a hydrogen atom, a methyl group, an ethyl group or a methylol group, and a hydrogen atom or a methyl group is preferable.
In formula (III), * represents a binding site with another structure.
In formula (III), R ²⁰¹ represents an alkylene group having 2 to 12 carbon atoms, -CH ₂ CH (OH) CH _2- , a cycloalkylene group or a polyalkyleneoxy group.
Examples of suitable R ²⁰¹ include alkylene groups such as ethylene group, propylene group, trimethylene group, tetramethylene group, pentamethylene group, hexamethylene group, octamethylene group and dodecamethylene group, 1,2-butanjiyl group, 1, 3-Butanjiyl group, -CH ₂ CH (OH) CH _2- , polyalkyleneoxy group, alkylene group such as ethylene group, propylene group, -CH ₂ CH (OH) CH _2- , cyclohexyl group, polyalkylene An oxy group is more preferable, and an alkylene group such as an ethylene group and a propylene group, or a polyalkylene oxy group is further preferable.
In the present invention, the polyalkyleneoxy group refers to a group to which two or more alkyleneoxy groups are directly bonded. The alkylene group in the plurality of alkyleneoxy groups contained in the polyalkyleneoxy group may be the same or different.
When the polyalkyleneoxy group contains a plurality of types of alkyleneoxy groups having different alkylene groups, the sequence of the alkyleneoxy groups in the polyalkyleneoxy group may be a random sequence or a sequence having a block. It may be an array having a pattern such as alternating.
The carbon number of the alkylene group (including the carbon number of 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 more preferable, 2 to 4 is 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.
The number of alkyleneoxy groups contained in the polyalkyleneoxy group (the number of repetitions of the polyalkyleneoxy group) is preferably 2 to 20, more preferably 2 to 10, and even more preferably 2 to 6.
As the polyalkyleneoxy group, from the viewpoint of solvent solubility and solvent resistance, a polyethyleneoxy group, a polypropyleneoxy group, a polytrimethylethyleneoxy group, a polytetramethyleneoxy group, or a plurality of ethyleneoxy groups and a plurality of propylenes. A group bonded to an oxy group is preferable, a polyethyleneoxy group or a polypropyleneoxy group is more preferable, and a polyethyleneoxy group is further preferable. In the group in which the plurality of ethyleneoxy groups and the plurality of propyleneoxy groups are bonded, the ethyleneoxy groups and the propyleneoxy groups may be randomly arranged or may be arranged by forming a block. , Alternate or the like may be arranged in a pattern. The preferred embodiment of the number of repetitions of the ethyleneoxy group and the like in these groups is as described above.

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

In formula (2), at least one of R ¹¹³ and R ¹¹⁴ may be a polar conversion group such as an acid-degradable group. The acid-degradable group is not particularly limited as long as it decomposes by the action of an acid to produce an alkali-soluble group such as a phenolic hydroxy group or a carboxy group, but is not particularly limited, but is an acetal group, a ketal group, a silyl group, or a silyl ether group. , A tertiary alkyl ester group or the like is preferable, and an acetal group or a ketal group is more preferable from the viewpoint of exposure sensitivity.
Specific examples of the acid-degradable group include tert-butoxycarbonyl group, isopropoxycarbonyl group, tetrahydropyranyl group, tetrahydrofuranyl group, ethoxyethyl group, methoxyethyl group, ethoxymethyl group, trimethylsilyl group and tert-butoxycarbonylmethyl. Examples include a group, a trimethylsilyl ether group and the like. From the viewpoint of exposure sensitivity, an ethoxyethyl group or a tetrahydrofuranyl group is preferable.

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

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

The repeating unit represented by the formula (2) is preferably a repeating unit represented by the formula (2-A). That is, it is preferable that at least one of the polyimide precursors used in the present invention is a precursor having a repeating unit represented by the formula (2-A). By including the repeating unit represented by the formula (2-A) in the polyimide precursor, it becomes possible to further widen the width of the exposure latitude.
Equation (2-A)

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

A ¹ , A ² , R ¹¹¹ , R ¹¹³ , and R ¹¹⁴ are independently synonymous with A ¹ , A ² , R ¹¹¹ , R ¹¹³ , and R ¹¹⁴ in the formula (2), and the preferred ranges are also the same. ..
R ¹¹² has the same meaning as R ¹¹² in the formula (5), and the preferred range is also the same.

The polyimide precursor may contain one type of repeating unit represented by the formula (2), but may contain two or more types. Further, it may contain a structural isomer of a repeating unit represented by the formula (2). Needless to say, the polyimide precursor may contain other types of repeating units in addition to the repeating units of the above formula (2).

The specific resin may contain one type of repeating unit represented by the formula (2), but may contain two or more types. Further, it may contain a structural isomer of a repeating unit represented by the formula (2). Needless to say, the specific resin may contain other types of repeating units in addition to the repeating unit of the above formula (2).

The specific resin contains a repeating unit represented by the following formula (3), and the ratio of the monovalent organic groups R ¹¹³ and R ¹¹⁴ to all R ¹¹³ and R ¹¹⁴ contained in the specific resin is 10 to 10. It is preferably 97 mol%.
The repeating unit represented by the formula (3) is one aspect of the repeating unit represented by the formula (2).

In formula (3), R ¹¹¹ represents a divalent organic group, R ¹¹⁵ represents a tetravalent organic group, and R ¹¹³ and R ¹¹⁴ independently represent a hydrogen atom or a monovalent organic group. show.
In the formula (3), R ¹¹¹ , R ¹¹⁵ , R ¹¹³ and R ¹¹⁴ are synonymous with R ¹¹¹ , R ¹¹⁵ , R ¹¹³ and R ¹¹⁴ in the formula (2), respectively, and the preferred embodiments are also the same.
The ratio of the monovalent organic groups R ¹¹³ and R ¹¹⁴ to all R ¹¹³ and R ¹¹⁴ contained in the specific resin is preferably 15 to 97 mol%, more preferably 20 to 95 mol%. ..

The specific resin was selected from the group consisting of repeating units represented by any of the following formulas (2-1) to (2-4) as a repeating unit having at least one of a cyclic imide structure and a cyclic isoimide structure. It preferably contains at least one repeating unit, and preferably contains at least one repeating unit selected from the group consisting of repeating units represented by any of the following formulas (2-1) to (2-2). Is more preferable.

In formulas (2-1) to (2-4), R ¹¹¹ , R ¹¹⁴ , R ¹¹⁵ and A ¹ are synonymous with R ¹¹¹ , R ¹¹⁴ , R ¹¹⁵ and A ¹ in the above formula (2), respectively. The same applies to the preferred embodiment.

The total content of the repeating unit represented by any of the formulas (2-1) to (2-4) is such that the total content of the cyclic imide structure and the cyclic isoimide structure in the specific resin is within the above range. And it is sufficient.

As one embodiment of the specific resin in the present invention, the total content of the repeating unit represented by the formula (2) and the repeating unit represented by any of the formulas (2-1) to (2-4). However, there is an embodiment in which 50 mol% or more of all repeating units is used. The total content is more preferably 70 mol% or more, further 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 the repeating units in the specific resin except the terminal are the repeating unit represented by the formula (2) and the formulas (2-1) to (2-4). ) May be any of the repeating units.
Further, as one embodiment of the specific resin in the present invention, the total of the repeating units represented by the formula (3) and the repeating units represented by any of the formulas (2-1) to (2-4). An embodiment in which the content is 50 mol% or more of all repeating units can be mentioned. The total content is more preferably 70 mol% or more, further 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 the repeating units in the specific resin except the terminal are the repeating unit represented by the formula (3) and the formulas (2-1) to (2-4). ) May be any of the repeating units.

As an embodiment of the polyimide precursor in the present invention, there is an embodiment in which the content of the repeating unit represented by the formula (2) is 50 mol% or more of all the repeating units. The total content is more preferably 70 mol% or more, further 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 the repeating units in the polyimide precursor except the terminal may be the repeating unit represented by the formula (2).

The weight average molecular weight (Mw) of the polyimide precursor is preferably 5,000 to 100,000, more preferably 10,000 to 50,000, and even more preferably 15,000 to 40,000. The number average molecular weight (Mn) is preferably 2,000 to 40,000, more preferably 3,000 to 30,000, and even more preferably 4,000 to 20,000.
The degree of dispersion of the molecular weight of the polyimide precursor is preferably 1.5 or more, more preferably 1.8 or more, and further preferably 2.0 or more. The upper limit of the dispersity of the molecular weight of the polyimide precursor is not particularly determined, but for example, it is preferably 7.0 or less, more preferably 6.5 or less, still more preferably 6.0 or less.
In the present specification, the degree of molecular weight dispersion is a value calculated by weight average molecular weight / number average molecular weight.
When the resin composition contains a plurality of types of polyimide precursors as the specific resin, it is preferable that the weight average molecular weight, the number average molecular weight, and the degree of dispersion of at least one type of polyimide precursor are in the above range. Further, it is also preferable that the weight average molecular weight, the number average molecular weight, and the degree of dispersion calculated by using the plurality of types of polyimide precursors as one resin are within the above ranges.

[Manufacturing method of specific resin]
A preferred first aspect of the method for producing a specific resin includes an amidation step of reacting a dicarboxylic acid compound with a diamine compound to obtain an amide compound, and a partial imidization step of partially imidizing the amide compound.

The amidation step may be carried out by a known method, but for example, it is preferable that the dicarboxylic acid or the dicarboxylic acid derivative is halogenated with a halogenating agent and then reacted with a diamine.
Examples of the halogenating agent include thionyl chloride and phosphoryl chloride.
Further, it can also be synthesized by using a non-halogen catalyst without using the above-mentioned halogenating agent. As the non-halogen catalyst, a known amidation catalyst containing no halogen atom can be used without particular limitation. For example, a boroxin compound, an N-hydroxy compound, a tertiary amine, a phosphoric acid ester, or an amine can be used. Examples thereof include carbodiimide compounds such as salts and urea compounds. Examples of the carbodiimide compound include N, N'-diisopropylcarbodiimide, N, N'-dicyclohexylcarbodiimide, 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide, 1- [3- (dimethylamino) propyl]. -3-Ethylcarbodiimide methiodide and the like can be mentioned.
It is also preferable to carry out the amidation step at −10 ° C. or lower.

In the first aspect described above, the amidation step can be performed in an organic solvent.
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.

In the above amidation step, acid anhydride, monocarboxylic acid, monoacid chloride compound, and monoactivity are used to further improve storage stability and keep the acid value within the above range in the production of polyimide precursors and the like. The end of the polyimide precursor or the like may be sealed with a terminal sealant such as an ester compound. It is more preferable to use monoamine as the terminal encapsulant, and preferred compounds of monoamine are aniline, 2-ethynylaniline, 3-ethynylaniline, 4-ethynylaniline, 5-amino-8-hydroxyquinoline, 1-. Hydroxy-7-aminonaphthalene, 1-hydroxy-6-aminonaphthalene, 1-hydroxy-5-aminonaphthalene, 1-hydroxy-4-aminonaphthalene, 2-hydroxy-7-aminonaphthalene, 2-hydroxy-6-amino Naphthalene, 2-hydroxy-5-aminonaphthalene, 1-carboxy-7-aminonaphthalene, 1-carboxy-6-aminonaphthalene, 1-carboxy-5-aminonaphthalene, 2-carboxy-7-aminonaphthalene, 2-carboxy -6-Aminonaphthalene, 2-carboxy-5-Aminonaphthalene, 2-Aminobenzoic acid, 3-Aminobenzoic acid, 4-Aminobenzoic acid, 4-Aminosalicylic acid, 5-Aminosalicylic acid, 6-Aminosalicylic acid, 2- Aminobenzene sulfonic acid, 3-aminobenzene sulfonic acid, 4-aminobenzene sulfonic acid, 3-amino-4,6-dihydroxypyrimidine, 2-aminophenol, 3-aminophenol, 4-aminophenol, 2-aminothiophenol , 3-Aminothiophenol, 4-Aminothiophenol and the like. Two or more of these may be used, or a plurality of different end groups may be introduced by reacting a plurality of terminal encapsulants.

The method for producing the specific resin may include a dicarboxylic acid compound synthesis step of reacting a tetracarboxylic acid dianhydride with an alcohol compound to obtain a dicarboxylic acid compound (diester compound of the tetracarboxylic acid dianhydride).
The above reaction can be carried out with reference to a known esterification reaction.
The dicarboxylic acid compound obtained in the dicarboxylic acid compound synthesis step can be used as the dicarboxylic acid compound in the amidation step.

The partial imidization step may be carried out by thermal imidization or by chemical imidization using a base or the like (for example, imidization using a base). These methods can be performed by known methods.
The partial imidization step can be performed by adjusting the total content of the cyclic imide structure and the cyclic isoimide structure in the finally obtained specific resin within the above range.

The first aspect of the method for producing the specific resin may include a quenching step of adding water or an alcohol compound to the reaction solution containing the amide compound after the amidation step.
The quenching step may be performed after the amidation step and before the partial imidization step, or may be performed after the partial imidization step, but it is preferably performed after the amidation step and before the partial imidization step. ..

The method for producing the specific resin may further include a reprecipitation step.
Specific examples of the reprecipitation step include a step of adding the reaction solution after the quenching step to water or alcohol to precipitate the polyimide precursor.
The reprecipitation step may be performed after the quenching step. When the partial imidization step is included, it may be performed before the partial imidization step or after the partial imidization step, but it is preferably performed after the quenching step and before the partial imidization step.

The method for producing the specific resin may include a re-dissolution step after the re-precipitation step.
As the redissolving step, specifically, for example, the precipitated resin after the above-mentioned reprecipitation step is obtained by filtration or the like, and the obtained product is dissolved in a solvent in which a specific resin such as tetrahydrofuran is soluble to prepare a dissolution liquid. The process can be mentioned.
The reprecipitation step and the redissolution step may be repeated a plurality of times.
For example, an embodiment in which the re-dissolution step is performed after the re-precipitation step and the re-dissolution step is performed again with respect to the solution obtained after the re-dissolution step can be mentioned.

The first aspect may further include a drying step.
The drying step is preferably, for example, a step of acquiring the precipitated resin after the above-mentioned reprecipitation step by filtration or the like and drying the obtained product.
The drying method is not particularly limited, and a known method may be used. For example, drying with a known vacuum dryer can be mentioned.
The drying conditions are not particularly limited, and examples thereof include conditions such as drying at 20 ° C. to 60 ° C. under reduced pressure.

In addition, the first aspect may further include a purification step of purifying the specific resin.
By the above purification step, for example, the residue of the catalyst such as the above-mentioned halogenating agent, the base added in the above-mentioned partial imidization step, and the like can be removed.
The purification method is not particularly limited, and a known method can be used, and examples thereof include a method in which an ion exchange resin is brought into contact with a solution containing a specific resin.

A preferred second aspect of the method for producing a specific resin comprises an amidation step of reacting a dicarboxylic acid compound with a diamine compound in the presence of a basic catalyst to obtain an amide compound.
Examples of the basic catalyst include tertiary amines, amine salts and carbodiimide compounds, with carbodiimide compounds being preferred. Examples of the carbodiimide compound include N, N'-diisopropylcarbodiimide, N, N'-dicyclohexylcarbodiimide, 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide, 1- [3- (dimethylamino) propyl]. -3-Ethylcarbodiimide methiodide and the like can be mentioned.

In the second aspect described above, the amidation step can be performed in an organic solvent.
The organic solvent can be appropriately determined depending on the raw material, and the same solvent as in the first aspect described above can be used, but a low-polarity solvent is used for the purpose of leaving the carboxy group at the resin terminal. Is also preferable.
Examples of the low-polarity solvent include tetrahydrofuran, PGMEA (propylene glycol monoethyl ether acetate), diglyme (diglyme, diethylene glycol dimethyl ether) and the like.

The second aspect may further include the above-mentioned dicarboxylic acid compound synthesis step, the above-mentioned quenching step, the above-mentioned reprecipitation step, the above-mentioned redissolution step, the above-mentioned drying step, the above-mentioned purification step, and the like.

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

Further, it is also preferable that the resin composition of the present invention contains at least two kinds of resins.
Specifically, the resin composition of the present invention may contain two or more kinds of the specific resin and another resin described later in total, or may contain two or more kinds of the specific resin, but the specific resin may be contained. It is preferable to include two or more kinds.
When the curable resin composition of the present invention contains two or more kinds of polyimide precursors, the total content and acid value of the cyclic imide structure and the cyclic isoimide structure contained in at least one kind of polyimide precursor are within the above ranges. It is preferable that the total content and acid value of the cyclic imide structure and the cyclic isoimide structure contained in all the polyimide precursors are in the above range, as opposed to the case where the total amount of all the polyimide precursors is 1 g. For each of the polyimide precursors contained in the curable resin composition, the total content of the cyclic imide structure and the cyclic isoimide structure and the acid value are more preferably in the above ranges.
When the resin composition of the present invention contains two or more kinds of specific resins, for example, two or more kinds of polyimides which are polyimide precursors and have different structures derived from dianhydride (R ¹¹⁵ in the above formula (2)). It is preferable to include a precursor.

<Other resins>
The resin composition of the present invention may contain the above-mentioned specific resin and another resin different from the specific resin (hereinafter, also simply referred to as “other resin”).
Other resins include phenolic resin, polyamide, epoxy resin, polysiloxane, resin containing siloxane structure, (meth) acrylic resin, (meth) acrylamide resin, urethane resin, butyral resin, styryl resin, polyether resin, polyester resin. And so on.
For example, by further adding a (meth) acrylic resin, a resin composition having excellent coatability can be obtained, and a pattern (cured product) having excellent solvent resistance can be obtained.
For example, instead of the polymerizable compound described later, or in addition to the polymerizable compound described later, a high polymerizable base value having a weight average molecular weight of 20,000 or less (for example, the molar amount of the polymerizable group contained in 1 g of the resin). (1 × 10 ^-3 mol / g or more) By adding a (meth) acrylic resin to the resin composition, the coatability of the resin composition, the solvent resistance of the pattern (cured product), etc. can be improved. can.

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

<Organometallic complex>
From the viewpoint of chemical resistance, the curable resin composition of the present invention preferably contains an organometallic complex.
By containing the specific resin and the organometallic complex, at least one of the cyclic imide structure and the cyclic isoimide structure contained in the specific resin interacts with the organometallic complex, so that the organometallic complex in the photosensitive film and the cured product It is presumed that the aggregation of metal is suppressed.
Therefore, it is presumed that the chemical resistance is further improved as compared with the case where the conventional polyimide precursor different from the specific resin and the organometallic complex are used in combination.

The organic metal complex may be an organic complex compound containing a metal atom, but is preferably a complex compound containing a metal atom and an organic group, and is a compound in which an organic group is coordinated with respect to the metal atom. It is more preferably a metallocene compound, and even more preferably a metallocene compound.
In the present invention, the metallocene compound refers to an organic metal complex having two cyclopentadienyl anion derivatives which may have a substituent as η5-ligands.
The organic group is not particularly limited, but a hydrocarbon group or a group consisting of a hydrocarbon group and a heteroatom is preferable. As the hetero atom, 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 at least two are more preferably 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 cyclic group may be a hydrocarbon ring or a heterocycle, but a hydrocarbon ring is preferable.
As the cyclic group of the 5-membered ring, a cyclopentadienyl group is preferable.
Further, the organometallic complex used in the present invention preferably contains 2 to 4 cyclic groups in one molecule.

The metal contained in the organic metal complex is not particularly limited, but is preferably a metal corresponding to a Group 4 element, and is at least one metal selected from the group consisting of titanium, zirconium and hafnium. More preferably, it is more preferably at least one metal selected from the group consisting of titanium and zirconium, and particularly preferably titanium.

The organometallic complex may contain two or more metal atoms or may contain 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 may contain two or more kinds of metal atoms.

The organic metal complex is preferably a ferrocene compound, a titanosen compound, a zirconocene compound or a hafnosen compound, more preferably a titanosen compound, a zirconosen compound or a hafnosen compound, and even more preferably a titanosen compound or a zirconosen compound. , Titanosen compounds are particularly preferred.

An embodiment in which the organometallic complex has an ability to initiate photoradical polymerization is also one of the preferred embodiments of the present invention.
According to the present invention, it is considered that the use of the specific resin suppresses the aggregation of the organometallic complex as described above, and the organometallic complex is dispersed in the membrane in a nearly uniform state.
Therefore, when the organic metal complex has the ability to initiate photoradical polymerization, it is considered that the local aggregation of the radical polymerization initiator due to the aggregation of the organic metal complex is suppressed.
It is considered that the degree of polymerization of the specific resin or the polymerizable compound tends to be close to uniform in the membrane by suppressing the aggregation of the radical polymerization initiator. Therefore, it is considered that the generation of development residue and the disconnection of the pattern are unlikely to occur, and the resolution is likely to be improved.
In the present invention, having the ability to initiate photoradical polymerization means that free radicals capable of initiating radical polymerization can be generated by irradiation with light. For example, when a composition containing a radical cross-linking agent and an organic metal complex is irradiated with light in a wavelength range in which the organic metal complex absorbs light and the radical cross-linking agent does not absorb light, radicals are generated. By confirming the presence or absence of the disappearance of the cross-linking agent, the presence or absence of the photoradical polymerization initiation ability can be confirmed. In order to confirm the presence or absence of disappearance, an appropriate method can be selected depending on the type of radical cross-linking agent, and for example, it may be confirmed by IR measurement (infrared spectroscopy measurement) or HPLC measurement (high performance liquid chromatography).
When the organometallic complex has a photoradical polymerization initiating ability, the organometallic complex is preferably a metallocene compound, more preferably a titanosen compound, a zirconocene compound or a hafnosen compound, and more preferably a titanosen compound or a zirconocene compound. Is more preferable, and a titanosen compound is particularly preferable.
When the organic metal complex does not have the ability to initiate photoradical polymerization, the organic metal complex is selected from the group consisting of a titanosen compound, a tetraalkoxytitanium compound, a titanium acylate compound, a titanium chelate compound, a zirconocene compound and a hafnosen compound. It is preferably a compound of a species, more preferably at least one compound selected from the group consisting of a titanosen compound, a zirconocene compound and a hafnosen compound, and more preferably at least one selected from the group consisting of a titanosen compound and a zirconosen compound. It is more preferably a species compound, and particularly preferably a titanosen 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 R is an independent substituent.
It is preferable that the R is independently selected from an aromatic group, an alkyl group, a halogen atom and an alkylsulfonyloxy group.

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

Specific examples of the organic metal complex are not particularly limited, but are tetraisopropoxytitanium, tetrakis (2-ethylhexyloxy) titanium, diisopropoxybis (ethylacetacetate) titanium, and diisopropoxybis (acetylacetate). Nato) Titanium, bis (η5-2,4-cyclopentadiene-1-yl) bis (2,6-difluoro-3- (1H-pyrrole-1-yl) phenyl) titanium, pentamethylcyclopentadiene titanium tri Examples thereof include methoxide, bis (η5-2,4-cyclopentadiene-1-yl) bis (2,6-difluorophenyl) titanium, and the following compounds.

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

The content of the organometallic complex is preferably 0.1 to 30% by mass with respect to 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, further 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.
As the organometallic complex, one kind or two or more kinds can be used. When two or more types are used, the total amount is preferably in the above range.

<Solvent>
The resin composition of the present invention preferably contains a solvent.
As the solvent, a known solvent can be arbitrarily used. The solvent is preferably an organic solvent. Examples of the organic solvent include compounds such as esters, ethers, ketones, cyclic hydrocarbons, sulfoxides, amides, 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, and γ-butyrolactone. , Ε-caprolactone, δ-valerolactone, alkyl oxyacetate (eg, methyl alkyloxyacetate, ethyl alkyloxyacetate, butyl alkyloxyacetate (eg, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, etc.) Ethyl ethoxyacetate, etc.)), 3-alkyloxypropionate alkyl esters (eg, methyl 3-alkyloxypropionate, ethyl 3-alkyloxypropionate, etc.) (eg, methyl 3-methoxypropionate, 3-methoxypropionate, etc.) Ethyl, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, etc.)), 2-alkyloxypropionate alkyl esters (eg, methyl 2-alkyloxypropionate, ethyl 2-alkyloxypropionate, 2-alkyl) Propyl oxypropionate and the like (eg, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate), 2-alkyloxy- Methyl 2-methylpropionate and ethyl 2-alkyloxy-2-methylpropionate (eg, methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, etc.), methyl pyruvate, pyruvin Suitable examples thereof include ethyl acid, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutanoate, ethyl 2-oxobutate, ethyl hexanoate, ethyl heptate, dimethyl malonate, diethyl malonate and the like. ..

Examples of ethers include ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether, diethylene glycol butyl methyl ether, triethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, and ethylene glycol monoethyl ether. Methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol dimethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether, ethylene glycol Suitable examples include monobutyl ether acetate, diethylene glycol ethyl methyl ether, propylene glycol monopropyl ether acetate, dipropylene glycol dimethyl ether and the like.

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

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

As the sulfoxides, for example, dimethyl sulfoxide is preferable.

As amides, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N-cyclohexyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, N, N-dimethylisobutyramide, Suitable examples include 3-methoxy-N, N-dimethylpropionamide, 3-butoxy-N, N-dimethylpropionamide, N-formylmorpholine, N-acetylmorpholine and the like.

As ureas, N, N, N', N'-tetramethylurea, 1,3-dimethyl-2-imidazolidinone and the like are preferable.

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

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

In the present invention, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, methyl 3-methoxypropionate, 2-heptanone, cyclohexanone, cyclopentanone, γ- One solvent selected from butyrolactone, dimethyl sulfoxide, ethyl carbitol acetate, butyl carbitol acetate, N-methyl-2-pyrrolidone, propylene glycol methyl ether, and propylene glycol methyl ether acetate, levoglucosenone, dihydrolevoglucosenone, Alternatively, a mixed solvent composed of two or more kinds is preferable. The combined use of dimethyl sulfoxide and γ-butyrolactone or the combined use of N-methyl-2-pyrrolidone and ethyl lactate is particularly preferable.

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

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

[Initiator of polymerization]
The resin composition of the present invention preferably contains a polymerization initiator that can initiate polymerization by light and / or heat. In particular, it is preferable to include a photopolymerization initiator.
The photopolymerization initiator is preferably a photoradical polymerization initiator. The photoradical polymerization initiator is not particularly limited and may be appropriately selected from known photoradical polymerization initiators. For example, a photoradical polymerization initiator having photosensitivity to light rays in the ultraviolet region to the visible region is preferable. Further, it may be an active agent that causes some action with a photoexcited sensitizer and generates an active radical.

The photoradical polymerization initiator contains at least one compound having a molar extinction coefficient of at least about 50 L · mol ^-1 · cm ^-1 within a wavelength range of about 240 to 800 nm (preferably 330 to 500 nm). Is preferable. 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, a known compound can be arbitrarily used. For example, halogenated hydrocarbon derivatives (for example, compounds having a triazine skeleton, compounds having an oxadiazole skeleton, compounds having a trihalomethyl group, etc.), acylphosphine compounds such as acylphosphine oxide, hexaarylbiimidazole, oxime derivatives and the like. Oxyme compounds, organic peroxides, thio compounds, ketone compounds, aromatic onium salts, ketooxime ethers, α-aminoketone compounds such as aminoacetophenone, α-hydroxyketone compounds such as hydroxyacetophenone, azo compounds, azido compounds, Examples thereof include metallocene compounds, organic boron compounds, and iron arene complexes. For details thereof, the description in paragraphs 0165 to 0182 of JP2016-027357 and paragraphs 0138 to 0151 of International Publication No. 2015/199219 can be referred to, and the contents thereof are incorporated in the present specification. Further, paragraphs 0065 to 0111 of JP-A-2014-130173, compounds described in Japanese Patent No. 6301489, MATERIAL STAGE 37-60p, vol. 19, No. 3, 2019 Peroxide-based Photopolymerization Initiator, International Publication No. 2018/221177, Photopolymerization Initiator, International Publication No. 2018/110179, Photopolymerization Initiator, JP-A-2019-043864. Examples thereof include the photopolymerization initiator described in JP-A-2019-044030, the photopolymerization initiator described in JP-A-2019-167313, and the contents thereof are also described in this publication. Incorporated in the specification.

As the ketone compound, for example, the compound described in paragraph 0087 of JP-A-2015-087611 is exemplified, and the content thereof is incorporated in the present specification. As a commercially available product, Kayacure-DETX-S (manufactured by Nippon Kayaku Co., Ltd.) is also preferably used.

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

Examples of the α-hydroxyketone initiator include Omnirad 184, Omnirad 1173, Omnirad 2959, Omnirad 127 (all manufactured by IGM Resins BV), IRGACURE 184 (IRGACURE is a registered trademark), DAROCUR 1173, and DAROCUR 1173. -2959, IRGACURE 127 (trade name: both manufactured by BASF) can be used.

As the α-aminoketone-based initiators, Omnirad 907, Omnirad 369, Omnirad 369E, Omnirad 379EG (all manufactured by IGM Resins BV), IRGACURE 907, IRGACURE 369, and IRGACURE 369, all of which are IRGACURE 37. (Manufactured by the company) can be used.

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

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

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

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

Specific examples of the oxime compound include the compound described in JP-A-2001-233842, the compound described in JP-A-2000-080068, the compound described in JP-A-2006-342166, and J. Am. C. S. The compound according to Perkin II (1979, pp. 1653-1660), J. Mol. C. S. The compound described in Perkin II (1979, pp. 156-162), the compound described in Journal of Photopolisr Science and Technology (1995, pp. 202-232), the compound described in JP-A-2000-066385, the compound described in JP-A-2000-066385. Compounds described in JP-A-2004-534797, compounds described in JP-A-2017-109766, compounds described in Japanese Patent No. 6065596, compounds described in International Publication No. 2015/152153, International Publication No. 2017. The compound described in / 051680, the compound described in JP-A-2017-198865, the compound described in paragraphs 0025 to 0038 of International Publication No. 2017/164127, the compound described in International Publication No. 2013/167515, etc. And this content is incorporated herein by reference.

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

Commercially available products include IRGACURE OXE 01, IRGACURE OXE 02, IRGACURE OXE 03, IRGACURE OXE 04 (above, manufactured by BASF), ADEKA PTOMER N-1919 (manufactured by ADEKA Corporation, JP-A-2012-014052). A radical polymerization initiator 2) is also preferably used. In addition, TR-PBG-304, TR-PBG-305 (manufactured by Changzhou Powerful Electronics New Materials Co., Ltd.), Adeka Arkuru's NCI-730, NCI-831 and Adeka Arkuru's NCI-930 (manufactured by ADEKA Corporation) are also used. be able to. Further, DFI-091 (manufactured by Daito Chemix Co., Ltd.) and SpeedCure PDO (manufactured by SARTOMER ARCEMA) can be used. Further, an oxime compound having the following structure can also be used.

As the photoradical polymerization initiator, an oxime compound having a fluorene ring can also be used. Specific examples of the oxime compound having a fluorene ring include the compound described in JP-A-2014-137466 and the compound described in Japanese Patent No. 06636081, and the contents thereof are incorporated in the present specification.

As the photoradical polymerization initiator, an oxime compound having a skeleton in which at least one benzene ring of the carbazole ring is a naphthalene ring can also be used. Specific examples of such oxime compounds include the compounds described in WO 2013/083505, the contents of which are incorporated herein.

It is also possible to use an oxime compound having a fluorine atom. Specific examples of such an oxime compound include the compounds described in JP-A-2010-262028, the compounds 24, 36-40 described in paragraph 0345 of JP-A-2014-500852, and JP-A-2013. The compound (C-3) and the like described in paragraph 0101 of the publication No. 164471 are mentioned, and the contents thereof are incorporated in the present specification.

As the photopolymerization initiator, an oxime compound having a nitro group can be used. The oxime compound having a nitro group is also preferably a dimer. Specific examples of the oxime compound having a nitro group include the compounds described in paragraphs 0031 to 0047 of JP2013-114249A and paragraphs 0008-0012 and 0070-0079 of JP-A-2014-137466. Examples of the compounds described in paragraphs 0007 to 0025 of Japanese Patent No. 4223071 are incorporated herein by reference. Further, examples of the oxime compound having a nitro group include ADEKA ARKULS NCI-831 (manufactured by ADEKA Corporation).

As the photoradical polymerization initiator, an oxime compound having a benzofuran skeleton can also be used. Specific examples include OE-01 to OE-75 described in International Publication No. 2015/036910.

As the photoradical polymerization initiator, an oxime compound in which a substituent having a hydroxy group is bonded to the carbazole skeleton can also be used. Examples of such a photopolymerization initiator include the compounds described in International Publication No. 2019/088055, and the contents thereof are incorporated in the present specification.

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

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

In the formula, ^RX1 is an alkyl group, an alkenyl group, an alkoxy group, an aryl group, an aryloxy group, a heterocyclic group, a heterocyclic oxy group, an alkylsulfanyl group, an arylsulfanyl group, an alkylsulfinyl group, an arylsulfinyl group, an alkylsulfonyl group. Represents a group, arylsulfonyl group, acyl group, acyloxy group, amino group, phosphinoyl group, carbamoyl group or sulfamoyl group.
^RX2 contains an alkyl group, an alkenyl group, an alkoxy group, an aryl group, an aryloxy group, a heterocyclic group, a heterocyclic oxy group, an alkylsulfanyl group, an arylsulfanyl group, an alkylsulfinyl group, an arylsulfinyl group, an alkylsulfonyl group and an aryl. Represents a sulfonyl group, an acyloxy group or an amino group
^{RX3 to RX14} ^{independently} represent a hydrogen atom or a substituent.
However, at least one of ^RX10 to ^RX14 is an electron-withdrawing group.

In the above formula, it is preferable that ^RX12 is an electron-withdrawing group and ^RX10 , ^RX11 , ^RX13 and ^RX14 are hydrogen atoms.

Specific examples of the oxime compound OX include the compounds described in paragraphs 0083 to 0105 of Japanese Patent No. 4600600, the contents of which are incorporated in the present specification.

The most preferable oxime compound includes an oxime compound having a specific substituent shown in JP-A-2007-269779 and an oxime compound having a thioaryl group shown in JP-A-2009-191061. Incorporated herein.

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

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

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

In formula (I), 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, and the like. Alternatively, the number of carbon atoms interrupted by an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, a halogen atom, a cyclopentyl group, a cyclohexyl group, an alkenyl group having 2 to 12 carbon atoms, or one or more oxygen atoms. It is a phenyl group or a biphenyl group substituted with at least one of an alkyl group of 2 to 18 and an alkyl group having 1 to 4 carbon atoms, and ^RI01 is a group represented by the formula (II). It is the same group as ^RI00 , and ^RI02 to ^RI04 are independently alkyl groups having 1 to 12 carbon atoms, alkoxy groups having 1 to 12 carbon atoms, or halogen atoms.

In the formula, R ^I05 to R I ⁰⁷ are the same as R I ⁰² to R I ⁰⁴ of the above formula (I).

Further, as the photoradical polymerization initiator, the compounds described in paragraphs 0048 to 0055 of International Publication No. 2015/125469 can also be used, and the contents thereof are incorporated in the present specification.

As the photoradical polymerization initiator, a bifunctional or trifunctional or higher functional photoradical polymerization initiator may be used. By using such a photoradical polymerization initiator, two or more radicals are generated from one molecule of the photoradical polymerization initiator, so that good sensitivity can be obtained. Further, when a compound having an asymmetric structure is used, the crystallinity is lowered, the solubility in a solvent or the like is improved, the precipitation is less likely to occur with time, and the stability of the resin composition with time can be improved. .. Specific examples of the bifunctional or trifunctional or higher functional photo-radical polymerization initiator are described in JP-A-2010-527339, JP-A-2011-524436, International Publication No. 2015/004565, and JP-A-2016-532675. Dimerics of oxime compounds described in paragraphs 0407 to 0412, paragraphs 0039 to 0055 of International Publication No. 2017/033680, compounds (E) and compounds described in JP-A-2013-522445. G), the oxime esters photoinitiator described in paragraph No. 0007 of Cmpd1-7 described in International Publication No. 2016/034943, JP-A-2017-523465, JP-A-2017-167399. The photoinitiator described in paragraphs 0020 to 0033, the photopolymerization initiator (A) described in paragraphs 0017 to 0026 of JP-A-2017-151342, is described in Japanese Patent No. 6469669. Examples include oxime ester photoinitiators, the contents of which are incorporated herein.

When the photopolymerization initiator is contained, the content thereof is preferably 0.1 to 30% by mass, more preferably 0.1 to 20% by mass, based on the total solid content of the resin composition of the present invention. It is more preferably 0.5 to 15% by mass, and even more preferably 1.0 to 10% by mass. Only one type of photopolymerization initiator may be contained, or two or more types may be contained. When two or more kinds of photopolymerization initiators are contained, the total amount is preferably in the above range.
Since the photopolymerization initiator may also function as a thermal polymerization initiator, cross-linking with the photopolymerization initiator may be further promoted by heating an oven, a hot plate, or the like.

[Sensitizer]
The resin composition may contain a sensitizer. The sensitizer absorbs specific active radiation and becomes an electronically excited state. The sensitizer in the electron-excited state comes into contact with the thermal radical polymerization initiator, the photoradical polymerization initiator, and the like, and acts such as electron transfer, energy transfer, and heat generation occur. As a result, the thermal radical polymerization initiator and the photoradical polymerization initiator undergo a chemical change and decompose to generate a radical, an acid or a base.
Usable sensitizers include benzophenone, Michler's ketone, coumarin, pyrazole azo, anilino azo, triphenylmethane, anthracinone, anthracene, anthrapyridone, benzylidene, oxonol, pyrazole triazole azo. , Pyridone azo, cyanine, phenothiazine, pyrrolopyrazole azomethine, xanthene, phthalocyanine, penzopyran, indigo and the like can be used.
Examples of the sensitizer include Michler's ketone, 4,4'-bis (diethylamino) benzophenone, 2,5-bis (4'-diethylaminobenzal) cyclopentane, and 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-dimethylaminophenylbinylene) benzothiazole, 2- (p-dimethylaminophenylbinylene) iso Naftthiazole, 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-diethylamino Kumarin (7- (diethylamino) coumarin-3-carboxylate ethyl), N-phenyl-N'-ethylethanolamine, N-phenyldiethanolamine, Np-tolyldiethanolamine, N-phenylethanolamine, 4-morpholinobenzophenone, Isoamyl dimethylaminobenzoate, isoamyl diethylaminobenzoate, 2-mercaptobenzimidazole, 1-phenyl-5-mercaptotetrazole, 2-mercaptobenzothiazole, 2- (p-dimethylaminostyryl) benzoxazole, 2- (p-dimethyl) Aminostyryl) benzothiazole, 2- (p-dimethylaminostyryl) naphtho (1,2-d) thiazole, 2- (p-dimethylaminobenzoyl) styrene, diphenylacetamide, benzanilide, N-methylacetanilide, 3', 4 '-Dimethylacetanilide and the like can be mentioned.
Moreover, you may use other sensitizing dyes.
For details of the sensitizing dye, the description in paragraphs 0161 to 0163 of JP-A-2016-027355 can be referred to, and the content thereof is incorporated in the present specification.

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

[Chain transfer agent]
The resin composition of the present invention may contain a chain transfer agent. Chain transfer agents are defined, for example, in the Polymer Dictionary, Third Edition (edited by the Society of Polymer Science, 2005), pp. 683-684. Examples of the chain transfer agent include RAFT (Reversible Addition Fragmentation chain Transfer), which is a group of compounds having -S-S-, _-SO2 -S-, -NO-, SH, PH, SiH, and GeH in the molecule. ) Dithiobenzoate having a thiocarbonylthio group, trithiocarbonate, dithiocarbamate, xantate compound and the like used for polymerization are used. They can donate hydrogen to low-activity radicals to generate radicals, or they can be oxidized and then deprotonated to generate radicals. In particular, thiol compounds can be preferably used.

Further, as the chain transfer agent, the compounds described in paragraphs 0152 to 0153 of International Publication No. 2015/199219 can also be used, and the contents thereof are incorporated in the present specification.

When the resin composition of the present invention has a chain transfer agent, the content of the chain transfer agent is preferably 0.01 to 20 parts by mass with respect to 100 parts by mass of the total solid content of the resin composition of the present invention. 1 to 10 parts by mass is more preferable, and 0.5 to 5 parts by mass is further preferable. The chain transfer agent may be only one kind or two or more kinds. When there are two or more types of chain transfer agents, the total is preferably in the above range.

[Photoacid generator]
The resin composition of the present invention preferably contains a photoacid generator.
The photoacid generator represents a compound that generates at least one of Bronsted acid and Lewis acid by irradiation with light of 200 nm to 900 nm. The irradiated light is preferably light having a wavelength of 300 nm to 450 nm, and more preferably light having a wavelength of 330 nm to 420 nm. It is preferable that the photoacid generator is a photoacid generator capable of generating an acid by being exposed to light when used alone or in combination with a sensitizer.
Examples of generated acids include hydrogen halide, carboxylic acid, sulfonic acid, sulfinic acid, thiosulfinic acid, phosphoric acid, phosphoric acid monoester, phosphoric acid diester, boron derivative, phosphorus derivative, antimony derivative, halogen peroxide, etc. Sulfonamide and the like are preferably mentioned.

Examples of the photoacid generator used in the resin composition of the present invention include quinone diazide compounds, oxime sulfonate compounds, organic halogenated compounds, organic borate compounds, disulfone compounds, onium salt compounds and the like.
Organic halogen compounds, oxime sulfonate compounds, and onium salt compounds are preferable from the viewpoint of sensitivity and storage stability, and oxime esters are preferable from the viewpoint of mechanical properties of the film to be formed.

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

Specifically, as the hydroxy compound, phenol, trihydroxybenzophenone, 4methoxyphenol, isopropanol, octanol, t-Bu alcohol, cyclohexanol, naphthol, Bis-Z, BisP-EZ, TekP-4HBPA, TrisP-HAP, TrisP- PA, TrisP-SA, TrisOCR-PA, BisOCHP-Z, BisP-MZ, BisP-PZ, BisP-IPZ, BisOCP-IPZ, BisP-CP, BisRS-2P, BisRS-3P, BisP-OCHP, Methylenetris-FR -CR, BisRS-26X, DML-MBPC, DML-MBOC, DML-OCHP, DML-PCHP, DML-PC, DML-PTBP, DML-34X, DML-EP, DML-POP, Dimethylol-BisOC-P, DML -PFP, DML-PSBP, DML-MTrisPC, TriML-P, TriML-35XL, TML-BP, TML-HQ, TML-pp-BPF, TML-BPA, TMOM-BP, HML-TPPHBA, HML-TPHAP (and above) , Product name, manufactured by Honshu Kagaku Kogyo), BIR-OC, BIP-PC, BIR-PC, BIR-PTBP, BIR-PCHP, BIP-BIOC-F, 4PC, BIR-BIPC-F, TEP-BIP-A, 46DMOC, 46DMEEP, TM-BIP-A (trade name, manufactured by Asahi Organic Materials Industry Co., Ltd.), 2,6-dimethoxymethyl-4-t-butylphenol, 2,6-dimethoxymethyl-p-cresol, 2,6- Examples thereof include diacetoxymethyl-p-cresol, naphthol, tetrahydroxybenzophenone, gallic acid methyl ester, bisphenol A, bisphenol E, methylene bisphenol, BisP-AP (trade name, manufactured by Honshu Chemical Industry Co., Ltd.), and novolak resin. , Not limited to these.

Specifically, the amino compounds include aniline, methylaniline, diethylamine, butylamine, 1,4-phenylenediamine, 1,3-phenylenediamine, 4,4'-diaminodiphenyl ether, 4,4'-diaminodiphenylmethane, 4,4. ′ -Diaminodiphenyl sulfone, 4,4′-diaminodiphenyl sulfide and the like can be mentioned, but the present invention is not limited thereto.

Specific examples of the polyhydroxypolyamino compound include, but are not limited to, 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane and 3,3'-dihydroxybenzidine. ..

Among these, it is preferable that the quinone diazide compound contains an ester with a phenol compound and a 4-naphthoquinone diazidosulfonyl group. This makes it possible to obtain higher sensitivity to i-line exposure and higher resolution.

The content of the quinonediazide compound used in the resin composition of the present invention is preferably 1 to 50 parts by mass, more preferably 10 to 40 parts by mass with respect to 100 parts by mass of the resin. It is preferable to set the content of the quinonediazide compound in this range because the contrast between the exposed portion and the unexposed portion can be obtained and the sensitivity can be further increased. Further, a sensitizer or the like may be added as needed.

The photoacid generator is preferably 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, but the following formula (OS-1), the formula (OS-103) described later, the formula (OS-104), or the formula (OS-). It is preferably the oxime sulfonate compound represented by 105).

In formula (OS- ¹ ), X3 represents an alkyl group, an alkoxy group, or a halogen atom. When a plurality of ^X3s exist, they may be the same or different from each other. The alkyl group and the alkoxy group in ^X3 may have a substituent. As the alkyl group in X3 ^, a linear or branched alkyl group having 1 to 4 carbon atoms is preferable. As the alkoxy group in X3 ^, a linear or branched alkoxy group having 1 to 4 carbon atoms is preferable. As the halogen atom in X3 ^, a chlorine atom or a fluorine atom is preferable.
In the formula (OS-1), m3 represents an integer of 0 to 3, and 0 or 1 is preferable. When m3 is 2 or ³ , the plurality of X3s may be the same or different.
In the formula (OS-1), R ³⁴ represents an alkyl group or an aryl group, which is an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an alkyl halide group having 1 to 5 carbon atoms, and carbon. It is preferably an alkoxy group of numbers 1 to 5, a phenyl group which may be substituted with W, a naphthyl group which may be substituted with W, or an anthranyl group which may be substituted with W. W is a halogen atom, a cyano group, a nitro group, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an alkyl halide group having 1 to 5 carbon atoms or an alkoxy halide having 1 to 5 carbon atoms. Represents a group, an aryl group having 6 to 20 carbon atoms, and an aryl halide group having 6 to 20 carbon atoms.

In the formula (OS-1), m3 is ³ , X3 is a methyl group ^, the substitution position of X3 is the ortho position, and ^R34 is a linear alkyl group having 1 to 10 carbon atoms, 7, A compound having a 7-dimethyl-2-oxonorbornylmethyl group or a p-tolyl group is particularly preferable.

Specific examples of the oxime sulfonate compound represented by the formula (OS-1) are described in paragraphs 0064 to 0068 of JP2011-200969A and paragraph numbers 0158 to 0167 of JP2015-194674A. The following compounds are exemplified and their contents 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 be present in a plurality of R ^s2 , independently represents a hydrogen atom, an alkyl group and an aryl group. R ^s6 , which represents a group or a halogen atom and may be present in a plurality, 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. Represented, ns represents 1 or 2, ms represents an integer from 0 to 6.
In formulas (OS-103) to (OS-105), an alkyl group represented by R ^s1 (preferably 1 to 30 carbon atoms), an aryl group (preferably 6 to 30 carbon atoms) or a heteroaryl group (carbon). (Preferably numbers 4 to 30) may have a known substituent as long as the effects of the present invention can be obtained.

In the 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). , Hydrogen atom or alkyl group is more preferable. Of the ^Rs2 that may be present in two or more in the compound, one or two are preferably an alkyl group, an aryl group or a halogen atom, and one is more preferably an alkyl group, an aryl group or a halogen atom. It is particularly preferable that one is an alkyl group and the rest is a hydrogen atom. The alkyl group or aryl group represented by R ^s2 may have a known substituent as long as the effects of the present invention can be obtained.
In the formula (OS-103), the formula (OS-104), or the 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 the formulas (OS-103) to (OS-105), ns represents 1 or 2, and when Xs is O, ns is preferably 1, and when Xs is S, ns is. It is preferably 2.
In the formulas (OS-103) to (OS-105), the alkyl group represented by R ^s6 (preferably having 1 to 30 carbon atoms) and the alkyloxy group (preferably having 1 to 30 carbon atoms) are substituted groups. You may have.
In the 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 preferable.

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 a compound represented by the following formula (OS-105). -108) or a compound represented by the formula (OS-109) is particularly preferable.

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

In the 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.
Further, in the above-mentioned oxime sulfonate compound, the three-dimensional structure (E, Z) of the oxime may be either one or a mixture.
Specific examples of the oxime sulfonate compound represented by the above formulas (OS-103) to (OS-105) include paragraph numbers 008 to 0995 of JP2011-209692 and paragraphs of JP-A-2015-194674. The compounds of Nos. 0168 to 0194 are exemplified and their contents are incorporated herein.

Other suitable 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 the formula (OS-101) or the formula (OS-102), ^Ru9 is a hydrogen atom, an alkyl group, an alkenyl group, an alkoxy group, an alkoxycarbonyl group, an acyl group, a carbamoyl group, a sulfamoyl group, a sulfo group, a cyano group, and the like. Represents an aryl group or a heteroaryl group. The embodiment in which R ^u9 is a cyano group or an aryl group is more preferable, and the embodiment in which R ^u9 is a cyano group, a phenyl group or a naphthyl group is further preferable.
In formula (OS-101) or formula (OS-102), ^Ru2a 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. -, R ^u5 to R ^u7 independently represent an alkyl group or an aryl group, respectively.

In the formula (OS-101) or the formula (OS-102), ^Ru1 to ^Ru4 are independently hydrogen atom, halogen atom, alkyl group, alkenyl group, alkoxy group, amino group, alkoxycarbonyl group and alkylcarbonyl group, respectively. , Arylcarbonyl group, amide group, sulfo group, cyano group or aryl group. Two of R ^u1 to R ^u4 may be bonded to each other to form a ring. At this time, the ring may be condensed to form a fused ring together with the benzene ring. As R ^u1 to ^Ru4 , a hydrogen atom, a halogen atom or an alkyl group is preferable, and an embodiment in which at least two of ^Ru1 to ^Ru4 are bonded to each other to form an aryl group is also preferable. Above all, it is preferable that all of ^Ru1 to ^Ru4 are hydrogen atoms. Any of the above-mentioned 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 three-dimensional structure (E, Z, etc.) of the oxime and the benzothiazole ring may be either one or a mixture.
Specific examples of the compound represented by the formula (OS-101) include the compounds described in paragraphs 0102 to 0106 of JP-A-2011-20969 and paragraph numbers 0195 to 0207 of JP-A-2015-194674. And these contents are incorporated herein.
Among the above compounds, the following b-9, b-16, b-31, and b-33 are preferable.

Examples of commercially available products include WPAG-336 (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), WPAG-443 (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), MBZ-101 (manufactured by Midori Kagaku Co., Ltd.), and the like. Can be done.

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

Specific examples of the organic halogenated compound include Wakabayashi et al., “Bull Chem. Soc Japan” 42, 2924 (1969), US Pat. No. 3,905,815, Japanese Patent Publication No. 46-4605, JP-A. 48-36281, 55-32070, 60-239736, 61-169835, 61-169837, 62-58241, , Japanese Patent Application Laid-Open No. 62-212401, Japanese Patent Application Laid-Open No. 63-70243, Japanese Patent Application Laid-Open No. 63-298339, M.D. P. The compounds described in Hutt “Jurnal of Heterocyclic Chemistry” 1 (No3), (1970) and the like are mentioned, and the contents thereof are incorporated in the present specification. In particular, an oxazole compound substituted with a trihalomethyl group: an S-triazine compound is given as a preferable example.
More preferably, an s-triazine derivative in which at least one mono, di, or trihalogen-substituted methyl group is attached to the s-triazine ring, specifically, for example, 2,4,6-tris (monochromomethyl)-. 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-natoxynaphthyl) -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 thereof include triazine, 2-methyl-4,6-bis (tribromomethyl) -s-triazine, 2-methoxy-4,6-bis (tribromomethyl) -s-triazine and the like.

Examples of the organic borate compound include JP-A-62-143044, JP-A-62-150242, JP-A-9-188685, JP-A-9-188686, and JP-A-9-188710. Japanese Patent Application Laid-Open No. 2000-131837, Japanese Patent Application Laid-Open No. 2002-107916, Japanese Patent Application Laid-Open No. 2764769, Japanese Patent Application Laid-Open No. 2002-116539, etc., and Kunz, Martin "Rad Tech '98. , 1998, Chicago ”, etc., the organic boron sulfonium complex or the organic boron oxosulfonium described in JP-A-6-157623, JP-A-6-175564, JP-A-6-175561. Complex, organic boron iodonium complex described in JP-A-6-175554, JP-A-6-175553, organic boron phosphonium complex described in JP-A-9-188710, JP-A-6-348011, JP-A. Specific examples thereof include organic boron transition metal coordination complexes of JP-A-7-128785, JP-A-7-140589, JP-A-7-306527, JP-A-7-292014, and the like. Incorporated herein.

Examples of the disulfone compound include compounds described in JP-A-61-166544, Japanese Patent Application Laid-Open No. 2001-132318, and diazodisulfone compounds.

Examples of the onium salt compound include S. I. Schlesinger, Photogr. Sci. Eng. , 18,387 (1974), T.I. S. The diazonium salt described in Bal et al, Polymer, 21, 423 (1980), the ammonium salt described in US Pat. No. 4,069,055, JP-A-4-365049, etc., US Pat. No. 4,069 , 055, 4,069,056, European Patents 104, 143, US Patents 339, 049, 410, 201, Japanese Patent Application Laid-Open No. Iodonium salt described in Japanese Patent Application Laid-Open No. 2-150848, Japanese Patent Application Laid-Open No. 370,693, 390,214, 233,567, 297,443, 297,442, US Pat. Nos. 4,933,377, 161,811, 410,201, 339,049, 4,760,013, 4,734,444, 2,833,827 The sulfonium salt according to No. 2,904,626, 3,604,580, and 3,604,581 of the German Patent No. 2, J. V. Crivello et al, Macromolecules, 10 (6), 1307 (1977), J. Mol. V. Crivello et al, J. et al. Polymer Sci. , Polymer Chem. Ed. , 17, 1047 (1979), selenonium salt, C.I. S. Wen et al, Theh, Proc. Conf. Rad. Examples thereof include onium salts such as alsonium salt and pyridinium salt described in Curing ASIA, p478 Tokyo, Oct (1988), and these contents are incorporated in the present specification.

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

In the formula (RI-I), Ar ₁₁ represents an aryl group having 20 or less carbon atoms which may have 1 to 6 substituents, and preferred substituents are an alkyl group having 1 to 12 carbon atoms and 2 carbon atoms. ~ 12 alkenyl groups, alkynyl groups with 2-12 carbon atoms, aryl groups with 6-12 carbon atoms, alkoxy groups with 1-12 carbon atoms, allyloxy groups with 1-12 carbon atoms, halogen atoms, 1-12 carbon atoms Alkylamino group, dialkylamino group with 2 to 12 carbon atoms, alkylamide group with 1 to 12 carbon atoms or arylamide group with 6 to 20 carbon atoms, carbonyl group, carboxy group, cyano Examples thereof include a group, a sulfonyl group, a thioalkyl group having 1 to 12 carbon atoms, and a thioaryl group having 1 to 12 carbon atoms. Z ₁₁ ^- represents a monovalent anion, which is a halogen ion, a perchlorate ion, a hexafluorophosphate ion, a tetrafluoroborate ion, a sulfonic acid ion, a sulfinate ion, a thiosulfonic acid ion, and a sulfate ion, and is stable. From the aspect, perchlorate ion, hexafluorophosphate ion, tetrafluoroborate ion, sulfonic acid ion, and sulfinate ion are preferable. In the formula (RI-II), Ar ₂₁ and Ar ₂₂ each represent an aryl group having 1 to 20 carbon atoms which may independently have 1 to 6 substituents, and preferred substituents have 1 to 12 carbon atoms. Alkyl group, alkenyl group with 2 to 12 carbon atoms, alkynyl group with 2 to 12 carbon atoms, aryl group with 1 to 12 carbon atoms, alkoxy group with 1 to 12 carbon atoms, allyloxy group with 1 to 12 carbon atoms, halogen An atom, a monoalkylamino group having 1 to 12 carbon atoms, a dialkylamino group having 1 to 12 carbon atoms independently of the alkyl group, an alkylamide group or an arylamide group having 1 to 12 carbon atoms in the alkyl group, Examples thereof include a carbonyl group, a carboxy group, a cyano group, a sulfonyl group, a thioalkyl group having 1 to 12 carbon atoms, and a thioaryl group having 1 to 12 carbon atoms. Z21 ^- represents a monovalent anion, which is a halogen ion, a perchlorate ion, a hexafluorophosphate ion, a tetrafluoroborate ion, a sulfonic acid ion, a sulfinate ion, a thiosulfonic acid ion, and a sulfate ion, and is stable and reacts. From the viewpoint of sex, perchlorate ion, hexafluorophosphate ion, tetrafluoroborate ion, sulfonic acid ion, sulfinate ion and carboxylate ion are preferable. In formula (RI-III), R ₃₁ , R ₃₂ , and R ₃₃ each have an aryl group or an alkyl group, an alkenyl group, or an alkynyl group having 6 to 20 carbon atoms, which may independently have 1 to 6 substituents. It is preferably an aryl group from the viewpoint of reactivity and stability. Preferred substituents include an alkyl group having 1 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, an alkynyl group having 2 to 12 carbon atoms, an aryl group having 1 to 12 carbon atoms, and an alkoxy group having 1 to 12 carbon atoms. An aryloxy group having 1 to 12 carbon atoms, a halogen atom, a monoalkylamino group having 1 to 12 carbon atoms, a dialkylamino group having 1 to 12 carbon atoms independently of each other, and an alkyl group having 1 to 12 carbon atoms. Examples thereof include an alkylamide group having 1 to 12 or an arylamide group, a carbonyl group, a carboxy group, a cyano group, a sulfonyl group, a thioalkyl group having 1 to 12 carbon atoms and a thioaryl group having 1 to 12 carbon atoms. Z ₃₁ ^- represents a monovalent anion, which is a halogen ion, a perchlorate ion, a hexafluorophosphate ion, a tetrafluoroborate ion, a sulfonic acid ion, a sulfinate ion, a thiosulfonic acid ion, a sulfate ion, and stability. From the viewpoint of reactivity, perchlorate ion, hexafluorophosphate ion, tetrafluoroborate ion, sulfonic acid ion, sulfinate ion and carboxylate ion are preferable.

Specific examples of preferable photoacid generators include the following.

The photoacid generator is preferably used in an amount of 0.1 to 20% by mass, more preferably 0.5 to 18% by mass, and more preferably 0.5 to 10% by mass, based on the total solid content of the resin composition. It is more preferably used, more preferably 0.5 to 3% by mass, and even more preferably 0.5 to 1.2% by mass.
The photoacid generator may be used alone or in combination of two or more. In the case of a combination of a plurality of types, it is preferable that the total amount thereof is within the above range.
It is also preferable to use it in combination with a sensitizer in order to impart photosensitivity to a desired light source.

<Thermal acid generator>
The composition of the present invention may contain a thermoacid generator.
The thermoacid generator generates an acid by heating and promotes a cross-linking reaction of at least one compound selected from a compound 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 making it.

The thermal decomposition start temperature of the thermal acid generator is preferably 50 ° C. to 270 ° C., more preferably 50 ° C. to 250 ° C. Further, no acid is generated when the composition is dried after being applied to the substrate (pre-bake: about 70 to 140 ° C.), and when the final heating (cure: about 100 to 400 ° C.) is performed after patterning by subsequent exposure and development. It is preferable to select an acid-generating agent as the thermal acid generator because it can suppress a decrease in sensitivity during development.
The thermal decomposition start temperature is determined as the peak temperature of the exothermic peak, which is the lowest temperature when the thermal acid generator is heated to 500 ° C. at 5 ° C./min in a pressure-resistant capsule.
Examples of the device used for measuring the thermal decomposition start temperature include Q2000 (manufactured by TA Instruments).

The acid generated from the thermal acid generator is preferably a strong acid, for example, aryl sulfonic acid such as p-toluene sulfonic acid and benzene sulfonic acid, alkyl sulfonic acid such as methane sulfonic acid, ethane sulfonic acid and butane sulfonic acid, or trifluoromethane. Haloalkyl sulfonic acid such as sulfonic acid is preferable. Examples of such a thermoacid generator include those described in paragraph 0055 of JP2013-072935.

Among them, those that generate an alkyl sulfonic acid having 1 to 4 carbon atoms or a haloalkyl sulfonic acid having 1 to 4 carbon atoms are more preferable from the viewpoint that there is little residue in the organic film and it is difficult to deteriorate the physical properties of the organic film. (4-Hydroxyphenyl) dimethylsulfonium, methanesulfonic acid (4-((methoxycarbonyl) oxy) phenyl) dimethylsulfonium, benzyl methanesulfonic acid (4-hydroxyphenyl) methylsulfonium, benzyl methanesulfonic acid (4-((methoxycarbonyl)) Carbonyl) oxy) phenyl) methyl sulfonium, methanesulfonic acid (4-hydroxyphenyl) methyl ((2-methylphenyl) methyl) sulfonium, trifluoromethanesulfonic acid (4-hydroxyphenyl) dimethylsulfonium, trifluoromethanesulfonic acid (4-) ((Methoxycarbonyl) oxy) phenyl) dimethylsulfonium, benzyl trifluoromethanesulfonate (4-hydroxyphenyl) methylsulfonium, benzyl trifluoromethanesulfonate (4-((methoxycarbonyl) oxy) phenyl) methylsulfonium, trifluoromethanesulfonic acid (4-Hydroxyphenyl) Methyl ((2-Methylphenyl) Methyl) Sulfonium, 3-(5-(((propylsulfonyl) Oxy) Imino) Thiophen-2 (5H) -Ilidene) -2- (o-Trill) Propanenitrile and 2,2-bis (3- (methanesulfonylamino) -4-hydroxyphenyl) hexafluoropropane are preferred as the thermal acid generator.

Further, the compound described in paragraph 0059 of JP2013-167742A is also preferable as the thermal acid generator.

The content of the thermoacid generator is preferably 0.01 part by mass or more, more preferably 0.1 part by mass or more with respect to 100 parts by mass of the specific resin. By containing 0.01 part 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, 20 parts by mass or less is preferable, 15 parts by mass or less is more preferable, and 10 parts by mass or less is further preferable.

<Base generator>
The resin composition of the present invention may contain a base generator. Here, the base generator is a compound capable of generating a base by a physical or chemical action. Preferred base generators for the resin composition of the present invention include thermal base generators and photobase generators.
In particular, when the resin composition contains a precursor of a cyclized resin, it is preferable that the resin composition contains a base generator. When the resin composition contains a thermal base generator, for example, the cyclization reaction of the precursor can be promoted by heating, and the mechanical properties and chemical resistance of the cured product become good. The performance as an interlayer insulating film for a wiring layer is improved.
The base generator may be an ionic base generator or a nonionic base generator. Examples of the base generated from the base generator include secondary amines and tertiary amines.
The base generator according to the present invention is not particularly limited, and a known base generator can be used. Known base generators include, for example, carbamoyloxime compounds, carbamoylhydroxylamine compounds, carbamic acid compounds, formamide compounds, acetoamide compounds, carbamates compounds, benzylcarbamate compounds, nitrobenzylcarbamate compounds, sulfonamide compounds, imidazole derivative compounds, and amineimides. Compounds, pyridine derivative compounds, α-aminoacetophenone derivative compounds, quaternary ammonium salt derivative compounds, pyridinium salts, α-lactone ring derivative compounds, amineimide compounds, phthalimide derivative compounds, acyloxyimino compounds and the like can be used.
Specific examples of the compound of the nonionic base generator include a compound represented by the formula (B1), the formula (B2), or the formula (B3).

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

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

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

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

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

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

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

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

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

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

In the formula (B3), L is a divalent hydrocarbon group having a saturated hydrocarbon group on the path of the connecting chain connecting the adjacent oxygen atom and the carbon atom, and the number of atoms on the path of the connecting chain is Represents a hydrocarbon group having 3 or more. Further, ^RN1 and ^RN2 each independently represent a monovalent organic group.

As used herein, the term "linking chain" refers to an atomic chain on a path connecting two atoms or a group of atoms to be linked, which is connected at the shortest (minimum number of atoms). For example, in the compound represented by the following formula, L is composed of a phenylene ethylene group, has an ethylene group as a saturated hydrocarbon group, and the linking chain is composed of four carbon atoms, and is on the path of the linking chain. (That is, the number of atoms constituting the connecting chain, hereinafter also referred to as "linking chain length" or "connecting chain length") is 4.

The number of carbon atoms in L in the formula (B3) (including carbon atoms other than the carbon atoms in the linked chain) is preferably 3 to 24. The upper limit is more preferably 12 or less, further preferably 10 or less, and particularly preferably 8 or less. The lower limit is more preferably 4 or more. From the viewpoint of rapidly advancing the intramolecular cyclization reaction, the upper limit of the linking chain length of L is preferably 12 or less, more preferably 8 or less, still more preferably 6 or less, and 5 The following is particularly preferable. In particular, the chain length of L is preferably 4 or 5, and most preferably 4. Specific preferred compounds of the base generator include, for example, the compounds described in paragraphs 0102 to 0168 of International Publication No. 2020/06614 and the compounds described in paragraph numbers 0143 to 0177 of International Publication No. 2018/038002. Can be mentioned.

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

In formula ( ^N1 ), RN1 and ^RN2 each independently represent a monovalent organic group, RC1 represents a hydrogen atom or a protecting group, and L represents a divalent linking group.

L is a divalent linking group, preferably a divalent organic group. The linking chain length of the linking group is preferably 1 or more, and more preferably 2 or more. The upper limit is preferably 12 or less, more preferably 8 or less, and even more preferably 5 or less. The linking chain length is the number of atoms present in the atomic arrangement that is the shortest route between the two carbonyl groups in the equation.

In the formula ( ^N1 ), RN1 and ^RN2 each independently represent a monovalent organic group (preferably 1 to 24 carbon atoms, more preferably 2 to 18 carbon atoms, still more preferably 3 to 12 carbon atoms), and a hydrocarbon group (preferably 3 to 12 carbon atoms). It is preferably 1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms, still more preferably 1 to 10 carbon atoms), and specifically, an aliphatic hydrocarbon group (preferably 1 to 12 carbon atoms). Is more preferable) or an aromatic hydrocarbon group (preferably 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, still more preferably 6 to 10 carbon atoms), and an aliphatic hydrocarbon can be mentioned. Group is preferred. It is preferable to use an aliphatic hydrocarbon group as ^RN1 and ^RN2 because the basicity of the generated base is high. The aliphatic hydrocarbon group and the aromatic hydrocarbon group may have a substituent, and the aliphatic hydrocarbon group and the aromatic hydrocarbon group are contained in the aliphatic hydrocarbon chain or the aromatic ring. It may have an oxygen atom in the substituent. In particular, an embodiment in which the aliphatic hydrocarbon group has an oxygen atom in the hydrocarbon chain is exemplified.

As the aliphatic hydrocarbon group constituting ^RN1 and ^RN2 , a linear or branched chain alkyl group, a cyclic alkyl group, a group related to a combination of a chain alkyl group and a cyclic alkyl group, and an oxygen atom are contained in the chain. Examples thereof include alkyl groups having. The linear or branched chain alkyl group preferably has 1 to 24 carbon atoms, more preferably 2 to 18 carbon atoms, and even more preferably 3 to 12 carbon atoms. The linear or branched chain alkyl group is, for example, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, an undecyl group, a dodecyl group, or an isopropyl group. Examples thereof include a group, an isobutyl group, a secondary butyl group, a tertiary butyl group, an isopentyl group, a neopentyl group, a tertiary pentyl group, and an isohexyl group.
The cyclic alkyl group preferably has 3 to 12 carbon atoms, and more preferably 3 to 6 carbon atoms. Examples of the cyclic alkyl group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cyclooctyl group and the like.
The group related to the combination of the chain alkyl group and the cyclic alkyl group preferably has 4 to 24 carbon atoms, more preferably 4 to 18 carbon atoms, and even more preferably 4 to 12 carbon atoms. Examples of the group related to the combination of the chain alkyl group and the cyclic alkyl group include a cyclohexylmethyl group, a cyclohexylethyl group, a cyclohexylpropyl group, a methylcyclohexylmethyl group, an ethylcyclohexylethyl group and the like.
The alkyl group having an oxygen atom in the chain is preferably 2 to 12 carbon atoms, more preferably 2 to 6 carbon atoms, still more preferably 2 to 4 carbon atoms. The alkyl group having an oxygen atom in the chain may be chain-like or cyclic, and may be linear or branched.
Among them, alkyl groups having 5 to 12 carbon atoms are preferable for ^RN1 and ^RN2 from the viewpoint of increasing the boiling point of the decomposition-generated base described later. However, in a formulation that emphasizes adhesion when laminated with a metal (for example, copper) layer, a group having a cyclic alkyl group or an alkyl group having 1 to 8 carbon atoms is preferable.

^RN1 and ^RN2 may be connected to each other to form an annular structure. In forming the cyclic structure, oxygen atoms or the like may be contained in the chain. Further, the cyclic structure formed by ^RN1 and ^RN2 may be a monocyclic ring or a condensed ring, but a monocyclic ring is preferable. As the cyclic structure to be formed, a 5-membered ring or a 6-membered ring containing a nitrogen atom in the formula (N1) is preferable, and for example, a pyrrol ring, an imidazole ring, a pyrazole ring, a pyrroline ring, a pyrrolidine ring, an imidazolidine ring, and the like. Examples thereof include a pyrazolidine ring, a piperidine ring, a piperazine ring, a morpholine ring and the like, and a pyrroline ring, a pyrrolidine ring, a piperidine ring, a piperazine ring, a morpholine ring and the like are preferable.

^RC1 represents a hydrogen atom or a protecting group, and a hydrogen atom is preferable.

As the protecting group, a protecting group that decomposes by the action of an acid or a base is preferable, and a protecting group that decomposes by an acid is preferable.

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

The divalent linking group constituting L is not particularly specified, but a hydrocarbon group is preferable, and an aliphatic hydrocarbon group is more preferable. The hydrocarbon group may have a substituent, or may have an atom of a type other than a carbon atom in the hydrocarbon chain. More specifically, it is preferably a divalent hydrocarbon linking group which may have an oxygen atom in the chain, and a divalent aliphatic hydrocarbon which may have an oxygen atom in the chain. More preferably, a divalent aromatic hydrocarbon group, or a group relating to a combination of a divalent aliphatic hydrocarbon group which may have an oxygen atom in the chain and a divalent aromatic hydrocarbon group. A divalent aliphatic hydrocarbon group which may have an oxygen atom in the chain is more preferable. It is preferable that these groups do not have an oxygen atom.
The divalent hydrocarbon linking group preferably has 1 to 24 carbon atoms, more preferably 2 to 12 carbon atoms, and even more preferably 2 to 6 carbon atoms. The divalent aliphatic hydrocarbon group preferably has 1 to 12 carbon atoms, more preferably 2 to 6 carbon atoms, and even more preferably 2 to 4 carbon atoms. The divalent aromatic hydrocarbon group preferably has 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, and even more preferably 6 to 10 carbon atoms. The group (for example, an arylene alkyl group) relating to the combination of the divalent aliphatic hydrocarbon group and the divalent aromatic hydrocarbon group preferably has 7 to 22 carbon atoms, more preferably 7 to 18 carbon atoms, and 7 to 18 carbon atoms. 10 is more preferable.

Specific examples of the linking group L include a linear or branched chain alkylene group, a cyclic alkylene group, a group related to a combination of a chain alkylene group and a cyclic alkylene group, and an alkylene group having an oxygen atom in the chain. , A linear or branched chain alkaneylene group, a cyclic alkaneylene group, an arylene group, or an arylene alkylene group is preferable.
The linear or branched chain alkylene group preferably has 1 to 12 carbon atoms, more preferably 2 to 6 carbon atoms, and even more preferably 2 to 4 carbon atoms.
The cyclic alkylene group preferably has 3 to 12 carbon atoms, and more preferably 3 to 6 carbon atoms.
The group related to the combination of the chain alkylene group and the cyclic alkylene group preferably has 4 to 24 carbon atoms, more preferably 4 to 12 carbon atoms, and even more preferably 4 to 6 carbon atoms.
The alkylene group having an oxygen atom in the chain may be chain-like or cyclic, and may be linear or branched. The alkylene group having an oxygen atom in the chain is preferably 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, still more preferably 1 to 3 carbon atoms.

The linear or branched chain-like alkenylene group preferably has 2 to 12 carbon atoms, more preferably 2 to 6 carbon atoms, and even more preferably 2 to 3 carbon atoms. The linear or branched chain-like alkenylene group preferably has 1 to 10 C = C bonds, more preferably 1 to 6, and even more preferably 1 to 3.
The cyclic alkenylene group preferably has 3 to 12 carbon atoms, and more preferably 3 to 6 carbon atoms. For the cyclic alkenylene group, the number of C = C bonds is preferably 1 to 6, more preferably 1 to 4, and even more preferably 1 to 2.
The arylene group preferably has 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, and even more preferably 6 to 10 carbon atoms.
The arylene alkylene group preferably has 7 to 23 carbon atoms, more preferably 7 to 19 carbon atoms, and even more preferably 7 to 11 carbon atoms.
Among them, a chain alkylene group, a cyclic alkylene group, an alkylene group having an oxygen atom in the chain, a chain alkenylene group, an arylene group and an arylene alkylene group are preferable, and a 1,2-ethylene group and a propandiyl group (particularly 1, 3-Propanediyl group), cyclohexanediyl group (especially 1,2-cyclohexanediyl group), vinylene group (especially cisvinylene group), phenylene group (1,2-phenylene group), phenylene methylene group (especially 1,2-phenylene) Methylene group) and ethyleneoxyethylene group (particularly 1,2-ethyleneoxy-1,2-ethylene group) are more preferable.

Examples of the base generator include the following, but the present invention is not construed as being limited thereto.

The molecular weight of the non-ionic 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.

Specific preferable compounds of the ionic base generator include, for example, the compounds described in paragraphs 0148 to 0163 of International Publication No. 2018/038002.

Specific examples of the ammonium salt include, but are not limited to, the following compounds.

Specific examples of the iminium salt include, but are not limited to, the following compounds.

When the resin composition of the present invention contains a base generator, the content of the base generator is preferably 0.1 to 50 parts by mass with respect to 100 parts by mass of the resin in the resin composition of the present invention. The lower limit is more preferably 0.3 parts by mass or more, and further preferably 0.5 parts by mass or more. The upper limit is more preferably 30 parts by mass or less, further preferably 20 parts by mass or less, further preferably 10 parts by mass or less, 5 parts by mass or less, or 4 parts by mass or less.
As the base generator, one kind or two or more kinds can be used. When two or more types are used, the total amount is preferably in the above range.

<Polymerizable compound>
The resin composition of the present invention preferably contains a polymerizable compound.
Examples of the polymerizable compound include radical cross-linking agents and other cross-linking agents.

[Radical cross-linking agent]
The resin composition of the present invention preferably contains a radical cross-linking agent.
The radical cross-linking 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 a group having an ethylenically unsaturated bond such as a vinyl group, an allyl group, a vinylphenyl group, a (meth) acryloyl group, a maleimide group, and a (meth) acrylamide group.
Among these, as the group containing an ethylenically unsaturated bond, a (meth) acryloyl group, a (meth) acrylamide group and a vinylphenyl group are preferable, and from the viewpoint of reactivity, a (meth) acryloyl group is more preferable.

The radical cross-linking agent is preferably a compound having one or more ethylenically unsaturated bonds, but more preferably a compound having two or more ethylenically unsaturated bonds. The radical cross-linking agent may have three or more ethylenically unsaturated bonds.
As the compound having two or more ethylenically unsaturated bonds, a compound having 2 to 15 ethylenically unsaturated bonds is preferable, and a compound having 2 to 10 ethylenically unsaturated bonds is more preferable, and 2 to 6 compounds are more preferable. The compound having is more preferable.
Further, from the viewpoint of the film strength of the obtained pattern (cured product), the resin composition of the present invention comprises a compound having two ethylenically unsaturated bonds and a compound having three or more ethylenically unsaturated bonds. It is also preferable to include.

The molecular weight of the radical cross-linking 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 cross-linking agent is preferably 100 or more.

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

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

Further, as a preferable radical cross-linking agent other than the above, it has a fluorene ring and has an ethylenically unsaturated bond, which is described in JP-A-2010-160418, JP-A-2010-129825, Patent No. 4364216 and the like. Compounds having two or more groups and cardo resins can also be used.

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

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

Further, the compound described in JP-A No. 10-062986 together with specific examples as the formulas (1) and (2), which is obtained by adding ethylene oxide or propylene oxide to a polyfunctional alcohol and then (meth) acrylated, is also available. It can be used as a radical cross-linking agent.

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

As radical cross-linking agents, dipentaerythritol triacrylate (commercially available KAYARAD D-330; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol tetraacrylate (commercially available KAYARAD D-320; Nihon Kayaku Co., Ltd.) ), A-TMMT: Shin Nakamura Chemical Industry Co., Ltd.), Dipentaerythritol penta (meth) acrylate (commercially available KAYARAD D-310; Nippon Kayaku Co., Ltd.), Dipentaerythritol hexa (meth) ) Acrylate (commercially available KAYARAD DPHA; manufactured by Nippon Kayaku Co., Ltd., A-DPH; manufactured by Shin Nakamura Chemical Industry Co., Ltd.), and these (meth) acryloyl groups are mediated by ethylene glycol residues or propylene glycol residues. A structure that is bonded together is preferable. These oligomer types can also be used.

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

Examples of the radical cross-linking agent include urethane acrylates as described in Japanese Patent Publication No. 48-041708, Japanese Patent Application Laid-Open No. 51-037193, Japanese Patent Laid-Open No. 02-0322293, and Japanese Patent Laid-Open No. 02-016765. Urethane compounds having an ethylene oxide-based skeleton described in Japanese Patent Publication No. 58-049860, Japanese Patent Publication No. 56-017654, Japanese Patent Publication No. 62-039417, and Japanese Patent Publication No. 62-039418 are also suitable. Further, as the radical cross-linking 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 it.

The radical cross-linking agent may be a radical cross-linking agent having an acid group such as a carboxy group or a phosphoric acid group. The radical cross-linking agent having an acid group is preferably an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid, and an acid group is obtained by reacting an unreacted hydroxy group of the aliphatic polyhydroxy compound with a non-aromatic carboxylic acid anhydride. The radical cross-linking agent provided with the above is more preferable. Particularly preferably, in a radical cross-linking agent in which an unreacted hydroxy group of an aliphatic polyhydroxy compound is reacted with a non-aromatic carboxylic acid anhydride to give an acid group, the aliphatic polyhydroxy compound is pentaerythritol or dipentaerythritol. Is a compound. Examples of commercially available products include M-510 and M-520 as polybasic acid-modified acrylic oligomers manufactured by Toagosei Co., Ltd.

The acid value of the radical cross-linking agent having an acid group is preferably 0.1 to 300 mgKOH / g, and particularly preferably 1 to 100 mgKOH / g. When the acid value of the radical cross-linking agent is within the above range, it is excellent in manufacturable handling and further excellent in developability. Moreover, the polymerizability is good. The acid value is measured according to the description of JIS K 0070: 1992.

As the resin composition, it is preferable to use bifunctional methacrylate or acrylate from the viewpoint of pattern resolution and film elasticity.
Specific compounds include triethylene glycol diacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, tetraethylene glycol diacrylate, PEG (polyethylene glycol) 200 diacrylate, PEG200 dimethacrylate, PEG600 diacrylate, and PEG600 dimethacrylate. Methacrylate, 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, dimethyrole-tricyclodecanediacrylate, dimethyrole-tricyclodecanedimethacrylate, EO (ethylene oxide) adduct diacrylate of bisphenol A, EO adduct dimethalilate of bisphenol A, PO (propylene) of bisphenol A Oxide) Additive Diacrylate, EO Additive Dimetalylate of Bisphenol A, 2-Hydroxy-3-acryloyloxypropyl methacrylate, isocyanuric acid EO modified diacrylate, isocyanuric acid modified dimethacrylate, other bifunctional acrylate with urethane bond, urethane bond Bifunctional methacrylate having the above can be used. If necessary, two or more of these can be mixed and used.
For example, the PEG200 diacrylate is a polyethylene glycol diacrylate having a polyethylene glycol chain formula of about 200.
In the resin composition of the present invention, a monofunctional radical cross-linking agent can be preferably used as the radical cross-linking agent from the viewpoint of suppressing warpage associated with the control of the elastic modulus of the pattern (cured product). Examples of the monofunctional radical cross-linking agent include n-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, butoxyethyl (meth) acrylate, carbitol (meth) acrylate, and cyclohexyl (meth). ) 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. (meth) Acrylic acid derivatives, N-vinyl compounds such as N-vinylpyrrolidone and N-vinylcaprolactam, allylglycidyl ether and the like are preferably used. As the monofunctional radical cross-linking agent, a compound having a boiling point of 100 ° C. or higher under normal pressure is also preferable in order to suppress volatilization before exposure.
Other examples of the bifunctional or higher functional cross-linking agent include allyl compounds such as diallyl phthalate and triallyl trimellitate.

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

One type of radical cross-linking agent may be used alone, or two or more types may be mixed and used. When two or more types are used in combination, the total amount is preferably within the above range.

[Other cross-linking agents]
It is also preferable that the resin composition of the present invention contains another cross-linking agent different from the above-mentioned radical cross-linking agent.
In the present invention, the other cross-linking agent refers to a cross-linking agent other than the above-mentioned radical cross-linking agent, and is a reaction of another compound in the composition or a reaction thereof by exposure to the above-mentioned photoacid generator or photobase generator. A compound having a plurality of groups in the molecule that promotes a reaction to form a covalent bond with the product is preferable, and a covalent bond is formed with another compound in the composition or a reaction product thereof. A compound having a plurality of groups in the molecule in which the reaction to be formed is promoted by the action of an acid or a base is preferable.
The acid or base is preferably an acid or base generated from a photoacid generator or a photobase generator in the exposure step.
As the other cross-linking agent, a compound having at least one group selected from the group consisting of an acyloxymethyl group, a methylol group and an alkoxymethyl group is preferable, and the compound is selected from the group consisting of an acyloxymethyl group, a methylol group and an alkoxymethyl group. A compound having a structure in which at least one of the above groups is directly bonded to a nitrogen atom is more preferable.
As another cross-linking agent, for example, an amino group-containing compound such as melamine, glycoluril, urea, alkylene urea, or benzoguanamine is reacted with formaldehyde or formaldehyde and alcohol, and the hydrogen atom of the amino group is changed to an acyloxymethyl group, a methylol group or a methylol group. Examples thereof include compounds having a structure substituted with an alkoxymethyl group. 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. Further, it may be an oligomer formed by self-condensing the methylol groups of these compounds.
As the above amino group-containing compound, the cross-linking agent using melamine is a melamine-based cross-linking agent, the cross-linking agent using glycoluril, urea or alkylene urea is a urea-based cross-linking agent, and the cross-linking agent using alkylene urea is an alkylene urea-based cross-linking agent. A cross-linking agent using an agent or benzoguanamine is called a benzoguanamine-based cross-linking agent.
Among these, the resin composition of the present invention preferably contains at least one compound selected from the group consisting of a urea-based cross-linking agent and a melamine-based cross-linking agent, and is preferably a glycoluril-based cross-linking agent and a melamine-based cross-linking agent described later. It is more preferred to include at least one compound selected from the group consisting of agents.

As the compound containing at least one of the alkoxymethyl group and the acyloxymethyl group in the present invention, the alkoxymethyl group or the acyloxymethyl group is directly substituted on the aromatic group or the nitrogen atom having the following urea structure, or on triazine. Can be mentioned as a structural example.
The alkoxymethyl group or acyloxymethyl group contained in the above compound preferably has 2 to 5 carbon atoms, preferably 2 or 3 carbon atoms, and more preferably 2 carbon atoms.
The total number of alkoxymethyl groups and acyloxymethyl groups contained in the above compound is preferably 1 to 10, more preferably 2 to 8, and particularly preferably 3 to 6.
The molecular weight of the compound is preferably 1500 or less, preferably 180 to 1200.

R ₁₀₀ represents an alkyl group or an acyl group.
R ₁₀₁ and R ₁₀₂ each independently represent a monovalent organic group and may be bonded to each other to form a ring.

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

In the formula, X represents a single-bonded or divalent organic group, each R ₁₀₄ independently represents an alkyl group or an acyl group, and R ₁₀₃ is a hydrogen atom, an alkyl group, an alkenyl group, an aryl group or an aralkyl group. , Or a group that decomposes by the action of an acid to produce an alkali-soluble group (for example, a group that is desorbed by the action of an acid, a group represented by -C (R ⁴ ) ₂ COOR ⁵ (R ⁴ is independent of each other). It represents a hydrogen atom or an alkyl group having 1 to ⁴ carbon atoms, and R5 represents a group desorbed by the action of an acid.)).
R ₁₀₅ independently represents an alkyl group or an alkenyl group, a, b and c are independently 1 to 3, d is 0 to 4, e is 0 to 3, and f is 0 to 3. A + d is 5 or less, b + e is 4 or less, and c + f is 4 or less.
For R ⁵ in a group that decomposes by the action of an acid to produce an alkali-soluble group, a group that is eliminated by the action of an acid, and a group represented by -C (R ⁴ ) ₂ COOR ⁵ , for example, -C (R ₃₆ ). ) (R ₃₇ ) (R ₃₈ ), -C (R ₃₆ ) (R ₃₇ ) (OR ₃₉ ), -C (R ₀₁ ) (R ₀₂ ) (OR ₃₉ ) and the like.
In the formula, R ₃₆ to R ₃₉ each independently represent an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group or an alkenyl group. R ₃₆ and R ₃₇ may be coupled to each other to form a ring.
As the alkyl group, an alkyl group having 1 to 10 carbon atoms is preferable, and an alkyl group having 1 to 5 carbon atoms is more preferable.
The alkyl group may be linear or branched.
As the cycloalkyl group, a cycloalkyl group having 3 to 12 carbon atoms is preferable, and a cycloalkyl group having 3 to 8 carbon atoms is more preferable.
The cycloalkyl group may have a monocyclic structure or a polycyclic structure such as a fused ring.
The aryl group is preferably an aromatic hydrocarbon group having 6 to 30 carbon atoms, and more preferably a phenyl group.
As the aralkyl group, an aralkyl group having 7 to 20 carbon atoms is preferable, and an aralkyl group having 7 to 16 carbon atoms is more preferable.
The above-mentioned aralkyl group is intended to be an aryl group substituted with an alkyl group, and preferred embodiments of these alkyl and aryl groups are the same as those of the above-mentioned preferred embodiments of alkyl and aryl groups.
The alkenyl group is preferably an alkenyl group having 3 to 20 carbon atoms, and more preferably an alkenyl group having 3 to 16 carbon atoms.
Further, these groups may further have a known substituent as long as the effect of the present invention can be obtained.

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

The group that decomposes by the action of an acid to produce an alkali-soluble group, or the group that is desorbed by the action of an acid is preferably a tertiary alkyl ester group, an acetal group, a cumyl ester group, an enol ester group, or the like. More preferably, it is a tertiary alkyl ester group or an acetal group.

Specific examples of the compound having an alkoxymethyl group include the following structures. Examples of the compound having an acyloxymethyl group include compounds in which the alkoxymethyl group of the following compound is changed to an acyloxymethyl group. Examples of the compound having an alkoxymethyl group or acyloxymethyl in the molecule include, but are not limited to, the following compounds.

As the compound containing at least one of an alkoxymethyl group and an acyloxymethyl group, a commercially available compound may be used, or a compound synthesized by a known method may be used.
From the viewpoint of heat resistance, a compound in which an alkoxymethyl group or an acyloxymethyl group is directly substituted on an aromatic ring or a triazine ring is preferable.

Specific examples of the melamine-based cross-linking agent include hexamethoxymethyl melamine, hexaethoxymethyl melamine, hexapropoxymethyl melamine, hexabutoxybutyl melamine and the like.

Specific examples of the urea-based cross-linking agent include monohydroxymethylated glycol uryl, dihydroxymethylated glycol uryl, trihydroxymethylated glycol uryl, tetrahydroxymethylated glycol uryl, monomethoxymethylated glycol uryl, and dimethoxymethylated glycol. Uril, trimethoxymethylated glycol uryl, tetramethoxymethylated glycol uryl, monoethoxymethylated glycol uryl, diethoxymethylated glycol uryl, triethoxymethylated glycol uryl, tetraethoxymethylated glycol uryl, monopropoxymethylated glycol uryl , Dipropoxymethylated glycol uryl, tripropoxymethylated glycol uryl, tetrapropoxymethylated glycol uryl, monobutoxymethylated glycol uryl, dibutoxymethylated glycol uryl, tributoxymethylated glycol uryl, or tetrabutoxymethylated glycol Glycoluril-based cross-linking agents such as uryl;
Urea-based cross-linking agents such as bismethoxymethylurea, bisethoxymethylurea, bispropoxymethylurea, and bisbutoxymethylurea,
Monohydroxymethylated ethylene urea or dihydroxymethylated ethylene urea, monomethoxymethylated ethylene urea, dimethoxymethylated ethylene urea, monoethoxymethylated ethylene urea, diethoxymethylated ethylene urea, monopropoxymethylated ethylene urea, dipropoxymethyl Ethyleneurea-based cross-linking agents such as ethyleneurea, monobutoxymethylated, or dibutoxymethylated ethyleneurea,
Monohydroxymethylated propylene urea, dihydroxymethylated propylene urea, monomethoxymethylated propylene urea, dimethoxymethylated propylene urea, monoethoxymethylated propylene urea, diethoxymethylated propylene urea, monopropoxymethylated propylene urea, dipropoxymethyl A propylene urea-based cross-linking agent such as propylene dioxide, monobutoxymethylated propylene urea, or dibutoxymethylated propylene urea,
Examples thereof include 1,3-di (methoxymethyl) 4,5-dihydroxy-2-imidazolidinone and 1,3-di (methoxymethyl) -4,5-dimethoxy-2-imidazolidinone.

Specific examples of the benzoguanamine-based cross-linking agent include monohydroxymethylated benzoguanamine, dihydroxymethylated benzoguanamine, trihydroxymethylated benzoguanamine, tetrahydroxymethylated benzoguanamine, monomethoxymethylated benzoguanamine, dimethoxymethylated benzoguanamine, and trimethoxymethylated benzoguanamine. , Tetramethoxymethylated benzoguanamine, monoethoxymethylated benzoguanamine, diethoxymethylated benzoguanamine, triethoxymethylated benzoguanamine, tetraethoxymethylated benzoguanamine, monopropoxymethylated benzoguanamine, dipropoxymethylated benzoguanamine, tripropoxymethylated benzoguanamine, tetra Examples thereof include propoxymethylated benzoguanamine, monobutoxymethylated benzoguanamine, dibutoxymethylated benzoguanamine, tributoxymethylated benzoguanamine, tetrabutoxymethylated benzoguanamine and the like.

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 selected from the group consisting of a methylol group and an alkoxymethyl group on an aromatic ring (preferably a benzene ring). Compounds to which the group of the species is 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, and hydroxymethylphenyl hydroxymethylbenzoate. , Bis (hydroxymethyl) biphenyl, dimethylbis (hydroxymethyl) biphenyl, bis (methoxymethyl) benzene, bis (methoxymethyl) cresol, bis (methoxymethyl) dimethoxybenzene, bis (methoxymethyl) diphenyl ether, bis (methoxymethyl) Benzenephenone, methoxymethylphenyl methoxymethylbenzoate, bis (methoxymethyl) biphenyl, dimethylbis (methoxymethyl) biphenyl, 4,4', 4''-ethylidentris [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 ( Examples thereof include methoxymethyl) -1,1'-biphenyl-4,4'-diol and the like.

Commercially available products may be used as other cross-linking agents, and suitable commercially available products include 46DMOC, 46DMOEP (all manufactured by Asahi Organic Materials Industry 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 (above, Honshu) Nikarak (registered trademark, the same applies hereinafter) MX-290, Nikarak MX-280, Nikarak MX-270, Nikarak MX-279, Nikarak MW-100LM, Nikarak MX-750LM (all manufactured by Sanwa Chemical Co., Ltd.) ) And so on.

Further, it is also preferable that the resin composition of the present invention contains at least one compound selected from the group consisting of an epoxy compound, an oxetane compound, and a benzoxazine compound as another cross-linking agent.

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

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

Examples of epoxy compounds include bisphenol A type epoxy resin; bisphenol F type epoxy resin; propylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, ethylene glycol diglycidyl ether, butylene glycol diglycidyl ether, hexamethylene glycol diglycidyl ether. , Trimethylol propane Triglycidyl ether and other alkylene glycol type epoxy resins or polyhydric alcohol hydrocarbon type epoxy resins; Polyalkylene glycol type epoxy resins such as polypropylene glycol diglycidyl ether; Polymethyl (glycidyloxypropyl) siloxane and other epoxy groups Examples include, but are not limited to, contained silicone. Specifically, Epicron® 850-S, Epicron® HP-4032, Epicron® HP-7200, Epicron® HP-820, Epicron® HP-4700, Epicron® HP-4770, Epicron® EXA-830LVP, Epicron® EXA-8183, Epicron® EXA-8169, Epicron® N-660, Epicron® N-665-EXP-S, Epicron (registered trademark) N-740 (trademark, manufactured by DIC Co., Ltd.), Ricaresin (registered trademark) BEO-20E, Ricaresin (registered trademark) BEO-60E, Ricaresin (registered trademark) ) HBE-100, Ricaresin (registered trademark) DME-100, Ricaresin (registered trademark) L-200 (trade name, Shin Nihon Rika Co., Ltd.), EP-4003S, EP-4000S, EP-4088S, EP-3950S ( Product names, ADEKA Co., Ltd., celoxide (registered trademark) 2021P, celoxide (registered trademark) 2081, celoxide (registered trademark) 2000, EHPE3150, Epolide (registered trademark) GT401, Epolide (registered trademark) PB4700, Epolide ( Registered trademark) PB3600 (trade name, manufactured by Daicel Co., Ltd.), NC-3000, NC-3000-L, NC-3000-H, NC-3000-FH-75M, NC-3100, CER-3000-L, NC-2000-L, XD-1000, NC-7000L, NC-7300L, EPPN-501H, EPPN-501HY, EPPN-502H, EOCN-1020, EOCN-102S, EOCN-103S, EOCN-104S, CER-1020, EPPN-201, BREN-S, BREN-10S (trade name, manufactured by Nippon Kayaku Co., Ltd.) and the like can be mentioned. The following compounds are also preferably used. The

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

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

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

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

Preferred examples of the benzoxazine compound include Pd-type benzoxazine, Fa-type benzoxazine (trade name, manufactured by Shikoku Kasei Kogyo Co., Ltd.), a benzoxazine adduct of a polyhydroxystyrene resin, and a phenol novolac-type dihydrobenzo. Examples include oxazine compounds. These may be used alone or in combination of two or more.

The content of the other cross-linking agent is preferably 0.1 to 30% by mass, more preferably 0.1 to 20% by mass, and 0. It is more preferably 5 to 15% by mass, and particularly preferably 1.0 to 10% by mass. The other cross-linking agent may be contained in only one kind, or may be contained in two or more kinds. When two or more other cross-linking agents are contained, the total is preferably in the above range.

<Metal adhesion improver>
The resin composition of the present invention preferably contains a metal adhesiveness improving agent for improving the adhesiveness with a metal material used for electrodes, wiring and the like. Examples of the metal adhesion improver include a silane coupling agent having an alkoxysilyl group, an aluminum-based adhesive aid, a titanium-based adhesive aid, a compound having a sulfone amide structure and a compound having a thiourea structure, a phosphoric acid derivative compound, and a β-ketoester. Examples thereof include compounds and amino compounds.

〔Silane coupling agent〕
Examples of the silane coupling agent include the compound described in paragraph 0167 of International Publication No. 2015/199219, the compound described in paragraphs 0062 to 0073 of JP-A-2014-191002, paragraph of International Publication No. 2011/080992. The compounds described in 0063 to 0071, the compounds described in paragraphs 0060 to 0061 of JP-A-2014-191252, the compounds described in paragraphs 0045-0052 of JP-A-2014-041264, International Publication No. 2014/097594. Examples thereof include the compounds described in paragraph 0055 and the compounds described in paragraphs 0067 to 0078 of JP-A-2018-173573, the contents of which are incorporated herein by reference. Further, it is also preferable to use two or more different silane coupling agents as described in paragraphs 0050 to 0058 of JP-A-2011-128358. Further, it is also preferable to use the following compounds as the silane coupling agent. In the following formula, Me represents a methyl group and Et represents an ethyl group.

Examples of other silane coupling agents include vinyltrimethoxysilane, vinyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, and 3-glycid. Xipropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, p-styryltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxy 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-Phyl-3-aminopropyltrimethoxysilane, Tris- (trimethoxysilylpropyl) isocyanurate, 3-ureidopropyltrialkoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-isocyanate Examples thereof include propyltriethoxysilane and 3-trimethoxysilylpropylsuccinic anhydride. These can be used alone or in combination of two or more.

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

As other metal adhesion improving agents, the compounds described in paragraphs 0046 to 0049 of JP2014-186186A and the sulfide compounds described in paragraphs 0032 to 0043 of JP2013-072935 are used. These may also be incorporated herein by reference.

The content of the metal adhesive improving agent is preferably 0.01 to 30 parts by mass, more preferably 0.1 to 10 parts by mass, and further preferably 0. It is in the range of 5 to 5 parts by mass. When it is at least the above lower limit value, the adhesiveness between the pattern and the metal layer is good, and when it is at least the above upper limit value, the heat resistance and mechanical properties of the pattern are good. The metal adhesiveness improving agent may be only one kind or two or more kinds. When two or more types are used, it is preferable that the total is in the above range.

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

The migration inhibitor is not particularly limited, but has a heterocyclic ring (pyran ring, furan ring, thiophene ring, imidazole ring, oxazole ring, thiazole ring, pyrazole ring, isooxazole ring, isothiazole ring, tetrazole ring, pyridine ring, etc. Pyridazine ring, pyrimidine ring, pyrazine ring, piperidine ring, piperazine ring, morpholin ring, 2H-pyran ring and 6H-pyran ring, triazine ring), thiourea and sulfanyl group compounds, hindered phenolic compounds , Salicylic acid derivative compound, hydrazide derivative compound and the like. In particular, triazole compounds such as 1,2,4-triazole, benzotriazole, 3-amino-1,2,4-triazole, 3,5-diamino-1,2,4-triazole, 1H-tetrazole, 5- Tetrazole-based compounds such as phenyltetrazole and 5-amino-1H-tetrazole can be preferably used.

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

Examples of other migration inhibitors include the rust preventive agent described in paragraph 0094 of JP2013-015701, the compound described in paragraphs 0073 to 0076 of JP2009-283711, and JP-A-2011-059656. The compounds described in paragraph 0052, the compounds described in paragraphs 0114, 0116 and 0118 of JP2012-194520A, the compounds described in paragraph 0166 of International Publication No. 2015/199219, and the like can be used. The content is incorporated herein.

Specific examples of the migration inhibitor include the following compounds.

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

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

<Polymerization inhibitor>
The resin composition of the present invention preferably contains a polymerization inhibitor. Examples of the polymerization inhibitor include phenol-based compounds, quinone-based compounds, amino-based compounds, N-oxyl-free radical compound-based compounds, nitro-based compounds, nitroso-based compounds, heteroaromatic ring-based compounds, and metal compounds.

Specific compounds of the polymerization inhibitor include p-hydroquinone, o-hydroquinone, o-methoxyphenol, p-methoxyphenol, di-tert-butyl-p-cresol, pyrogallol, p-tert-butylcatechol, 1, 4-benzoquinone, diphenyl-p-benzoquinone, 4,4'-thiobis (3-methyl-6-tert-butylphenol), 2,2'-methylenebis (4-methyl-6-tert-butylphenol), N-nitrosophenyl Hydroxyamine primary cerium salt, N-nitroso-N-phenylhydroxyamine aluminum salt, N-nitrosodiphenylamine, N-phenylnaphthylamine, ethylenediamine tetraacetic acid, 1,2-cyclohexanediamine tetraacetic acid, glycol etherdiamine tetraacetic acid, 2, 6-di-tert-butyl-4-methylphenol, 5-nitroso-8-hydroxyquinoline, 1-nitroso-2-naphthol, 2-nitroso-1-naphthol, 2-nitroso-5 (N-ethyl-N) -Sulfospropylamino) phenol, N-nitroso-N- (1-naphthyl) hydroxyamine ammonium salt, bis (4-hydroxy-3,5-tert-butyl) phenylmethane, 1,3,5-tris (4-) t-Butyl-3-hydroxy-2,6-dimethylbenzyl) -1,3,5-triazine-2,4,6- (1H, 3H, 5H) -trione, 4-hydroxy-2,2,6 6-Tetramethylpiperidine 1-oxyl-free radical, 2,2,6,6-tetramethylpiperidine 1-oxyl-free radical, phenothiazine, phenoxazine, 1,1-diphenyl-2-picrylhydrazyl, dibutyldithiocarbanate Copper (II), nitrobenzene, N-nitroso-N-phenylhydroxylamine aluminum salt, N-nitroso-N-phenylhydroxylamine ammonium salt and the like are preferably used. Further, the polymerization inhibitor described in paragraph 0060 of JP-A-2015-127817 and the compound described in paragraphs 0031 to 0046 of International Publication No. 2015/125469 can also be used, and the contents thereof are described in the present specification. Be incorporated.

When the resin composition of the present invention has a polymerization inhibitor, the content of the polymerization inhibitor is preferably 0.01 to 20% by mass, preferably 0 to 20% by mass, based on the total solid content of the resin composition of the present invention. It is more preferably 0.02 to 15% by mass, and even more preferably 0.05 to 10% by mass.

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

<Acid scavenger>
The resin composition of the present invention preferably contains an acid scavenger in order to reduce the change in performance over time from exposure to heating. Here, the acid scavenger refers to a compound that can capture the generated acid by being present in the system, and is preferably a compound having low acidity and high pKa. As the acid trapping agent, a compound having an amino group is preferable, a primary amine, a secondary amine, a tertiary amine, an ammonium salt, a tertiary amine and the like are preferable, and a primary amine, a secondary amine, a tertiary amine and an ammonium salt are preferable. Is preferable, and secondary amines, tertiary amines, and ammonium salts are more preferable.
Examples of the acid scavenger include a compound having an imidazole structure, a diazabicyclo structure, an onium structure, a trialkylamine structure, an aniline structure or a pyridine structure, an alkylamine derivative having a hydroxyl group and / or an ether bond, and an aniline having a hydroxyl group and / or an ether bond. Derivatives and the like can be preferably mentioned. When having an onium structure, the acid scavenger is a salt having a cation selected from ammonium, diazonium, iodonium, sulfonium, phosphonium, pyridinium and the like, and an anion of an acid having a lower acidity than the acid generated by the acid generator. Is preferable.

Examples of the acid scavenger having an imidazole structure include imidazole, 2,4,5-triphenylimidazole, benzimidazole, 2-phenylbenzimidazole and the like. As an acid scavenger having a diazabicyclo structure, 1,4-diazabicyclo [2,2,2] octane, 1,5-diazabicyclo [4,3,0] nona-5-ene, 1,8-diazabicyclo [5,4] , 0] Undekar 7-En and the like. Examples of the acid trapping agent having an onium structure include tetrabutylammonium hydroxide, triarylsulfoniumhydroxydo, phenacylsulfoniumhydroxydo, sulfoniumhydroxydo having a 2-oxoalkyl group, specifically triphenylsulfoniumhydroxydo and tris (specifically, triphenylsulfonium hydroxide, tris ( Examples thereof include t-butylphenyl) sulfonium hydroxide, bis (t-butylphenyl) iodonium hydroxide, phenacylthiophenium hydroxide, and 2-oxopropylthiophenium hydroxide. Examples of the acid scavenger having a trialkylamine structure include tri (n-butyl) amine and tri (n-octyl) amine. Examples of the acid scavenger having an aniline structure include 2,6-diisopropylaniline, N, N-dimethylaniline, N, N-dibutylaniline, N, N-dihexylaniline and the like. Examples of the acid scavenger having a pyridine structure include pyridine, 4-methylpyridine and the like. Examples of the alkylamine derivative having a hydroxyl group and / or an ether bond include ethanolamine, diethanolamine, triethanolamine, N-phenyldiethanolamine, tris (methoxyethoxyethyl) amine and the like. Examples of the aniline derivative having a hydroxyl group and / or an ether bond include N, N-bis (hydroxyethyl) aniline and the like.

Specific examples of preferred acid trapping agents include ethanolamine, diethanolamine, triethanolamine, ethylamine, diethylamine, triethylamine, hexylamine, dodecylamine, cyclohexylamine, cyclohexylmethylamine, cyclohexyldimethylamine, aniline, N-methylaniline, N. , N-dimethylaniline, diphenylamine, pyridine, butylamine, isobutylamine, dibutylamine, tributylamine, dicyclohexylamine, DBU (diazabicycloundecene), DABCO (1,4-diazabicyclo [2.2.2] octane), N, N-diisopropylethylamine, tetramethylammonium hydroxide, ethylenediamine, 1,5-diaminopentane, N-methylhexylamine, N-methyldicyclohexylamine, trioctylamine, N-ethylethylenediamine, N, N-diethylethylenediamine, N, N, N', N'-tetrabutyl-1,6-hexanediamine, spermidin, diaminocyclohexane, bis (2-methoxyethyl) amine, piperidine, methylpiperidin, piperazine, tropane, N-phenylbenzylamine, 1, 2 -Dianilinoetan, 2-aminoethanol, toluidine, aminophenol, hexylaniline, phenylenediamine, phenylethylamine, dibenzylamine, pyrrol, N-methylpyrol, guanidine, aminopyrrolidin, pyrazole, pyrazoline, aminomorpholin, aminoalkylmorpholin, etc. Can be given.

These acid scavengers may be used alone or in combination of two or more.
The composition according to the present invention may or may not contain an acid scavenger, but when it is contained, the content of the acid scavenger is usually 0.001 to 0 based on the total solid content of the composition. It is 10% by mass, preferably 0.01 to 5% by mass.

The ratio of the acid generator to the acid scavenger is preferably acid generator / acid scavenger (molar ratio) = 2.5 to 300. That is, the molar ratio is preferably 2.5 or more from the viewpoint of sensitivity and resolution, and preferably 300 or less from the viewpoint of suppressing the decrease in resolution due to the thickening of the relief pattern over time from the exposure to the heat treatment. The acid generator / acid scavenger (molar ratio) is more preferably 5.0 to 200, still more preferably 7.0 to 150.

<Other additives>
The resin composition of the present invention comprises various additives such as a surfactant, a higher fatty acid derivative, a thermal polymerization initiator, an inorganic particle, and an ultraviolet absorber, if necessary, as long as the effects of the present invention can be obtained. Organic titanium compounds, antioxidants, antiaggregating agents, phenolic compounds, other polymer compounds, plasticizers and other auxiliaries (eg, antifoaming agents, flame retardant agents, etc.) can be blended. By appropriately containing these components, properties such as film physical characteristics can be adjusted. These components are described in, for example, paragraph No. 0183 or later of JP2012-003225A (paragraph number 0237 of the corresponding US Patent Application Publication No. 2013/0034812), paragraph 2008-250074. The description of numbers 0101 to 0104, 0107 to 0109, etc. can be taken into consideration, and these contents are incorporated in the present specification. When these additives are blended, the total blending amount is preferably 3% by mass or less of the solid content of the resin composition of the present invention.

[Surfactant]
As the surfactant, various surfactants such as a fluorine-based surfactant, a silicone-based surfactant, and a hydrocarbon-based surfactant can be used. The surfactant may be a nonionic surfactant, a cationic surfactant, or an anionic surfactant.

By containing a surfactant in the photosensitive resin composition of the present invention, the liquid characteristics (particularly, fluidity) when prepared as a coating liquid are further improved, and the uniformity of the coating thickness and the liquid saving property are further improved. can do. That is, when a film is formed by using a coating liquid to which a composition containing a surfactant is applied, the interfacial tension between the surface to be coated and the coating liquid is reduced, and the wettability to the surface to be coated is improved. , The applicability to the surface to be coated is improved. Therefore, it is possible to more preferably form a film having a uniform thickness with small thickness unevenness.

Examples of the fluorine-based surfactant include Megafuck F171, F172, F173, F176, F177, F141, F142, F143, F144, R30, F437, F475, and F479. F482, F554, F780, RS-72-K (above, manufactured by DIC Co., Ltd.), Florard FC430, FC431, FC171, Novek FC4430, FC4432 (above, manufactured by 3M Japan Ltd.), Surfron S-382, SC-101, SC-103, SC-104, SC-105, SC-1068, SC-381, SC-383, S-393, KH-40 (and above) , Asahi Glass Co., Ltd.), PF636, PF656, PF6320, PF6520, PF7002 (manufactured by OMNOVA) and the like. As the fluorine-based surfactant, the compounds described in paragraphs 0015 to 0158 of JP-A-2015-117327 and the compounds described in paragraphs 0117 to 0132 of JP-A-2011-132503 can also be used. Incorporated herein. A block polymer can also be used as the fluorine-based surfactant, and specific examples thereof include compounds described in JP-A-2011-89090, the contents of which are incorporated in the present specification.
The fluorine-based surfactant has a repeating unit derived from a (meth) acrylate compound having a fluorine atom and 2 or more (preferably 5 or more) alkyleneoxy groups (preferably ethyleneoxy groups and propyleneoxy groups) (meth). A fluorine-containing polymer compound containing a repeating unit derived from an acrylate compound can also be preferably used, and the following compounds are also exemplified as the fluorine-based surfactant used in the present invention.

The weight average molecular weight of the above compounds is preferably 3,000 to 50,000, more preferably 5,000 to 30,000.
As the fluorine-based surfactant, a fluorine-containing polymer having an ethylenically unsaturated group in the side chain can also be used as the fluorine-based surfactant. Specific examples thereof include the compounds described in paragraphs 0050 to 0090 and 0289 to 0295 of JP2010-164965, the contents of which are incorporated in the present specification. Examples of commercially available products include Megafuck RS-101, RS-102, and RS-718K manufactured by DIC Corporation.

The fluorine content in the fluorine-based surfactant is preferably 3 to 40% by mass, more preferably 5 to 30% by mass, and particularly preferably 7 to 25% by mass. A fluorine-based surfactant having a fluorine content within this range is effective in terms of uniformity in the thickness of the coating film and liquid saving, and has good solubility in the composition.

Examples of the silicone-based surfactant include Torre Silicone DC3PA, Torre Silicone SH7PA, Torre Silicone DC11PA, Torre Silicone SH21PA, Torre Silicone SH28PA, Torre Silicone SH29PA, Torre Silicone SH30PA, Torre Silicone SH8400 (all, Toray Dow Corning Co., Ltd.). ), TSF-4440, TSF-4300, TSF-4445, TSF-4460, TSF-4452 (all manufactured by Momentive Performance Materials), KP-341, KF6001, KF6002 (all manufactured by Shinetsu Silicone Co., Ltd.) ), BYK307, BYK323, BYK330 (all manufactured by Big Chemie Co., Ltd.) and the like.

Examples of the hydrocarbon-based surfactant include Pionin A-76, Newcalgen FS-3PG, Pionin B-709, Pionin B-811-N, Pionin D-1004, Pionin D-3104, Pionin D-3605, and Pionin. D-6112, Pionin D-2104-D, Pionin D-212, Pionin D-931, Pionin D-941, Pionin D-951, Pionin E-5310, Pionin P-1050-B, Pionin P-1028-P, Pionin P-4050-T and the like (all manufactured by Takemoto Oil & Fat Co., Ltd.) and the like can be mentioned.

Nonionic surfactants include glycerol, trimethylolpropane, trimethylolethane and their ethoxylates and propoxylates (eg, glycerol propoxylate, glycerol ethoxylate, etc.), polyoxyethylene lauryl ethers, polyoxyethylene stearyl ethers, etc. Examples thereof include polyoxyethylene oleyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, and sorbitan fatty acid ester. Commercially available products include Pluronic (registered trademark) L10, L31, L61, L62, 10R5, 17R2, 25R2 (manufactured by BASF), Tetronic 304, 701, 704, 901, 904, 150R1 (manufactured by BASF), Solspers 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 (Takemoto Oil and Fat (Takemoto Oil & Fat) (Manufactured by Nisshin Chemical Industries, Ltd.), Orfin E1010, Surfinol 104, 400, 440 (manufactured by Nissin Chemical Industries, Ltd.) and the like.

Specifically, as a cationic surfactant, organosiloxane polymer KP-341 (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 Chemical Co., Ltd.), W001 (manufactured by Yusho Co., Ltd.) and the like can be mentioned.

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

Only one type of surfactant may be used, or two or more types may be combined.
The content of the surfactant is preferably 0.001 to 2.0% by mass, more preferably 0.005 to 1.0% by mass, based on the total solid content of the composition.

[Higher fatty acid derivative]
In order to prevent polymerization inhibition caused by oxygen, the resin composition of the present invention is added with a higher fatty acid derivative such as behenic acid or behenic acid amide, and the resin composition of the present invention is dried in the process of drying after application. It may be unevenly distributed on the surface of.

Further, as the higher fatty acid derivative, the compound described in paragraph 0155 of International Publication No. 2015/199219 can also be used, and this content is incorporated in the present specification.

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

[Thermal polymerization initiator]
The resin composition of the present invention may contain a thermal polymerization initiator, and may particularly contain a thermal radical polymerization initiator. The thermal radical polymerization initiator is a compound that generates radicals by heat energy to initiate or accelerate the polymerization reaction of a polymerizable compound. Since the polymerization reaction of the resin and the polymerizable compound can be promoted by adding the thermal radical polymerization initiator, the solvent resistance can be further improved. Further, the above-mentioned photopolymerization initiator may also have a function of initiating polymerization by heat, and may be added as a thermal polymerization initiator.

Specific examples of the thermal radical polymerization initiator include the compounds described in paragraphs 0074 to 0118 of JP-A-2008-063554, the contents of which are incorporated in the present specification.

When the thermal polymerization initiator is contained, the content thereof is preferably 0.1 to 30% by mass, more preferably 0.1 to 20% by mass, based on the total solid content of the resin composition of the present invention. , More preferably 0.5 to 15% by mass. Only one type of thermal polymerization initiator may be contained, or two or more types may be contained. When two or more kinds of thermal polymerization initiators are contained, the total amount is preferably in the above range.

[Inorganic particles]
The resin composition of the present invention may contain inorganic particles. Specific examples of the inorganic particles include calcium carbonate, calcium phosphate, silica, kaolin, talc, titanium dioxide, alumina, barium sulfate, calcium fluoride, lithium fluoride, zeolite, molybdenum sulfide, and glass.

The average particle size of the inorganic particles is preferably 0.01 to 2.0 μm, more preferably 0.02 to 1.5 μm, further preferably 0.03 to 1.0 μm, and 0.04 to 0.5 μm. Especially preferable.
The average particle size of the inorganic particles is a primary particle size and a volume average particle size. The volume average particle size can be measured by a dynamic light scattering method using Nanotrac WAVE II EX-150 (manufactured by Nikkiso Co., Ltd.).
If the above measurement is difficult, it can be measured by a centrifugal sedimentation light transmission method, an X-ray transmission method, or a laser diffraction / scattering method.

[UV absorber]
The composition of the present invention may contain an ultraviolet absorber. As the ultraviolet absorber, an ultraviolet absorber such as salicylate-based, benzophenone-based, benzotriazole-based, substituted acrylonitrile-based, or triazine-based can be used.
Examples of salicylate-based ultraviolet absorbers include phenylsalicylate, p-octylphenyl salicylate, pt-butylphenyl salicylate and the like, and examples of benzophenone-based ultraviolet 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- Hydroxyl-4-octoxybenzophenone and the like can be mentioned. Examples of benzotriazole-based ultraviolet absorbers include 2- (2'-hydroxy-3', 5'-di-tert-butylphenyl) -5-chlorobenzotriazole and 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 can be mentioned.

Examples of the substituted acrylonitrile-based ultraviolet absorber include ethyl 2-cyano-3,3-diphenylacrylate, 2-ethylhexyl 2-cyano-3,3-diphenylacrylate, and the like. Further, as an example of the triazine-based ultraviolet absorber, 2- [4-[(2-hydroxy-3-dodecyloxypropyl) oxy] -2-hydroxyphenyl] -4,6-bis (2,4-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 and other bis (hydroxyphenyl) triazine compounds; 2,4-bis (2-hydroxy-4-butoxyphenyl) -6- (2,4-dibutoxyphenyl) ) -1,3,5-triazine, 2,4,6-tris (2-hydroxy-4-octyloxyphenyl) -1,3,5-triazine, 2,4,6-tris [2-hydroxy-4 -(3-Butoxy-2-hydroxypropyloxy) phenyl] -1,3,5-triazine and other tris (hydroxyphenyl) triazine compounds and the like can be mentioned.

In the present invention, the above-mentioned various ultraviolet absorbers 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 when it is contained, the content of the ultraviolet absorber is 0.001% by mass with respect to the total solid content 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.

[Organic titanium compound]
The resin composition of the present embodiment may contain an organic titanium compound. Since 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 the organic titanium compound 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 the organic titanium compound are shown in I) to VII) below:
I) Titanium chelate compound: Among them, a titanium chelate compound having two or more alkoxy groups is more preferable because the resin composition has good storage stability and a good curing pattern can be obtained. Specific examples include titanium bis (triethanolamine) diisopropoxyside, titanium di (n-butoxide) bis (2,4-pentanegenate), and titanium diisopropoxiside bis (2,4-pentanegeonate). ), Titanium diisopropoxyside bis (tetramethylheptandionate), titanium diisopropoxyside bis (ethylacetacetate) and the like.
II) Titanium Alkoxy Titanium Compounds: For example, Titanium Tetra (n-Butoxide), Titanium Tetraethoxide, Titanium Tetra (2-ethylhexoxyside), Titanium Tetraisobutoxide, Titanium Tetraisopropoxyside, Titanium Tetramethoxide , Titanium Tetramethoxypropoxyside, Titanium Tetramethylphenoxide, Titanium Tetra (n-Noniloxide), Titanium Tetra (n-Propoxide), Titanium Tetrasteeryloxyside, Titanium Tetrakiss [Bis {2,2- (Aryloxymethyl) Butokiside}] etc.
III) Titanocene compounds: for example, pentamethylcyclopentadienyl titanium trimethoxide, bis (η5-2,4-cyclopentadiene-1-yl) bis (2,6-difluorophenyl) titanium, bis (η5-2, 2). 4-Cyclopentadiene-1-yl) bis (2,6-difluoro-3- (1H-pyrrole-1-yl) phenyl) titanium and the like.
IV) Monoalkoxytitanium compound: For example, titaniumtris (dioctylphosphate) isopropoxyside, titaniumtris (dodecylbenzenesulfonate) isopropoxyside and the like.
V) Titanium oxide compound: For example, titanium oxide bis (pentanionate), titanium oxide bis (tetramethylheptandionate), phthalocyanine titanium oxide and the like.
VI) Titanium tetraacetylacetonate compound: For example, titanium tetraacetylacetonate and the like.
VII) Titanate Coupling Agent: For example, isopropyltridodecylbenzenesulfonyl titanate and the like.

Among them, as the organic titanium compound, at least one compound selected from the group consisting of the above-mentioned I) titanium chelate compound, II) tetraalkoxytitanium compound, and III) titanosen compound has better chemical resistance. It is preferable from the viewpoint of playing. In particular, titanium diisopropoxyside bis (ethylacetacetate), titanium tetra (n-butoxide), and bis (η5-2,4-cyclopentadiene-1-yl) bis (2,6-difluoro-3- (1H)). -Pyrrole-1-yl) phenyl) titanium is preferred.

When the organic titanium compound is blended, the blending amount is preferably 0.05 to 10 parts by mass, more preferably 0.1 to 2 parts by mass with respect to 100 parts by mass of the specific resin. When the blending amount is 0.05 parts by mass or more, good heat resistance and chemical resistance are more effectively exhibited in the obtained curing pattern, while when it is 10 parts by mass or less, the storage stability of the composition Excellent.

〔Antioxidant〕
The composition of the present invention may contain an antioxidant. By containing an antioxidant as an additive, it is possible to improve the elongation characteristics of the film after curing and the adhesion with a metal material. Examples of the antioxidant include a phenol compound, a phosphite ester compound, a thioether compound and the like. As the phenol compound, any phenol compound known as a phenolic antioxidant can be used. Preferred phenolic compounds include hindered phenolic compounds. A compound having a substituent at a site (ortho position) adjacent to the phenolic hydroxy group is preferable. As the above-mentioned substituent, a substituted or unsubstituted alkyl group having 1 to 22 carbon atoms is preferable. Further, as the antioxidant, a compound having a phenol group and a phosphite ester group in the same molecule is also preferable. Further, as the antioxidant, a phosphorus-based antioxidant can also be preferably used. As a phosphorus-based antioxidant, Tris [2-[[2,4,8,10-tetrakis (1,1-dimethylethyl) dibenzo [d, f] [1,3,2] dioxaphosphepine-6] -Il] Oxy] Ethyl] amine, Tris [2-[(4,6,9,11-tetra-tert-butyldibenzo [d, f] [1,3,2] dioxaphosphepin-2-yl] ) Oxy] ethyl] amine, ethylbis phosphite (2,4-di-tert-butyl-6-methylphenyl) and the like. Commercially available products of 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, and Adekastab AO-80. , ADEKA STAB AO-330 (above, manufactured by ADEKA Corporation) and the like. Further, as the antioxidant, the compounds described in paragraphs 0023 to 0048 of Japanese Patent No. 6268967 can also be used, and the contents thereof are incorporated in the present specification. In addition, the composition of the present invention may contain a latent antioxidant, if necessary. The latent antioxidant is a compound in which the site that functions as an antioxidant is protected by a protecting group, and is heated at 100 to 250 ° C. or at 80 to 200 ° C. in the presence of an acid / base catalyst. This includes compounds in which the protecting group is desorbed and functions as an antioxidant. Examples of the latent antioxidant include compounds described in International Publication No. 2014/021023, International Publication No. 2017/030005, and JP-A-2017-008219, the contents of which are incorporated in the present specification. Examples of commercially available products of latent antioxidants include ADEKA ARKULS GPA-5001 (manufactured by ADEKA Corporation).
Examples of preferred antioxidants include 2,2-thiobis (4-methyl-6-t-butylphenol), 2,6-di-t-butylphenol and compounds of formula (3).

In the general formula (3), R ⁵ represents a hydrogen atom or an alkyl group having 2 or more carbon atoms (preferably 2 to 10 carbon atoms), and R ⁶ represents an alkylene having 2 or more carbon atoms (preferably 2 to 10 carbon atoms). Represents a group. R ⁷ represents a 1- to tetravalent organic group containing at least one of an alkylene group having 2 or more carbon atoms (preferably 2 to 10 carbon atoms), an oxygen atom, and a nitrogen atom. k represents an integer of 1 to 4.

The compound represented by the formula (3) suppresses the oxidative deterioration of the aliphatic group and the phenolic hydroxyl group of the resin. In addition, metal oxidation can be suppressed by the rust preventive action on the metal material.

Since it can act on the resin and the metal material at the same time, k is more preferably an integer of 2 to 4. Examples of R ⁷ include an alkyl group, a cycloalkyl group, an alkoxy group, an alkyl ether group, an alkylsilyl group, an alkoxysilyl group, an aryl group, an arylether group, a carboxyl group, a carbonyl group, an allyl group, a vinyl group and a heterocyclic group. -O-, -NH-, -NHNH-, a combination thereof and the like can be mentioned, and may further have a substituent. Among these, it is preferable to have an alkyl ether group and -NH- from the viewpoint of solubility in a developing solution and metal adhesion, and -NH- is preferable from the viewpoint of interaction with a resin and metal adhesion due to metal complex formation. More preferred.

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

The amount of the antioxidant added is preferably 0.1 to 10 parts by mass, more preferably 0.5 to 5 parts by mass with respect to the resin. When the addition amount is 0.1 part by mass or more, the effect of improving the elongation property and the adhesion to the metal material can be easily obtained even in a high temperature and high humidity environment, and when the addition amount is 10 parts by mass or less, for example, photosensitive is exhibited. The interaction with the agent improves the sensitivity of the resin composition. Only one kind of antioxidant may be used, or two or more kinds may be used. When two or more types are used, it is preferable that the total amount thereof is within the above range.

[Anti-coagulation agent]
The resin composition of the present embodiment may contain an anti-aggregation agent, if necessary. Examples of the antiaggregating agent include sodium polyacrylate and the like.

In the present invention, one type of anti-aggregation agent may be used alone, or two or more types may be used in combination.
The composition of the present invention may or may not contain an anti-aggregation agent, but when it is contained, the content of the anti-aggregation agent is 0.01% by mass with respect to the total solid content mass of the composition of the present invention. It is preferably 10% by mass or less, and more preferably 0.02% by mass or more and 5% by mass or less.

[Phenolic compounds]
The resin composition of the present embodiment may contain a phenolic compound, if necessary. Examples of the phenolic compound include Bis-Z, BisP-EZ, TekP-4HBPA, TrisP-HAP, TrisP-PA, BisOCHP-Z, BisP-MZ, BisP-PZ, BisP-IPZ, BisOCP-IPZ, and BisP-CP. BisRS-2P, BisRS-3P, BisP-OCHP, Methylenetris-FR-CR, BisRS-26X (trade name, manufactured by Honshu Chemical Industry Co., Ltd.), BIP-PC, BIR-PC, BIR-PTBP, BIR -BIPC-F (above, trade name, manufactured by Asahi Organic Materials Industry Co., Ltd.) and the like can be mentioned.

In the present invention, one type of phenolic compound may be used alone, or two or more types may be used in combination.
The composition of the present invention may or may not contain a phenolic compound, but when it is contained, the content of the phenolic compound is 0.01% by mass with respect to the total solid content mass of the composition of the present invention. It is preferably 30% by mass or more, and more preferably 0.02% by mass or more and 20% by mass or less.

[Other polymer compounds]
Examples of other polymer compounds include siloxane resins, (meth) acrylic polymers copolymerized with (meth) acrylic acid, novolak resins, resole resins, polyhydroxystyrene resins and copolymers thereof. The other polymer compound may be a modified product into which a cross-linking group such as a methylol group, an alkoxymethyl group, or an epoxy group is introduced.

In the present invention, one type of other polymer compound may be used alone, or two or more types may be used in combination.
The composition of the present invention may or may not contain other polymer compounds, but when it is contained, the content of the other polymer compounds is 0 with respect to the total solid content mass of the composition of the present invention. It is preferably 0.01% by mass or more and 30% by mass or less, and more preferably 0.02% by mass or more and 20% by mass or less.

<Characteristics of resin composition>
The viscosity of the resin composition of the present invention can be adjusted by adjusting the solid content concentration of the resin composition. From the viewpoint of the coating film thickness, 1,000 mm ² / s to 12,000 mm ² / s is preferable, 2,000 mm ² / s to 10,000 mm ² / s is more preferable, and 3,000 mm ² / s to 8,000 mm. ² / s is more preferable. Within the above range, it becomes easy to obtain a highly uniform coating film. At 1,000 mm ² / s or less, it is difficult to apply the film with a film thickness required as an insulating film for rewiring, for example, and at 12,000 mm ² / s or more, the coated surface condition may deteriorate. ..

<Restrictions on substances contained in the resin composition>
The water content of the resin composition of the present invention is preferably less than 2.0% by mass, more preferably less than 1.5% by mass, and even more preferably less than 1.0% by mass. If it is 2.0% or more, the storage stability of the resin composition may be impaired.
Examples of the method for maintaining the water content include adjusting the humidity under storage conditions and reducing the porosity of the storage container during storage.

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

Further, as a method for reducing metal impurities unintentionally contained in the resin composition of the present invention, the resin composition of the present invention selects a raw material having a low metal content as the raw material constituting the resin composition of the present invention. Examples thereof include a method of filtering the raw materials constituting the product by a filter, a method of lining the inside of the device with polytetrafluoroethylene or the like, and performing distillation under conditions in which contamination is suppressed as much as possible.

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

A conventionally known storage container can be used as the storage container for the resin composition of the present invention. Further, as the storage container, a multi-layer bottle having a container inner wall made of 6 types and 6 layers of resin and 6 types of resin are used for the purpose of suppressing contamination of raw materials and the resin composition of the present invention with impurities. It is also preferable to use a bottle having a 7-layer structure. Examples of such a container include the container described in Japanese Patent Application Laid-Open No. 2015-123351.

<Cured product of resin composition>
By curing the resin composition of the present invention, a cured product of this resin composition can be obtained.
The cured product of the present invention is a cured product obtained by curing the resin composition of the present invention.
The curing of the resin composition is preferably by heating, more preferably the heating temperature is in the range of 120 ° C to 400 ° C, further preferably in the range of 140 ° C to 380 ° C, and 170 ° C. It is particularly preferable that the temperature is in the range of about 350 ° C. The form of the cured product of the resin composition is not particularly limited, and can be selected according to the intended use, such as a film shape, a rod shape, a spherical shape, and a pellet shape. In the present invention, the cured product is preferably in the form of a film. In addition, by pattern processing of the resin composition, this cured product can be used for forming a protective film on the wall surface, forming via holes for conduction, adjusting impedance, capacitance or internal stress, and providing heat dissipation function. You can also choose the shape. The film thickness of this cured product (film made of the cured product) is preferably 0.5 μm or more and 150 μm or less.
The shrinkage rate of the resin composition of the present invention when cured is preferably 50% or less, more preferably 45% or less, still more preferably 40% or less. Here, the shrinkage ratio refers to the percentage of the volume change of the resin composition before and after curing, and can be calculated from the following formula.
Shrinkage rate [%] = 100- (volume after curing ÷ volume before curing) x 100

<Characteristics of cured product of resin composition>
The imidization reaction rate of the cured product of the resin composition of the present invention is preferably 70% or more, more preferably 80% or more, still more preferably 90% or more. If it is less than 70%, the mechanical properties of the cured product may be inferior.
The elongation at break of the cured product of the resin composition of the present invention is preferably 30% or more, more preferably 40% or more, still more preferably 50% or more.
The glass transition temperature (Tg) of the cured product of the resin composition of the present invention is preferably 180 ° C. or higher, more preferably 210 ° C. or higher, and even more preferably 230 ° C. or higher.

<Preparation of resin composition>
The resin composition of the present invention can be prepared by mixing each of the above components. The mixing method is not particularly limited, and a conventionally known method can be used.
For mixing, mixing with a stirring blade, mixing with a ball mill, mixing by rotating the tank itself, or the like can be adopted.
The temperature during mixing is preferably 10 to 30 ° C, more preferably 15 to 25 ° C.

Further, it is preferable to perform filtration using a filter for the purpose of removing foreign substances such as dust and fine particles in the resin composition of the present invention. The filter hole diameter may be, for example, 5 μm or less, preferably 1 μm or less, more preferably 0.5 μm or less, still more preferably 0.1 μm or less. The filter material is preferably polytetrafluoroethylene, polyethylene or nylon. When the material of the filter is polyethylene, it is more preferable to use HDPE (high density polyethylene). The filter may be one that has been pre-cleaned with an organic solvent. In the filter filtration step, a plurality of types of filters may be connected in series or in parallel for use. When using a plurality of types of filters, filters having different pore diameters or materials may be used in combination. Examples of the connection mode include a mode in which an HDPE filter having a hole diameter of 1 μm is connected in series as the first stage and an HDPE filter having a hole diameter of 0.2 μm is connected in series as the second stage. In addition, various materials may be filtered a plurality of times. When filtering multiple times, circulation filtration may be used. Moreover, you may pressurize and perform filtration. When pressurizing and filtering, the pressure to be pressurized is, for example, 0.01 MPa or more and 1.0 MPa or less, preferably 0.03 MPa or more and 0.9 MPa or less, and more preferably 0.05 MPa or more and 0.7 MPa or less. , 0.05 MPa or more and 0.5 MPa or less is more preferable.
In addition to filtration using a filter, impurities may be removed using an adsorbent. Filter filtration and impurity removal treatment using an adsorbent may be combined. As the adsorbent, a known adsorbent can be used. Examples thereof include inorganic adsorbents such as silica gel and zeolite, and organic adsorbents such as activated carbon.
Further, after filtration using a filter, the resin composition filled in the bottle may be placed under reduced pressure to perform a step of degassing.

(Manufacturing method of cured product)
The method for producing a cured product of the present invention preferably includes a film forming step of applying a resin composition onto a substrate to form a film.
Further, in the method for producing a cured product of the present invention, the film forming step, the exposure step of selectively exposing the film formed by the film forming step, and the film exposed by the exposure step are developed using a developing solution. It is more preferable to include a developing step of forming a pattern.
The method for producing a cured product of the present invention includes the film forming step, the exposure step, the developing step, and the heating step for heating the pattern obtained by the developing step and the post-development for exposing the pattern obtained by the developing step. It is particularly preferred to include at least one of the exposure steps.
Moreover, it is also preferable that the production method of the present invention includes the above-mentioned film forming step and the above-mentioned step of heating the film.
Hereinafter, details of each step will be described.

<Membrane formation process>
The resin composition of the present invention can be applied to a substrate to form a film and can be used in a film forming step.
The method for producing a cured product of the present invention preferably includes a film forming step of applying a resin composition onto a substrate to form a film.

〔Base material〕
The type of base material can be appropriately determined depending on the application, but semiconductor-made base materials such as silicon, silicon nitride, polysilicon, silicon oxide, and amorphous silicon, quartz, glass, optical film, ceramic material, and thin-film deposition film, Any of a metal base material such as a magnetic film, a reflective film, Ni, Cu, Cr, Fe (for example, a base material formed of metal, or a base material in which a metal layer is formed by, for example, plating or thin film deposition). (May be good), paper, SOG (Spin On Glass), TFT (thin film film) array base material, mold base material, electrode plate of plasma display panel (PDP), and the like, and are not particularly limited. In the present invention, a semiconductor-made base material is particularly preferable, and a silicon base material, a Cu base material, and a molded base material are more preferable.
Further, these substrates may be provided with a layer such as an adhesion layer or an oxide layer made of hexamethyldisilazane (HMDS) or the like on the surface thereof.
Further, the shape of the base material is not particularly limited, and may be circular or rectangular.
The size of the base material is, for example, 100 to 450 mm in diameter, preferably 200 to 450 mm in a circular shape. If it is rectangular, for example, the length of the short side is 100 to 1000 mm, preferably 200 to 700 mm.
Further, as the base material, for example, a plate-shaped base material (substrate), preferably a panel-shaped base material (board) is used.

Further, when a resin composition is applied to the surface of a resin layer (for example, a layer made of a cured product) or the surface of a metal layer to form a film, the resin layer or the metal layer becomes a base material.

Coating is preferable as a means for applying the resin composition of the present invention on a substrate.

Specifically, the means to be applied include a dip coating method, an air knife coating method, a curtain coating method, a wire bar coating method, a gravure coating method, an extrusion coating method, a spray coating method, a spin coating method, and a slit coating method. An inkjet method and the like are exemplified. From the viewpoint of film thickness uniformity, a spin coating method, a slit coating method, a spray coating method, or an inkjet method is more preferable, and spin coating is performed from the viewpoint of film thickness uniformity and productivity. The method and the slit coating method are preferable. By adjusting the solid content concentration and the coating conditions of the resin composition according to the method, a film having a desired thickness can be obtained. Further, the coating method can be appropriately selected depending on the shape of the substrate. For a circular substrate such as a wafer, a spin coating method, a spray coating method, an inkjet method, etc. are preferable, and for a rectangular substrate, a slit coating method or a spray coating method is preferable. The method, the inkjet method and the like are preferable. In the case of the spin coating method, for example, it can be applied at a rotation speed of 500 to 3,500 rpm for about 10 seconds to 3 minutes.
Further, it is also possible to apply a method of transferring a coating film previously applied onto a temporary support by the above-mentioned application method onto a substrate.
Regarding the transfer method, the production method described in paragraphs 0023 and 0036 to 0051 of JP-A-2006-023696 and paragraphs 0090 to 0108 of JP-A-2006-047592 can be suitably used in the present invention.
Further, a step of removing the excess film at the end of the base material may be performed. Examples of such a process include edge bead rinse (EBR), back rinse and the like.
Further, a pre-wet step of applying various solvents to the base material before applying the resin composition to the base material to improve the wettability of the base material and then applying the resin composition may be adopted.

<Drying process>
The film may be subjected to a step (drying step) of drying the film (layer) formed to remove the solvent after the film forming step (layer forming step).
That is, the method for producing a cured product of the present invention may include a drying step of drying the film formed by the film forming step.
Further, it is preferable that the drying step is performed after the film forming step and before the exposure step.
The drying temperature of the film in the drying step is preferably 50 to 150 ° C, more preferably 70 ° C to 130 ° C, still more preferably 90 ° C to 110 ° C. Further, drying may be performed by reducing the pressure. The drying time is exemplified by 30 seconds to 20 minutes, preferably 1 minute to 10 minutes, more preferably 2 minutes to 7 minutes.

<Exposure process>
The film may be subjected to an exposure step of selectively exposing the film.
That is, the method for producing a cured product of the present invention may include an exposure step of selectively exposing the film formed by the film forming step.
Selective exposure means exposing a part of the film. Further, by selectively exposing the film, an exposed region (exposed portion) and an unexposed region (non-exposed portion) are formed on the film.
The exposure amount is not particularly determined as long as the resin composition of the present invention can be cured, but for example, it is preferably 50 to 10,000 mJ / cm ² in terms of exposure energy at a wavelength of 365 nm, and 200 to 8,000 mJ / cm ² . Is more preferable.

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

The exposure wavelengths are as follows: (1) semiconductor laser (wavelength 830 nm, 532 nm, 488 nm, 405 nm, 375 nm, 355 nm etc.), (2) metal halide lamp, (3) high-pressure mercury lamp, g-ray (wavelength). 436 nm), h line (wavelength 405 nm), i line (wavelength 365 nm), broad (3 wavelengths of g, h, i line), (4) excimer laser, KrF excimer laser (wavelength 248 nm), ArF excimer laser (wavelength 193 nm) ), F2 excimer laser (wavelength 157 nm), (5) extreme ultraviolet rays; EUV (wavelength 13.6 nm), (6) electron beam, (7) YAG laser second harmonic 532 nm, third harmonic 355 nm, etc. Will be. The resin composition of the present invention is particularly preferably exposed to a high-pressure mercury lamp, and above all, to be exposed to i-rays. As a result, particularly high exposure sensitivity can be obtained.
It is also preferable that the exposure light used for exposure includes light having a wavelength of 405 nm.
The exposure method is not particularly limited as long as it is a method in which at least a part of the film made of the resin composition of the present invention is exposed, but exposure using a photomask, exposure by a laser direct imaging method, or the like is possible. Can be mentioned.

<Heating process after exposure>
The film may be subjected to a step of heating after exposure (post-exposure heating step).
That is, the method for producing a cured product of the present invention may include a post-exposure heating step of heating the film exposed by the exposure step.
The post-exposure heating step can be performed after the exposure step and before the developing step.
The heating temperature in the post-exposure heating step is preferably 50 ° C to 140 ° C, more preferably 60 ° C to 120 ° C.
The heating time in the post-exposure heating step is preferably 30 seconds to 300 minutes, more preferably 1 minute to 10 minutes.
The heating rate in the post-exposure heating step is preferably 1 to 12 ° C./min, more preferably 2 to 10 ° C./min, and even more preferably 3 to 10 ° C./min from the temperature at the start of heating to the maximum heating temperature.
Further, the heating rate may be appropriately changed during heating.
The heating means in the post-exposure heating step is not particularly limited, and a known hot plate, oven, infrared heater, or the like can be used.
Further, it is also preferable to carry out the heating in an atmosphere having a low oxygen concentration by flowing an inert gas such as nitrogen, helium or argon.

<Development process>
The film after exposure may be subjected to a developing step of developing with a developing solution to form a pattern.
That is, the method for producing a cured product of the present invention may include a developing step of developing a film exposed by the exposure step with a developing solution to form a pattern. By performing the development, one of the exposed portion and the non-exposed portion of the film is removed, and a pattern is formed.
Here, the development in which the non-exposed portion of the film is removed by the developing step is called negative type development, and the development in which the exposed portion of the film is removed by the developing step is called positive type development.

[Developer]
Examples of the developing solution used in the developing step include an alkaline aqueous solution or a developing solution containing an organic solvent.

When the developing solution is an alkaline aqueous solution, examples of the basic compound that the alkaline aqueous solution can contain include inorganic alkalis, primary amines, secondary amines, tertiary amines, and quaternary ammonium salts. , TMAH (Tetramethylammonium Hydroxide), potassium hydroxide, sodium carbonate, sodium hydroxide, sodium silicate, sodium metasilicate, ammonia, ethylamine, n-propylamine, diethylamine, di-n-butylamine, triethylamine, methyldiethylamine , Dimethylethanolamine, Triethanolamine, Tetraethylammonium Hydroxide, Tetrapropylammonium Hydroxide, Tetrabutylammonium Hydroxide, Tetrapentyl Ammonium Hydroxide, Tetrahexyl Ammonium Hydroxide, Tetraoctyl Ammonium Hydroxide, Ethyltrimethylammonium Hydroxide , Butyltrimethylammonium Hydroxide, Methyltriamylammonium Hydroxide, Dibutyldipentylammonium Hydroxide, dimethylbis (2-Hydroxyethyl) Ammonium Hydroxide, trimethylphenylammonium Hydroxide, trimethylbenzylammonium Hydroxide, Triethylbenzylammonium Hydroxide, Pyrol and piperidine are preferable, and TMAH is more preferable. When TMAH is used, for example, the content of the basic compound in the developing solution is preferably 0.01 to 10% by mass, more preferably 0.1 to 5% by mass, and 0.3 to 3% by mass in the total mass of the developing solution. Is more preferable.

When the developing solution contains an organic solvent, the organic solvent may be used as esters such as ethyl acetate, n-butyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, etc. Methyl lactate, ethyl lactate, γ-butyrolactone, ε-caprolactone, δ-valerolactone, alkyl alkyloxyacetate (eg, methyl alkyloxyacetate, ethyl alkyloxyacetate, butyl alkyloxyacetate (eg, methyl methoxyacetate, ethyl methoxyacetate) , Ethyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, etc.), 3-alkyloxypropionate alkyl esters (eg, methyl 3-alkyloxypropionate, ethyl 3-alkyloxypropionate, etc.), etc. (eg, 3-methoxy) Methyl propionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, etc.)), 2-alkyloxypropionate alkyl esters (eg, methyl 2-alkyloxypropionate, 2- Ethyl alkyloxypropionate, propyl 2-alkyloxypropionate and the like (eg, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, 2-ethoxypropionate) Ethyl)), methyl 2-alkyloxy-2-methylpropionate and ethyl 2-alkyloxy-2-methylpropionate (eg, methyl 2-methoxy-2-methylpropionate, 2-ethoxy-2-methylpropionate). Ethyl, etc.), methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutate, ethyl 2-oxobutate, etc., and as ethers, for example, diethylene glycol dimethyl ether, tetrahydrofuran, Ethyl 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 Glycolmonopropyl ether acetate and the like, and as ketones, for example, methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, N-methyl-2-pyrrolidone and the like, and as cyclic hydrocarbons, for example, for example. Aromatic hydrocarbons such as toluene, xylene and anisole, cyclic terpenes such as limonene, dimethylsulfoxide as sulfoxides, and methanol, ethanol, propanol, isopropanol, butanol, pentanol, octanol and diethylene glycol as alcohols. Preferable examples thereof include propylene glycol, methylisobutylcarbinol, triethyleneglycol and the like, and examples of the amides include N-methylpyrrolidone, N-ethylpyrrolidone and dimethylformamide.

When the developer contains an organic solvent, one type or a mixture of two or more types of organic solvent can be used. In the present invention, a developer containing at least one selected from the group consisting of cyclopentanone, γ-butyrolactone, dimethyl sulfoxide, N-methyl-2-pyrrolidone, and cyclohexanone is particularly preferable, and cyclopentanone and γ-butyrolactone are preferable. A developer containing at least one selected from the group consisting of dimethyl sulfoxide and dimethyl sulfoxide is more preferable, and a developer containing cyclopentanone is most preferable.

When the developer contains an organic solvent, the content of the organic solvent with respect to the total mass of the developer is preferably 50% by mass or more, more preferably 70% by mass or more, and more preferably 80% by mass or more. Is more preferable, and 90% by mass or more is particularly preferable. Further, the content may be 100% by mass.

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

[Method of supplying developer]
The method of supplying the developing solution is not particularly limited as long as a desired pattern can be formed, and the method of immersing the base material on which the film is formed in the developing solution and the method of supplying the developing solution to the film formed on the base material using a nozzle. There is a method of paddle development or a method of continuously supplying a developer. The type of nozzle is not particularly limited, and examples thereof include a straight nozzle, a shower nozzle, and a spray nozzle.
From the viewpoint of the permeability of the developing solution, the removability of the non-image area, and the manufacturing efficiency, the method of supplying the developing solution with a straight nozzle or the method of continuously supplying the developing solution with a spray nozzle is preferable. From the viewpoint of permeability, the method of supplying with a spray nozzle is more preferable.
Further, after the developer is continuously supplied by the straight nozzle, the base material is spun to remove the developer from the base material, and after spin drying, the developer is continuously supplied by the straight nozzle again, and then the base material is spun to use the developer as the base material. A step of removing from the top may be adopted, and this step may be repeated a plurality of times.
The method of supplying the developer in the developing process includes a process in which the developer is continuously supplied to the substrate, a process in which the developer is kept in a substantially stationary state on the substrate, and a process in which the developer is superposed on the substrate. A process of vibrating with a sound wave or the like and a process of combining them can be adopted.

The development time is preferably 10 seconds to 10 minutes, more preferably 20 seconds to 5 minutes. The temperature of the developing solution at the time of development is not particularly determined, but is preferably 10 to 45 ° C, more preferably 18 ° C to 30 ° C.

In the developing step, after the treatment using the developing solution, the pattern may be further washed (rinsed) with the rinsing solution. Further, a method such as supplying a rinse liquid before the developer in contact with the pattern is completely dried may be adopted.

[Rinse liquid]
When the developing solution is an alkaline aqueous solution, for example, water can be used as the rinsing solution. When the developer is a developer containing an organic solvent, for example, a solvent different from the solvent contained in the developer (for example, water or an organic solvent different from the organic solvent contained in the developer) is used as the rinse solution. be able to.

When the rinsing solution contains an organic solvent, the esters include, for example, ethyl acetate, -n-butyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate. , Methyl lactate, ethyl lactate, γ-butyrolactone, ε-caprolactone, δ-valerolactone, alkyl alkyloxyacetate (eg, methyl alkyloxyacetate, ethyl alkyloxyacetate, butyl alkyloxyacetate (eg, methyl methoxyacetate, methoxyacetic acid) Ethyl, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, etc.)), 3-alkyloxypropionate alkyl esters (eg, methyl 3-alkyloxypropionate, ethyl 3-alkyloxypropionate, etc.), etc. Methyl methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, etc.)), 2-alkyloxypropionate alkyl esters (eg, methyl 2-alkyloxypropionate, 2) -Ethyl alkyloxypropionate, propyl 2-alkyloxypropionate, etc. (eg, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, 2-ethoxypropion) Ethyl propionate)), methyl 2-alkyloxy-2-methylpropionate and ethyl 2-alkyloxy-2-methylpropionate (eg, methyl 2-methoxy-2-methylpropionate, 2-ethoxy-2-methylpropionate). Ethyl acid acid, etc.), methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutate, ethyl 2-oxobutate, etc., and as ethers, for example, diethylene glycol dimethyl ether, tetrahydrofuran. , Ethyl Glycol Monomethyl Ether, Ethyl Glycol Monoethyl Ether, Methyl Cellosolve Acetate, Ethyl Cellosolve Acetate, Diethylene Glycol Monomethyl Ether, Diethylene Glycol Monoethyl Ether, Diethylene Glycol Monobutyl Ether, Ethyl Glycol Monomethyl Ether (PGME), Ethyl Glycol Monomethyl Ether Acetate (PGMEA), Propylene glycol monoethyl ether acetate, propionate Lopyrene glycol monopropyl ether acetate and the like, and as ketones, for example, methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, N-methyl-2-pyrrolidone and the like, and as cyclic hydrocarbons, for example. , Aromatic hydrocarbons such as toluene, xylene, anisole, cyclic terpenes such as limonene, dimethylsulfoxide as sulfoxides, and methanol, ethanol, propanol, isopropanol, butanol, pentanol, octanol, diethylene glycol as alcohols. , Propylene glycol, methylisobutylcarbinol, triethyleneglycol and the like, and examples of the amides include N-methylpyrrolidone, N-ethylpyrrolidone, dimethylformamide and the like.

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

When the rinsing liquid contains an organic solvent, 50% by mass or more of the rinsing liquid is preferably an organic solvent, 70% by mass or more is more preferably an organic solvent, and 90% by mass or more is an organic solvent. Is more preferable. Further, the rinse liquid may be 100% by mass of an organic solvent.

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

[Supplying method of rinse liquid]
The method of supplying the rinsing liquid is not particularly limited as long as a desired pattern can be formed, and the method of immersing the base material in the rinsing liquid, the method of supplying the rinsing liquid to the base material by filling, and the method of supplying the rinsing liquid to the base material by a shower. There is a method of continuously supplying the rinse liquid onto the base material by means such as a straight nozzle.
From the viewpoint of the permeability of the rinse liquid, the removability of non-image areas, and the efficiency of manufacturing, there is a method of supplying the rinse liquid with a shower nozzle, a straight nozzle, a spray nozzle, etc., and a method of continuously supplying the rinse liquid with a spray nozzle is preferable. From the viewpoint of the permeability of the rinse liquid into the image portion, the method of supplying with a spray nozzle is more preferable. The type of nozzle is not particularly limited, and examples thereof include a straight nozzle, a shower nozzle, and a spray nozzle.
That is, the rinsing step is preferably a step of supplying the rinsing liquid to the exposed film by a straight nozzle or continuously, and more preferably a step of supplying the rinsing liquid by a spray nozzle.
Further, as a method of supplying the rinse liquid in the rinsing step, a step of continuously supplying the rinse liquid to the base material, a step of keeping the rinse liquid in a substantially stationary state on the base material, and a step of superimposing the rinse liquid on the base material. A process of vibrating with a sonic or the like and a process of combining them can be adopted.

The rinsing time is preferably 10 seconds to 10 minutes, more preferably 20 seconds to 5 minutes. The temperature of the rinsing liquid at the time of rinsing is not particularly determined, but is preferably 10 to 45 ° C, more preferably 18 ° C to 30 ° C.

<Heating process>
The pattern obtained by the developing step (in the case of performing the rinsing step, the pattern after rinsing) may be subjected to a heating step of heating the pattern obtained by the above-mentioned development.
That is, the method for producing a cured product of the present invention may include a heating step of heating the pattern obtained by the developing step.
Further, the method for producing a cured product of the present invention may include a pattern obtained by another method without performing a developing step, or a heating step of heating the film obtained by the film forming step.
In the heating step, the resin such as the polyimide precursor is cyclized to become the resin such as polyimide.
In addition, cross-linking of unreacted cross-linking groups with a specific resin or a cross-linking agent other than the specific resin also proceeds.
The heating temperature (maximum heating temperature) in the heating step is preferably 50 to 450 ° C, more preferably 150 to 350 ° C, further preferably 150 to 250 ° C, further preferably 160 to 250 ° C, and particularly preferably 160 to 230 ° C. preferable.

The heating step is preferably a step of promoting the cyclization reaction of the polyimide precursor in the pattern by the action of the base or the like generated from the base generator by heating.

The heating in the heating step is preferably performed at a heating rate of 1 to 12 ° C./min from the temperature at the start of heating to the maximum heating temperature. The temperature rising rate is more preferably 2 to 10 ° C./min, even more preferably 3 to 10 ° C./min. By setting the temperature rise rate to 1 ° C./min or more, it is possible to prevent excessive volatilization of the acid or solvent while ensuring productivity, and by setting the temperature rise rate to 12 ° C./min or less, curing is possible. The residual stress of the object can be relaxed.
In addition, in the case of an oven capable of rapid heating, it is preferable to carry out from the temperature at the start of heating to the maximum heating temperature at a heating rate of 1 to 8 ° C./sec, more preferably 2 to 7 ° C./sec, and 3 to 6 ° C. ℃ / sec is more preferable.

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

The heating time (heating time at the maximum heating temperature) is preferably 5 to 360 minutes, more preferably 10 to 300 minutes, and even more preferably 15 to 240 minutes.

In particular, when forming a multi-layered laminate, the heating temperature is preferably 30 ° C. or higher, more preferably 80 ° C. or higher, still more preferably 100 ° C. or higher, from the viewpoint of adhesion between layers. It is particularly preferable that the temperature is 120 ° C. or higher.
The upper limit of the heating temperature is preferably 350 ° C. or lower, more preferably 250 ° C. or lower, and even more preferably 240 ° C. or lower.

Heating may be performed in stages. As an example, the temperature is raised from 25 ° C. to 120 ° C. at 3 ° C./min and held at 120 ° C. for 60 minutes, the temperature is raised from 120 ° C. to 180 ° C. at 2 ° C./min, and the temperature is kept at 180 ° C. for 120 minutes. , And so on. It is also preferable to perform the treatment while irradiating with ultraviolet rays as described in US Pat. No. 9,159,547. It is possible to improve the characteristics of the film by such a pretreatment step. The pretreatment step may be performed in a short time of about 10 seconds to 2 hours, more preferably 15 seconds to 30 minutes. The pretreatment may be performed in two or more steps, for example, the first pretreatment step may be performed in the range of 100 to 150 ° C., and then the second pretreatment step may be performed in the range of 150 to 200 ° C. good.
Further, 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 carried out in an atmosphere having a low oxygen concentration by flowing an inert gas such as nitrogen, helium or argon or under reduced pressure in order to prevent decomposition of the specific resin. The oxygen concentration is preferably 50 ppm (volume ratio) or less, and more preferably 20 ppm (volume ratio) or less.
The heating means in the heating step is not particularly limited, and examples thereof include a hot plate, an infrared furnace, an electric heating oven, a hot air oven, and an infrared oven.

<Exposure process after development>
The obtained by the developing step (in the case of performing the rinsing step, the pattern after rinsing) is used in the post-development exposure step of exposing the pattern after the developing step in place of the above heating step or in addition to the above heating step. May be offered.
That is, the method for producing a cured product of the present invention may include a post-development exposure step for exposing the pattern obtained by the developing step. The method for producing a cured product of the present invention may include a heating step and a post-development exposure step, or may include only one of a heating step and a post-development exposure step.
In the post-development exposure step, for example, a reaction in which cyclization of a polyimide precursor or the like is promoted by exposure to a photobase generator or a reaction in which desorption of acid-degradable groups is promoted by exposure to a photoacid generator is promoted. can do.
In the post-development exposure step, at least a part of the pattern obtained in the development step may be exposed, but it is preferable that all of the above patterns are exposed.
The exposure amount in the post-development exposure step is preferably 50 to 20,000 mJ / cm ² and more preferably 100 to 15,000 mJ / cm ² in terms of exposure energy at a wavelength at which the photosensitive compound has sensitivity. preferable.
The post-development exposure step can be performed using, for example, the light source in the above-mentioned exposure step, and it is preferable to use broadband light.

<Metal layer forming process>
The pattern obtained by the developing step (preferably those subjected to at least one of the heating step and the post-exposure developing step) may be subjected to the metal layer forming step of forming the metal layer on the pattern.
That is, the method for producing a cured product of the present invention includes a metal layer forming step of forming a metal layer on a pattern obtained by a developing step (preferably one provided in at least one of a heating step and a post-development exposure step). Is preferable.

As the metal layer, existing metal species can be used without particular limitation, and examples thereof include copper, aluminum, nickel, vanadium, titanium, chromium, cobalt, gold, tungsten, tin, silver, and alloys containing these metals. Copper and aluminum are more preferred, and copper is even more preferred.

The method for forming the metal layer is not particularly limited, and an existing method can be applied. For example, the methods described in JP-A-2007-157879, JP-A-2001-521288, JP-A-2004-214501, JP-A-2004-101850, US Pat. No. 7,788,181B2, US Pat. No. 9,177,926B2 are used. can do. For example, photolithography, PVD (physical vapor deposition), CVD (chemical vapor deposition), lift-off, electroplating, electroless plating, etching, printing, and a combination of these can be considered. More specifically, a patterning method combining sputtering, photolithography and etching, and a patterning method combining photolithography and electrolytic plating can be mentioned. Preferred embodiments of plating include electrolytic plating using a copper sulfate or copper cyanide plating solution.

The thickness of the metal layer is preferably 0.01 to 50 μm, more preferably 1 to 10 μm in the thickest portion.

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

Further, the method for producing a cured product of the present invention, or the cured product of the present invention, is used for manufacturing a plate surface such as an offset plate surface or a screen plate surface, using it for etching molded parts, protective lacquer and dielectric in electronics, especially microelectronics. It can also be used for layer production and the like.

(Laminated body and method for manufacturing the laminated body)
The laminated body of the present invention refers to a structure having a plurality of layers made of the cured product of the present invention.
The laminated body of the present invention is a laminated body including two or more layers made of a cured product, and may be a laminated body in which three or more layers are laminated.
Of the two or more layers made of the cured product contained in the laminated body, at least one is a layer made of the cured product of the present invention, which causes shrinkage of the cured product or deformation of the cured product due to the shrinkage. From the viewpoint of suppressing, it is also preferable that the layer made of all the cured products contained in the laminated body is the layer made of the cured product of the present invention.

That is, the method for producing a laminated body of the present invention preferably includes the method for producing a cured product of the present invention, and more preferably includes repeating the method for producing a cured product of the present invention a plurality of times.

It is preferable that the laminated body of the present invention contains two or more layers made of a cured product and contains a metal layer between any of the layers made of the cured product. The metal layer is preferably formed by the metal layer forming step.
That is, it is preferable that the method for producing a laminated body of the present invention further includes a metal layer forming step of forming a metal layer on a layer made of the cured product between the methods for producing a cured product which is performed a plurality of times. The preferred embodiment of the metal layer forming step is as described above.
As the above-mentioned laminate, for example, a laminate including at least a layer structure in which three layers of a layer made of a first cured product, a metal layer, and a layer made of a second cured product are laminated in this order is preferable. Be done.
It is preferable that the layer made of the first cured product and the layer made of the second cured product are both layers made of the cured product of the present invention. The resin composition of the present invention used for forming the layer made of the first cured product and the resin composition of the present invention used for forming the layer made of the second cured product have the same composition. It may be a product or a composition having a different composition. The metal layer in the laminate of the present invention is preferably used as metal wiring such as a rewiring layer.

<Laminating process>
The method for producing a laminated body of the present invention preferably includes a laminating step.
The laminating step means that (a) a film forming step (layer forming step), (b) an exposure step, (c) a developing step, (d) a heating step and development are performed again on the surface of a pattern (resin layer) or a metal layer. It is a series of steps including performing at least one of the post-exposure steps in this order. However, it may be an embodiment in which at least one of the film forming step (a), the heating step and the post-development exposure step (d) is repeated. Further, (e) a metal layer forming step may be included after at least one of the (d) heating step and the post-development exposure step. Needless to say, the laminating step may further include the above-mentioned drying step and the like as appropriate.

When the laminating step is further performed after the laminating step, the surface activation treatment step may be further performed after the exposure step, the heating step, or the metal layer forming step. Plasma treatment is exemplified as the surface activation treatment. Details of the surface activation treatment will be described later.

The laminating step is preferably performed 2 to 20 times, more preferably 2 to 9 times.
For example, a structure having two or more and 20 or less resin layers, such as a resin layer / metal layer / resin layer / metal layer / resin layer / metal layer, is preferable, and a structure having two or more and 9 or less layers is more preferable. ..
The composition, shape, film thickness, etc. of each of the above layers may be the same or different.

In the present invention, it is particularly preferable to form a cured product (resin layer) of the resin composition of the present invention so as to further cover the metal layer after the metal layer is provided. Specifically, an embodiment in which (a) a film forming step, (b) an exposure step, (c) a developing step, (d) at least one of a heating step and a post-development exposure step (e) a metal layer forming step is repeated in this order. Alternatively, an embodiment in which (a) a film forming step, (d) at least one of a heating step and a post-development exposure step, and (e) a metal layer forming step is repeated in this order can be mentioned. By alternately performing the laminating step of laminating the resin composition layer (resin layer) of the present invention and the metal layer forming step, the resin composition layer (resin layer) of the present invention and the metal layer can be alternately laminated. can.

(Surface activation treatment process)
The method for producing a laminate of the present invention preferably includes a surface activation treatment step of surface activating at least a part of the metal layer and the resin composition layer.
The surface activation treatment step is usually performed after the metal layer forming step, but after the development step, the surface activation treatment step may be performed on the resin composition layer, and then the metal layer forming step may be performed.
The surface activation treatment may be performed on at least a part of the metal layer, on at least a part of the exposed resin composition layer, or on the metal layer and the exposed resin composition layer. For both, you may go to at least part of each. The surface activation treatment is preferably performed on at least a part of the metal layer, and it is preferable to perform the surface activation treatment on a part or all of the region forming the resin composition layer on the surface of the metal layer. By performing the surface activation treatment on the surface of the metal layer in this way, the adhesion to the resin composition layer (film) provided on the surface can be improved.
Further, it is preferable that the surface activation treatment is performed on a part or all of the resin composition layer (resin layer) after exposure. As described above, by performing the surface activation treatment on the surface of the resin composition layer, it is possible to improve the adhesion to the metal layer or the resin layer provided on the surface of the surface activation treatment. In particular, when the resin composition layer is cured, such as when negative type development is performed, it is less likely to be damaged by the surface treatment and the adhesion is likely to be improved.
Specific examples of the surface activation treatment include plasma treatment of various raw material gases (oxygen, hydrogen, argon, nitrogen, nitrogen / hydrogen mixed gas, argon / oxygen mixed gas, etc.), corona discharge treatment, and CF ₄ / O ₂ . , NF ₃ / O ₂ , SF ₆ , NF ₃ , NF ₃ / O ₂ , etching treatment, surface treatment by ultraviolet (UV) ozone method, immersion in hydrochloric acid aqueous solution to remove oxide film, then amino group and thiol group It is selected from a dipping treatment in an organic surface treatment agent containing at least one compound and a mechanical roughening treatment using a brush, and plasma treatment is preferable, and oxygen plasma treatment using oxygen as a raw material gas is particularly preferable. In the case of the 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 .

(Manufacturing method of electronic device)
The present invention also discloses a semiconductor device containing the cured product of the present invention or the laminate of the present invention.
The present invention also discloses a method for producing a cured product of the present invention, or a method for producing a semiconductor device including a method for producing a laminate of the present invention. As specific examples of the semiconductor device in which the resin composition of the present invention is used to form the interlayer insulating film for the rewiring layer, the description in paragraphs 0213 to 0218 and FIG. 1 of JP-A-2016-0273557 can be referred to. These contents are incorporated in the present specification.

(Polyimide precursor and its manufacturing method)
The polyimide precursor of the present invention has a total content of the cyclic imide structure and the cyclic isoimide structure of 0.28 to 1.68 mmol / g and an acid value of 5.6 to 22.5 mgKOH / g.
In addition, the polyimide precursor of the present invention has the same meaning as the above-mentioned specific resin, and is the same as the preferred embodiment.

Hereinafter, the first aspect and the second aspect of the method for producing a polyimide precursor of the present invention will be exemplified, but the method for producing a polyimide precursor of the present invention is not limited thereto.
The first aspect of the method for producing a polyimide precursor of the present invention is the method for producing a polyimide precursor of the present invention, which comprises reacting a dicarboxylic acid compound with a diamine compound to obtain an amide compound. It includes a partial imidization step of partially imidizing the amide compound.
The details of each of the above steps are the same as those described as the first aspect of the above-mentioned method for producing a specific resin, and the preferred embodiments are also the same.

The second aspect of the method for producing a polyimide precursor of the present invention is a method for producing a polyimide precursor of the present invention, in which a dicarboxylic acid compound and a diamine compound are amidated in the presence of a basic catalyst to form an amide compound. Includes an amidation step to obtain.
The details of each of the above steps are the same as those described as the second aspect of the above-mentioned method for producing the specific resin, and the preferred embodiments are also the same.

The present invention will be described in more detail with reference to examples below. The materials, amounts used, ratios, treatment contents, treatment procedures, etc. shown in the following examples can be appropriately changed as long as they do not deviate from the gist of the present invention. Therefore, the scope of the present invention is not limited to the specific examples shown below. Unless otherwise specified, "part" and "%" are based on mass.

<Resin manufacturing method>
Polymers A-1 to A-17 containing repeating units represented by the following formulas (A-1) to (A-17) were synthesized according to the method described in Synthesis Example 1 or Synthesis Example 2 below.
In addition, polymers A-18 to A-23 containing repeating units represented by the following formula (A-1) were synthesized according to the methods described in Synthesis Examples 3 to 8 below.
In the example described as "1" in the column of the synthetic method in the table below, the resin shown in the table among the polymers A-1 to A-17 is used by the same method as the method described in the synthetic example 1 below. The synthesized one was used.
In the example described as "2" in the column of the synthetic method in the table below, the resin shown in the table among the polymers A-1 to A-17 is used in the same manner as the method described in the synthetic example 2 below. The synthesized one was used.
The polymers A-1 to A-17 include at least one of the following repeating units having an amic acid structure or a part of the amic acid ester structure having a cyclic imide structure or a cyclic isoimide structure.
The total content (mmol / g) of the cyclic imide structure and the cyclic isoimide structure contained in the polymers A-1 to A-17 is described in the column of "Specific structure content (mmol / g)" in the table.
The acid value of the polymers A-1 to A-17 is described in the column of "acid value (mgKOH / g)" in the table.

[Synthesis Example 1: Synthesis of Polymer A-1]
23.48 g of 4,4'-oxydiphthalic acid dianhydride (ODPA) and 22.27 g of bisphthalic acid dianhydride (BPDA) were placed in a separable flask, and 2-hydroxyethyl methacrylate (HEMA) 39.69 g and tetrahydrofuran 136. 83 g was added and stirred at room temperature (25 ° C.), and 24.66 g of pyridine was added while stirring to obtain a reaction mixture. After the heat generated by the reaction was completed, the mixture was allowed to cool to room temperature and left for 16 hours.
Next, under ice-cooling, a solution of 62.46 g of dicyclohexylcarbodiimide (DCC) in 61.57 g of tetrahydrofuran was added to the reaction mixture over 40 minutes with stirring, followed by 4,4'-diaminodiphenyl ether (DADPE). A suspension of 27.42 g in THF 119.73 g 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 the mixture was stirred for 1 hour, and then 136.83 g of tetrahydrofuran was added. The precipitate formed in the reaction mixture was removed by filtration to obtain a reaction solution.
The obtained reaction solution was added to 716.21 g of ethyl alcohol to form a precipitate composed of a crude polymer. The produced crude polymer was filtered off and dissolved in 403.49 g of tetrahydrofuran to obtain a crude polymer solution. The obtained crude polymer solution was added dropwise to 8470.26 g of water to precipitate the polymer, and the obtained precipitate was filtered off and then vacuum dried to obtain 80.3 g of the powdery polymer A-1. When the molecular weight of the polymer A-1 was measured by gel permeation chromatography (standard polystyrene conversion), the weight average molecular weight (Mw) was 20,000.

[Synthesis Example 2: Synthesis of Polymer A-2]
21.2 g of 4,4'-oxydiphthalic anhydride, 18.0 g of 2-hydroxyethyl methacrylate, 23.9 g of pyridine and 250 mL of diglyme (Diglyme, diethylene glycol dimethyl ether) were mixed at 60 ° C. The mixture was stirred at temperature for 4 hours to synthesize a diester of 4,4'-oxydiphthalic acid and 2-hydroxyethyl methacrylate. The reaction mixture was then cooled to −10 ° C. and 17.0 g of thionyl chloride was added over 60 minutes while keeping the temperature at −10 ± 5 ° C. After diluting with 50 mL of N-methylpyrrolidone, a solution of 12.6 g of 4,4'-diaminodiphenyl ether dissolved in 100 mL of N-methylpyrrolidone is added dropwise to the reaction mixture at -10 ± 5 ° C. over 60 minutes. The mixture was then stirred at room temperature for 2 hours.
Then, 6000 g of water was added to precipitate the polyimide precursor, and the precipitate (water-polyimide precursor mixture) was stirred for 15 minutes. The stirred precipitate (solid polyimide precursor) was collected by filtration and dissolved in 500 g of tetrahydrofuran. 6000 g of water (poor solvent) was added to the obtained solution to precipitate the polyimide precursor, and the precipitate (water-polyimide precursor mixture) was stirred for 15 minutes. The stirred precipitate (solid polyimide precursor) was filtered again and dried under reduced pressure at 45 ° C. for 3 days.
After 46.6 g of the dried powder was dissolved in 419.6 g of tetrahydrofuran, 2.3 g of triethylamine was added and the mixture was stirred at room temperature for 35 minutes. Then, it was added to 3000 g of ethanol, and the precipitate was collected by filtration. The obtained precipitate was dissolved in 281.8 g of tetrahydrofuran. To this, 17.1 g of water and 46.6 g of ion exchange resin UP6040 (manufactured by AmberTech) were added, and the mixture was stirred for 4 hours. Then, the ion exchange resin was removed by filtration, and the obtained polymer solution was added to a mixed solution of 4500 g of heptane and 500 g of ethyl acetate to obtain a precipitate. The precipitate was collected by filtration and dried under reduced pressure at 45 ° C. for 24 hours to obtain 45.1 g of Polymer A-2.
When the molecular weight of the polymer A-2 was measured by gel permeation chromatography (standard polystyrene equivalent), the weight average molecular weight (Mw) was 20,000.

[Synthesis Examples 3 to 8: Synthesis of Polymers A-18 to A-23]
A-18 to A-20: In Synthesis Example 1, the stirring time (2 hours) at room temperature after the addition of DADPE was 6 hours for A-18, 10 hours for A-19, and 14 hours for A-20, respectively. Except for the changes, the raw materials described in Synthesis Example 1 were used, and the same operations as in Synthesis Example 1 were carried out to synthesize each resin.
A-21 to A-23: In Synthesis Example 1, the amount of DCC added (62.46 g) was changed to 61.26 g for A-21, 60.11 g for A-22, and 58.50 g for A-23, respectively. Except for the above, the raw materials described in Synthesis Example 1 were used, and the same operations as in Synthesis Example 1 were carried out to synthesize each resin.

[Synthesis of Polymer CA-1 for Comparative Examples]
21.2 g of 4,4'-oxydiphthalic anhydride, 18.0 g of 2-hydroxyethyl methacrylate, 23.9 g of pyridine and 250 mL of diglyme (Diglyme, diethylene glycol dimethyl ether) were mixed at 60 ° C. The mixture was stirred at temperature for 4 hours to synthesize a diester of 4,4'-oxydiphthalic acid and 2-hydroxyethyl methacrylate. The reaction mixture was then cooled to −10 ° C. and 17.0 g of thionyl chloride was added over 60 minutes while keeping the temperature at −10 ± 5 ° C. After diluting with 50 mL of N-methylpyrrolidone, a solution of 12.6 g of 4,4'-diaminodiphenyl ether dissolved in 100 mL of N-methylpyrrolidone is added dropwise to the reaction mixture at -10 ± 5 ° C. over 60 minutes. The mixture was then stirred for 2 hours.
Then, 6000 g of water was added to precipitate the polyimide precursor, and the precipitate (water-polyimide precursor mixture) was stirred for 15 minutes. The stirred precipitate (solid polyimide precursor) was collected by filtration and dissolved in 500 g of tetrahydrofuran. 6000 g of water (poor solvent) was added to the obtained solution to precipitate the polyimide precursor, and the precipitate (water-polyimide precursor mixture) was stirred for 15 minutes. The stirred precipitate (solid polyimide precursor) was filtered again and dried under reduced pressure at 45 ° C. for 3 days.
After 46.6 g of the dried powder was dissolved in 419.6 g of tetrahydrofuran, 0.5 g of triethylamine was added and the mixture was stirred at room temperature for 10 minutes. Then, it was added to 3000 g of ethanol, and the precipitate was collected by filtration. The obtained precipitate was dissolved in 281.8 g of tetrahydrofuran. To this, 17.1 g of water and 46.6 g of ion exchange resin UP6040 (manufactured by AmberTech) were added, and the mixture was stirred for 4 hours. Then, the ion exchange resin was removed by filtration, and the obtained polymer solution was added to a mixed solution of 4500 g of heptane and 500 g of ethyl acetate to obtain a precipitate. The precipitate was collected by filtration and dried under reduced pressure at 45 ° C. for 24 hours to obtain 45.1 g of polymer CA-1.
When the molecular weight of the polymer CA-1 was measured by gel permeation chromatography (standard polystyrene conversion), the weight average molecular weight (Mw) was 20,000.

[Synthesis of Polymer CA-2 for Comparative Examples]
23.48 g of 4,4'-oxydiphthalic acid dianhydride (ODPA) and 22.27 g of bisphthalic acid dianhydride (BPDA) were placed in a 500 mL separable flask with 39.69 g of 2-hydroxyethyl methacrylate (HEMA). NMP136.83 g was added and stirred at room temperature, and 24.66 g of pyridine was added while stirring to obtain a reaction mixture. After the heat generated by the reaction was completed, the mixture was allowed to cool to room temperature and left for 16 hours.
Next, under ice-cooling, a solution of 62.46 g of dicyclohexylcarbodiimide (DCC) dissolved in 61.57 g of NMP was added to the reaction mixture over 40 minutes with stirring, followed by 4,4'-diaminodiphenyl ether (DADPE) 27. A suspension of .42 g in NMP119.73 g 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 the mixture was stirred for 1 hour, and then NMP136.83 g was added. The precipitate formed in the reaction mixture was removed by filtration to obtain a reaction solution.
The obtained reaction solution was added to 716.21 g of ethyl alcohol to form a precipitate composed of a crude polymer. The produced crude polymer was filtered off and dissolved in 403.49 g of tetrahydrofuran to obtain a crude polymer solution. The obtained crude polymer solution was added dropwise to 8470.26 g of water to precipitate the polymer, and the obtained precipitate was filtered off and then vacuum dried to obtain 80.3 g of the powdery polymer CA-2. When the molecular weight of the polymer CA-2 was measured by gel permeation chromatography (standard polystyrene equivalent), the weight average molecular weight (Mw) was 20,000.

<Examples and comparative examples>
In each example, the components listed in the table below were mixed to obtain each curable resin composition. Further, in each comparative example, the components shown in the following table were mixed to obtain each comparative composition.
Specifically, the content of each component described in the table is the amount (parts by mass) described in parentheses in each column of the table.
The obtained curable resin composition and comparative composition were pressure-filtered using a filter made of polytetrafluoroethylene having a pore width of 0.8 μm.
Further, in the table, the description of "-" indicates that the composition does not contain the corresponding component.

Details of each component listed in Tables 1 to 5 are as follows.

〔resin〕
A-1 to A-23, CA-1 to CA-2: Polymers A-1 to A-23 and CA-1 to CA-2 obtained by the above synthetic examples.

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

[Organometallic complex]
-X-1: Bis (η5-2,4-cyclopentadiene-1-yl) Bis (2,6-difluoro-3- (1H-pyrrole-1-yl) phenyl) Titanium-X-2: Pentamethylcyclo Pentazienyl Titanium Trimethoxide ・ X-3: Bis (η5-2,4-Cyclopentadiene-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 Chemical Co., Ltd.)
X-6 to X-8: Compounds having the following structure.

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

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

[Polymerization inhibitor, migration inhibitor]
-D-1 to D-7: Compounds having 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.

[Solvent (solvent)]
-NMP: N-methyl-2-pyrrolidone-EL: ethyl lactate-DMSO: dimethyl sulfoxide-γBL: γ-butyrolactone

<Evaluation>
[Measurement of total content of cyclic imide structure and cyclic isoimide structure]
For the resin used in each Example or Comparative Example, the total molar amount of the cyclic imide structure and the cyclic isoimide structure contained in 1 g of the resin (polyimide precursor) was measured by the following method.
0.10 g of the resin was dissolved in 0.90 g of heavy DMSO (dimethyl sulfoxide-d6), and the total molar content of the polymer powder was measured using ¹ H NMR.
Specifically, the ratio of the cyclic imide structure and the cyclic isoimide structure was calculated from the ratio of the proton peaks of the cyclic imide structure and the cyclic isoimide structure to the proton peak of the total aromatic ring.
The measurement results of each resin are described in the column of "Specific structure content (mmol / g)" in the table.

[Measurement of acid value]
The acid value of the resin used in each Example or Comparative Example was measured by the following method.
After dissolving 0.30 g of the resin in 80 mL of NMP, 5 mL of water was added to prepare a measurement solution. The acid value of the resin was measured by titrating the solution with a 0.01 N (0.01 mol / L) aqueous solution of potassium hydroxide (KOH) and detecting the neutralization point.
The measurement results of each resin are described in the column of "acid value (mgKOH / g)" in the table.

[Evaluation of chemical resistance]
-Calculation of dissolution rate-
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 photosensitive film having a uniform thickness of 20 μm on the silicon wafer.
In the example described as "negative" in the development conditions and "M" in the exposure conditions, the curable resin composition layer on the silicon wafer was exposed using a stepper. The exposure was performed using light having the wavelength described in "Exposure wavelength nm" in the table, and the entire surface of the photosensitive film was exposed without using a photomask. The exposure amount was the exposure amount that minimizes the minimum line width in the evaluation of resolution described later.
In the example described as "negative" in the development conditions and "D" in the exposure conditions, exposure was performed using a direct exposure apparatus (Adtech DE-6UH III). The exposure was performed on the entire surface of the photosensitive film using light having the wavelength described in "Exposure wavelength nm" in the table. The exposure amount was the exposure amount that minimizes the minimum line width in the evaluation of resolution described later.
In the example described as "positive" in the development conditions, no exposure was performed.
Next, in the example described as "1" in the "Cure method" column, a hot plate was used to apply the resin film obtained in each Example or Comparative Example to 10 ° C./min under a nitrogen atmosphere. After reaching the temperature described in "Cure temperature (° C.)" in the table, the temperature was maintained for 3 hours to form a cured product (cured film).
In the example described as "2" in the "Cure method" column, the resin film obtained in each example was subjected to a nitrogen atmosphere using an infrared lamp heating device (RPP-6 manufactured by Advance Riko Co., Ltd.). Then, the temperature was raised at a heating rate of 10 ° C./min, and after reaching the temperature described in "Cure temperature (° C.)", the temperature was maintained for 3 hours to form a cured product (cured film).
The obtained cured product was immersed in the following chemicals under the following conditions, and the dissolution rate was calculated.
Chemicals: Mixture of dimethyl sulfoxide (DMSO) and 25% by mass tetramethylammonium hydroxide (TMAH) aqueous solution at 90:10 (mass ratio) Evaluation conditions: The cured product is immersed in the chemicals at 75 ° C. for 15 minutes. The thickness of the cured product before and after was compared, and the dissolution rate (nm / min) was calculated.
The obtained dissolution rate values were evaluated according to the following evaluation criteria and described in the "Chemical resistance" column. It can be said that the smaller the dissolution rate, the better the chemical resistance.
-Evaluation criteria-
A: The dissolution rate is less than 250 nm / min.
B: The dissolution rate is 250 nm / min or more and less than 500 nm / min.
C: The dissolution rate is 500 nm / min or more and less than 750 nm / min.
D: The dissolution rate is 750 nm / min or more.

[Evaluation of breaking elongation]
The curable resin composition or the comparative composition prepared in each Example and each Comparative Example was applied onto a silicon wafer by a spin coating method to form a resin layer.
The silicon wafer on which the obtained resin layer was formed was dried on a hot plate at 100 ° C. for 5 minutes to obtain a curable resin composition layer having a uniform thickness of about 15 μm on the silicon wafer.
In the example described as "negative" in the column of development conditions in the table, the entire surface of the curable resin composition layer on the silicon wafer was exposed with an exposure energy of 500 mJ / cm ² . The details of the exposure method were the same as the exposure method in the above-mentioned evaluation of chemical resistance. The exposure wavelength is described in "Exposure wavelength (nm)" in the table. In the example described as "positive" in the development condition column in the table, no exposure was performed.
In the example described as "1" in the "Cure method" column, a hot plate was used to heat the curable resin composition layer after exposure at a heating rate of 10 ° C./min under a nitrogen atmosphere. After reaching the temperature described in the column of "cure temperature (° C.)" in the table, the above temperature was maintained for 3 hours.
In the example described as "2" in the "Cure method" column, the resin film obtained in each example was subjected to a nitrogen atmosphere using an infrared lamp heating device (RPP-6 manufactured by Advance Riko Co., Ltd.). Then, the temperature was raised at a heating rate of 10 ° C./min, and after reaching the temperature described in "Cure temperature (° C.)", the above temperature was maintained for 3 hours.
The cured resin composition layer (cured product) was immersed in a 4.9 mass% hydrofluoric acid aqueous solution, and the cured product was peeled off from the silicon wafer. The peeled cured product was punched out using a punching machine to prepare a test piece having a sample width of 3 mm and a sample length of 30 mm. The elongation rate of the obtained test piece in the longitudinal direction was measured in JIS-K6251 in an environment of a crosshead speed of 300 mm / min, 25 ° C., and 65% RH (relative humidity) using a tensile tester (Tencilon). Measured in compliance. The measurement was carried out 5 times each, and the arithmetic mean value of the elongation rate (breaking elongation rate) when the test piece was broken in each of the 5 measurements was used as an index value.
The evaluation was performed according to the following evaluation criteria, and the evaluation results are described in the "break elongation" column of the table. It can be said that the larger the index value, the better the film strength of the cured product.
-Evaluation criteria-
A: The above index value was 60% or more.
B: The index value was 55% or more and less than 60%.
C: The above index value was less than 55%.

[Evaluation of resolution]
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 having 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. The exposure was performed using light having the wavelength described in "Exposure wavelength nm" in the table, and using a fuse box photomask from 5 μm to 25 μm in 1 μm increments. The exposure amount was the exposure amount that minimizes the minimum line width described later.
In the example described as "D" in the exposure condition, the exposure was performed using a direct exposure apparatus (Adtech DE-6UH III). The exposure was performed by laser direct imaging exposure at a wavelength of 405 nm so that the exposed portion became a line portion in a line and space pattern in 1 μm increments from 5 μm to 25 μm. The exposure amount was the exposure amount that minimizes the minimum line width described later.
In the example described as "Positive" in the "Development Conditions" column, the exposed curable resin composition layer was developed with a 2.5 mass% tetramethylammonium hydroxide aqueous solution for 60 seconds and then with pure water. Rinse for 20 seconds.
In the example described as "negative" in the "development conditions" column, the exposed curable resin composition layer was developed with cyclopentanone for 60 seconds and then with propylene glycol monomethyl ether acetate (PGMEA) for 20 seconds. Rinse.
In the pattern obtained after development, the line width of the line pattern in which the silicon wafer was exposed between the line patterns and the line width was the smallest 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 is, the better the resolution is, and for example, it means that the metal wiring width formed in the subsequent plating step can be miniaturized, which is a preferable result. The measurement limit is 5 μm. The evaluation results are described 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.

[Evaluation of rectangularity]
In each Example and Comparative Example, each curable resin composition or comparative composition was applied (coated) in layers on a silicon wafer by a spin coating method to form a resin composition film.
In each Example and Comparative Example, the silicon wafer to which the obtained resin composition film was applied was dried on a hot plate at 80 ° C. for 3 minutes to form a photocurable film on the silicon wafer.
In the example described as "M" in the exposure condition, the photocurable film on the silicon wafer was exposed to the same exposure amount as the exposure amount used in the above resolution evaluation using the exposure wavelength described in the examples. The exposure was performed with the exposure amount that minimizes the minimum line width). Exposure was performed via a mask (a binary mask with a pattern of 1: 1 line and space and a line width of 10 μm).
In the example described as "D" in the exposure condition, the exposure was performed using a direct exposure apparatus (Adtech DE-6UH III). The exposure was performed by laser direct imaging exposure at a wavelength of 405 nm so that the exposed portion became a line portion in a 1: 1 line-and-space pattern having a width of 10 μm. The exposure amount was the same as the exposure amount used in the above resolution evaluation (the exposure amount that minimizes the minimum line width).
After the above exposure, in the example of positive development (the example described as "positive" in the column of "development conditions"), development was performed for 60 seconds using a 2.5 mass% tetramethylammonium hydroxide aqueous solution, and then in pure water. Rinse for 20 seconds to obtain a line-and-space pattern of the photocurable film after exposure. In the negative development example (the example described as "negative" in the "development conditions" column), the product was developed with cyclopentanone for 60 seconds, rinsed with propylene glycol monomethyl ether acetate (PGMEA) for 20 seconds, and then rinsed with propylene glycol monomethyl ether acetate (PGMEA) for 20 seconds. A line-and-space pattern of the photocurable film was obtained.
For the silicon wafer on which the obtained line-and-space pattern was formed, the silicon wafer was cut so as to be perpendicular to the line-and-space pattern, and the cross section of the pattern was exposed. Using an optical microscope, the pattern cross section of the line and space pattern was observed at a magnification of 200 times, and the cross-sectional shape of the pattern was evaluated.
Specifically, in each Example and Comparative Example, the taper angle formed by the surface of the silicon wafer (surface of the substrate) and the side surface of the cured product was measured and evaluated according to the following evaluation criteria. The evaluation results are described in the "rectangularity" column in the table. It can be said that the closer the taper angle is to 90 °, the better the pattern shape is, the more the taper angle does not exceed 90 ° and the cross-sectional shape of the pattern is not constricted.
-Evaluation criteria-
A: The taper angle was 85 ° or more and 90 ° or less.
B: The taper angle was 80 ° or more and less than 85 ° C: The taper angle was less than 80 °, the cross-sectional shape of the pattern was a reverse taper shape with a taper angle of more than 90 °, or the pattern The cross-sectional shape was constricted.

[Evaluation of low shrinkage]
In each Example and Comparative Example, a cured product was formed by the same method as in the above evaluation of chemical resistance, and the film thickness immediately after exposure and before heating (film thickness before curing) and after heating were obtained. (Film thickness after curing) was measured respectively. The ratio (%) of the film thickness after curing to the film thickness before curing was calculated according to the following formula, and evaluated according to the following evaluation criteria. The evaluation results are described in the "low shrinkage" column in the table. It can be said that the larger the ratio (%) of the film thickness after curing to the film thickness before curing, the more the film shrinkage due to heating is suppressed.
Ratio of post-cure film thickness to pre-cure film thickness (%) = post-cure film thickness / pre-cure film thickness x 100
-Evaluation criteria-
A: The ratio (%) of the film thickness after curing to the film thickness before curing is 90% or more.
B: The ratio (%) of the film thickness after curing to the film thickness before curing is 80% or more and less than 90%.
C: The ratio (%) of the film thickness after curing to the film thickness before curing is less than 80%.

From the above results, it can be seen that the curable resin composition of the present invention has excellent chemical resistance.
The resin used in Comparative Example 1 has a total content of the cyclic imide structure and the cyclic isoimide structure of less than 0.28 mmol / g. It can be seen that when such a resin is used, the chemical resistance is inferior.
Further, the resin used in Comparative Example 2 has an acid value of less than 5.6 mgKOH / g. It can be seen that when such a resin is used, the chemical resistance is inferior.

<Example 101>
The curable resin composition used in Example 1 was applied in a layered manner on the surface of the copper thin layer of the resin substrate having the copper thin layer formed on the surface by a spin coating method, and dried at 100 ° C. for 4 minutes. After forming a photosensitive film having a thickness of 20 μm, exposure was performed using a stepper (NSR1505 i6, manufactured by Nikon Corporation). Exposure was performed via a mask (a binary mask with a pattern of 1: 1 line and space and a line width of 10 μm) at a wavelength of 365 nm. After the exposure, it was heated at 100 ° C. for 4 minutes. After the above 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 heating rate of 10 ° C./min under 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 the rewiring layer. The interlayer insulating film for the rewiring layer was excellent in insulating property.
Moreover, when a semiconductor device was manufactured using these interlayer insulating films for the rewiring layer, it was confirmed that the semiconductor device operated without any problem.

Claims

A curable resin composition containing a polyimide precursor having a total content of a cyclic imide structure and a cyclic isoimide structure of 0.28 to 1.68 mmol / g and an acid value of 5.6 to 22.5 mgKOH / g.
The curable resin composition according to claim 1, wherein the polyimide precursor has a carboxy group content of 5.6 to 22.5 mgKOH / g.
The ratio of the monovalent organic groups R 113 and R 114 to all the R 113 and R 114 contained in the polyimide precursor, wherein the polyimide precursor contains a repeating unit represented by the following formula (3). The curable resin composition according to claim 1 or 2, which is 10 to 97 mol%.

In formula (3), R 111 represents a divalent organic group, R 115 represents a tetravalent organic group, and R 113 and R 114 independently represent a hydrogen atom or a monovalent organic group. show.
The curable resin composition according to any one of claims 1 to 3, further containing a photopolymerization initiator.
The curable resin composition according to claim 4, wherein the photopolymerization initiator is an oxime compound.
The curable resin composition according to any one of claims 1 to 5, further containing a polymerizable compound.
The curable resin composition according to any one of claims 1 to 6, further containing an organometallic complex.
The curable resin composition according to claim 7, wherein the organometallic complex is a metallocene compound.
The curable resin composition according to claim 7 or 8, wherein the metal contained in the organic metal 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 9, which is used for forming a photosensitive film to be subjected to negative development.
The curable resin composition according to any one of claims 1 to 10, which is used for forming an interlayer insulating film for a rewiring layer.
A cured product obtained by curing the curable resin composition according to any one of claims 1 to 11.
A laminated body containing two or more layers made of the cured product according to claim 12, and containing a metal layer between any of the layers made of the cured product.
A method for producing a cured product, which comprises a film forming step of applying the curable resin composition according to any one of claims 1 to 11 onto a substrate to form a film.
The method for producing a cured product according to claim 14, further comprising an exposure step of selectively exposing the film and a developing step of developing the film with a developer to form a pattern.
The method for producing a cured product according to claim 15, wherein the exposure light used for the exposure includes light having a wavelength of 405 nm.
The method for producing a cured product according to claim 15 or 16, wherein the exposure is an exposure by a laser direct imaging method.
The method for producing a cured product according to any one of claims 14 to 17, which comprises a heating step of heating the film at 50 to 450 ° C.
A semiconductor device comprising the cured product according to claim 12 or the laminate according to claim 13.
A polyimide precursor having a total content of a cyclic imide structure and a cyclic isoimide structure of 0.28 to 1.68 mmol / g and an acid value of 5.6 to 22.5 mgKOH / g.
The method for producing a polyimide precursor according to claim 20.
An amidation step of reacting a dicarboxylic acid compound with a diamine compound to obtain an amide compound,
A method for producing a polyimide precursor, which comprises a partial imidization step of partially imidizing the amide compound.
The method for producing a polyimide precursor according to claim 20.
A method for producing a polyimide precursor, which comprises an amidation step of reacting a dicarboxylic acid compound with a diamine compound in the presence of a basic catalyst to obtain an amide compound.