KR20230005356A - Curable resin composition, cured film, laminate, method for producing cured film, and semiconductor device - Google Patents

Abstract

A curable resin composition comprising at least one resin selected from the group consisting of a polyimide precursor, a polybenzoxazole precursor, polyimide and polybenzoxazole, and Compound B, which is a compound having a polymerizable group and an azole group, the curable resin composition A cured film formed by curing, a laminate comprising the cured film, a method for producing the cured film, and a semiconductor device comprising the cured film or the laminate.

Description

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

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

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

For example, in the use described above, the polyimide or polybenzoxazole includes at least one resin selected from the group consisting of polyimide, polyimide precursor, polybenzoxazole, and polybenzoxazole precursor. It is used in the form of a curable resin composition.

A cured film can be formed on the substrate by applying such a curable resin composition to a substrate by, for example, coating to form a resin film, and then performing exposure, development, heating, etc. as necessary. there is.

The said polyimide precursor and the said polybenzoxazole precursor are cyclized by heating, for example, and become polyimide and polybenzoxazole in a cured film, respectively.

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

For example, in Patent Document 1, (A) a polyimide precursor, (B) a compound containing a nitrogen atom-containing heterocyclic structure having a pka of 8.30 to 8.80, and (C) 5-amino-1H- A resin composition comprising a tetrazole is described.

Patent Document 1: Japanese Unexamined Patent Publication No. 2012-002281

It is a cured film made of a curable resin composition, and in the production of a cured film in contact with a metal, improvement in the adhesion between the cured film and the metal is required.

Examples of the metal include metals contained as metal layers such as conductive layers, and examples thereof include copper, aluminum, nickel, vanadium, titanium, chromium, cobalt, gold, and tungsten. Alloys containing metals are preferred, copper or alloys containing copper are more preferred, and copper is more preferred.

For example, in a laminate comprising a metal layer and a cured film in contact with the metal layer, improvement in adhesion between the metal layer and the cured film is desired.

The present invention provides a curable resin composition from which a cured film having excellent adhesion to metal is obtained, a cured film obtained by curing the curable resin composition, a laminate comprising the cured film, a method for producing the cured film, and the cured film or the laminate. It is an object of the present invention to provide a semiconductor device including a sieve.

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

<1> at least one resin selected from the group consisting of a polyimide precursor, a polybenzoxazole precursor, a polyimide, and a polybenzoxazole, and

A curable resin composition comprising compound B, which is a compound having a polymerizable group and an azole group.

<2> The curable resin composition according to <1>, wherein the compound B has at least one group selected from the group consisting of an amide group, a urethane group, and a urea group.

<3> The curable resin composition according to <1> or <2>, wherein the compound B contains, as the polymerizable group, at least one group selected from the group consisting of a radical polymerizable group and an alkoxysilyl group.

<4> The curable resin composition according to any one of <1> to <3>, in which the azole group in the compound B is a group represented by the following formula (B-1) or the following formula (B-2);

[Formula 1]

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

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

<5> The curable resin composition according to any one of <1> to <4>, which contains a compound B having a molecular weight of less than 2,000 as the compound B.

<6> The curable resin composition according to any one of <1> to <5>, containing compound B which is a resin as the compound B.

<7> The curable resin composition according to any one of <1> to <6>, further comprising compound C which is a compound having an azole group without having a polymerizable group.

<8> The curable resin composition according to <7>, wherein the compound C is a compound represented by the following formula (C-1) or the following formula (C-2);

[Formula 2]

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

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

<9> wherein at least one resin selected from the group consisting of the polyimide precursor, polybenzoxazole precursor, polyimide, and polybenzoxazole has a polymerizable group polymerizable with the polymerizable group in the compound B, <1 The curable resin composition according to any one of > to <8>.

<10> The curable resin composition according to any one of <1> to <9>, further comprising Compound D, which is a silane coupling agent having a polymerizable group different from an alkoxysilyl group and not having an azole group.

<11> wherein at least one resin selected from the group consisting of the polyimide precursor, polybenzoxazole precursor, polyimide, and polybenzoxazole has a polymerizable group polymerizable with the polymerizable group in the compound D, <10 The curable resin composition described in >.

<12> The curable resin composition according to any one of <1> to <11>, further comprising compound E which is a silane coupling agent having neither a polymerizable group different from an alkoxysilyl group nor an azole group.

<13> The curable resin composition according to any one of <1> to <12>, which is used for forming an interlayer insulating film for a redistribution layer.

<14> A cured film formed by curing the curable resin composition according to any one of <1> to <13>.

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

<16> A method for producing a cured film including a film formation step of applying the curable resin composition according to any one of <1> to <13> to a substrate to form a film.

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

<18> The method for producing a cured film according to <16> or <17>, including a heating step of heating the film at 50 to 450°C.

<19> A semiconductor device comprising the cured film according to <14> or the laminate according to <15>.

According to the present invention, a curable resin composition from which a cured film having excellent adhesion to metal is obtained, a cured film formed by curing the curable resin composition, a laminate comprising the cured film, a method for producing the cured film, and the cured film or the above A semiconductor device including a laminate is provided.

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

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

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

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

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

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

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

In this specification, the total solid content refers to the total mass of the components excluding the solvent from all components of the composition. Moreover, in this specification, solid content concentration is the mass percentage of other components except a solvent with respect to the total mass of a composition.

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

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

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

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

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

(curable resin composition)

The curable resin composition of the present invention includes at least one resin selected from the group consisting of a polyimide precursor, a polybenzoxazole precursor, a polyimide, and a polybenzoxazole (hereinafter, also referred to as “specific resin”), and a polymerizable group. and Compound B, which is a compound having an azole group.

The curable resin composition of the present invention may be either a negative curable resin composition or a positive curable resin composition, but is preferably a negative curable resin composition.

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

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

ADVANTAGE OF THE INVENTION According to the curable resin composition of this invention, the cured film excellent in adhesiveness with metal is obtained.

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

The curable composition of the present invention contains the compound B having a polymerizable group and an azole group, so that the resulting cured film has excellent adhesion to metal.

It is believed that the polymer of the compound B exists on the surface of the metal side in the cured film when the azole group in the compound B coordinates to the metal surface and the polymerizable group in the compound B polymerizes in the cured film. I think.

It is thought that the presence of the above polymer exhibits an anchor effect to resin after curing such as polyimide, and improves adhesion.

The effect of the said adhesive improvement becomes remarkable when specific resin, such as a polyimide, has a polymeric group, or when curable resin composition contains a silane coupling agent.

It is estimated that this is because polymerization is formed also between specific resin and compound B in a cured film, or polymerization is formed also between a silane coupling agent and compound B.

In addition, in the production of a laminate comprising a film made of a curable resin composition, for example, a metal layer is formed on a cured film made of a curable resin composition, and another cured film made of a curable resin composition is formed on the metal layer. Similarly, there are cases in which a metal layer and a cured film are laminated and formed.

It is thought that according to the curable resin composition of the present invention, peeling between layers between resin layers/resin layers and between metal layers/resin layers is suppressed also in such a laminate.

This is presumed to be due to the existence of the relatively soft polymer of the above-described compound B between a hard metal and a resin such as hard polyimide.

In the present invention, suppression of peeling between resin layers/resin layers and between metal layers/resin layers in a laminate is also referred to as "excellent adhesion during multilayer lamination".

Here, in Patent Document 1, there is neither description nor suggestion about the curable resin composition containing the compound B having a polymerizable group and an azole group.

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

<specific resin>

The curable resin composition of the present invention contains at least one resin (specific resin) selected from the group consisting of polyimide, polyimide precursor, polybenzoxazole, and polybenzoxazole precursor.

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

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

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

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

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

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

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

According to the above aspect, in the cured film, the polymerizable group in the specific resin and the polymerizable group in the compound B polymerize, so that the bond between the specific resin and the compound B is strengthened, and the adhesion of the obtained cured film to the metal is higher. it is thought to improve

Moreover, when curable resin composition contains compound D mentioned later, it is preferable that specific resin has a polymerizable group in compound D and a polymerizable group polymerizable.

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

According to the above aspect, the polymerizable group in the specific resin and the polymerizable group in the compound D polymerize in the cured film, so that the bond between the specific resin and the compound D is strengthened, and the adhesion of the obtained cured film to the metal is higher. it is thought to improve

Moreover, in the said aspect, it is preferable that compound B has an alkoxysilyl group.

According to the above aspect, since the polymerizable group in the specific resin and the polymerizable group in the compound D polymerize in the cured film, the alkoxysilyl group in the compound B and the compound D as the silane coupling agent condense, respectively It is thought that the bond between the compounds becomes strong and the adhesiveness with the metal of the cured film obtained is further improved.

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

When a specific resin has a radical polymerizable group, the curable resin composition preferably contains a radical photopolymerization initiator described later as a photosensitizer, and further includes a radical photopolymerization initiator described later as a photosensitizer, and further includes a radical crosslinking agent described later. It is more preferable to include a radical photopolymerization initiator described later as a photosensitizer, a radical crosslinking agent described later, and further preferably a sensitizer described later. A negative photosensitive layer is formed from such a curable resin composition, for example.

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

When specific resin has an acid-decomposable group, it is preferable that curable resin composition contains the photo-acid generator mentioned later as a photosensitizer. From such a curable resin composition, a chemically amplified positive photosensitive layer or negative photosensitive layer is formed, for example.

[Polyimide precursor]

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

Equation (2)

[Formula 3]

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

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

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

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

Specifically, it is preferably diamine containing a group consisting of a straight-chain or branched aliphatic group having 2 to 20 carbon atoms, a cyclic aliphatic group having 6 to 20 carbon atoms, an aromatic group having 6 to 20 carbon atoms, or a combination thereof, It is more preferable that it is a diamine containing the group which consists of a C6-C20 aromatic group. As an example of an aromatic group, the following is mentioned.

[Formula 4]

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

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

As diamine, specifically, 1,2-diaminoethane, 1,2-diaminopropane, 1,3-diaminopropane, 1,4-diaminobutane, and 1,6-diaminohexyl three; 1,2- or 1,3-diaminocyclopentane, 1,2-, 1,3- or 1,4-diaminocyclohexane, 1,2-, 1,3- or 1,4-bis (Aminomethyl)cyclohexane, bis-(4-aminocyclohexyl)methane, bis-(3-aminocyclohexyl)methane, 4,4'-diamino-3,3'-dimethylcyclohexylmethane phosphorus and isophoronediamine; m- or p-phenylenediamine, diaminotoluene, 4,4'- or 3,3'-diaminobiphenyl, 4,4'-diaminodiphenyl ether, 3,3-diaminodiphenyl Ether, 4,4'- and 3,3'-diaminodiphenylmethane, 4,4'- and 3,3'-diaminodiphenylsulfone, 4,4'- and 3,3'-di Aminodiphenylsulfide, 4,4'- or 3,3'-diaminobenzophenone, 3,3'-dimethyl-4,4'-diaminobiphenyl, 2,2'-dimethyl-4,4 '-diaminobiphenyl, 3,3'-dimethoxy-4,4'-diaminobiphenyl, 2,2-bis (4-aminophenyl) propane, 2,2-bis (4-aminophenyl ) Hexafluoropropane, 2,2-bis (3-hydroxy-4-aminophenyl) propane, 2,2-bis (3-hydroxy-4-aminophenyl) hexafluoropropane, 2, 2-bis(3-amino-4-hydroxyphenyl)propane, 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane, bis(3-amino-4-hydroxyphenyl) )sulfone, bis(4-amino-3-hydroxyphenyl)sulfone, 4,4'-diaminoparaterphenyl, 4,4'-bis(4-aminophenoxy)biphenyl, bis[4-(4 -aminophenoxy)phenyl]sulfone, bis[4-(3-aminophenoxy)phenyl]sulfone, bis[4-(2-aminophenoxy)phenyl]sulfone, 1,4-bis(4-aminophenoxy) ) Benzene, 9,10-bis (4-aminophenyl) anthracene, 3,3'-dimethyl-4,4'-diaminodiphenylsulfone, 1,3-bis (4-aminophenoxy) benzene, 1 ,3-bis(3-aminophenoxy)benzene, 1,3-bis(4-aminophenyl)benzene, 3,3'-diethyl-4,4'-diaminodiphenylmethane, 3,3' -Dimethyl-4,4'-diaminodiphenylmethane, 4,4'-diaminooctafluorobiphenyl, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 2 ,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, 9,9-bis(4-aminophenyl)-10-hydroanthracene, 3,3',4,4'-tetra Aminobiphenyl, 3,3',4,4'-tetraaminodiphenyl ether, 1,4-diaminoanthraquinone, 1,5-diaminoanthraquinone, 3,3-dihydroxy-4,4 '-Diamino Biphenyl, 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, 2,7-diaminofluorene, 2 ,5-diaminopyridine, 1,2-bis(4-aminophenyl)ethane, diaminobenzanilide, diaminobenzoic acid ester, 1,5-diaminonaphthalene, diaminobenzotrifluoride, 1,3 -Bis(4-aminophenyl)hexafluoropropane, 1,4-bis(4-aminophenyl)octafluorobutane, 1,5-bis(4-aminophenyl)decafluoropentane, 1, 7-bis (4-aminophenyl) tetradecafluoroheptane, 2,2-bis [4- (3-aminophenoxy) phenyl] hexafluoropropane, 2,2-bis [4- (2- Aminophenoxy)phenyl]hexafluoropropane, 2,2-bis[4-(4-aminophenoxy)-3,5-dimethylphenyl]hexafluoropropane, 2,2-bis[4-( 4-aminophenoxy) -3,5-bis (trifluoromethyl) phenyl] hexafluoropropane, p-bis (4-amino-2-trifluoromethylphenoxy) benzene, 4,4'- Bis (4-amino-2-trifluoromethylphenoxy) biphenyl, 4,4'-bis (4-amino-3-trifluoromethylphenoxy) biphenyl, 4,4'-bis (4- Amino-2-trifluoromethylphenoxy)diphenylsulfone, 4,4'-bis(3-amino-5-trifluoromethylphenoxy)diphenylsulfone, 2,2-bis[4-(4- Amino-3-trifluoromethylphenoxy) phenyl] hexafluoropropane, 3,3', 5,5'-tetramethyl-4,4'-diaminobiphenyl, 4,4'-diamino- At least 1 selected from 2,2'-bis(trifluoromethyl)biphenyl, 2,2',5,5',6,6'-hexafluorotolidine and 4,4'-diaminoquaterphenyl species of diamines.

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

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

[Formula 1]

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

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

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

formula (51)

[Formula 5]

In Formula (51), R ⁵⁰ to R ⁵⁷ are each independently a hydrogen atom, a fluorine atom, or a monovalent organic group, and at least one of R ⁵⁰ to R ⁵⁷ is a fluorine atom, a methyl group, or a trifluoromethyl group.

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

[Formula 6]

In Formula (61), R ⁵⁸ and R ⁵⁹ are each independently a fluorine atom or a trifluoromethyl group.

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

Moreover, the structure containing a polymeric group may be sufficient as ^R111 .

For example, R ¹¹¹ can also be made into a structure derived from a diamine compound having a polymerizable group.

The diamine compound having a polymerizable group is not particularly limited, but is preferably a compound containing an aromatic ring structure, and more preferably a compound having a structure in which a structure containing an amino group and a polymerizable group is directly connected to the aromatic ring structure Do.

As the polymerizable group, a group containing an ethylenically unsaturated group, a cyclic ether group, a methylol group or an alkoxymethyl group is preferable, and a vinyl group, a (meth)allyl group, a (meth)acrylamide group, a (meth)acryloxy group, and a maleimide group. group, vinylphenyl group, epoxy group, oxetanyl group, methylol group or alkoxymethyl group is more preferred, and (meth)acryloxy group, (meth)acrylamide group, epoxy group, methylol group or alkoxymethyl group is more preferred.

Moreover, when R ¹¹¹ is a structure containing a polymerizable group, it is preferable that R ¹¹¹ is a structure represented by the following formula (1-1).

[Formula 7]

In formula (1-1), Y ¹ represents an n+2 valent group containing an aromatic hydrocarbon group, P ¹ represents a group containing a polymerizable group, n represents an integer greater than or equal to 1, and * represents the formula ( 2) shows the bonding site to the nitrogen atom to which R ¹¹¹ in 2) is bonded.

-Y ¹ -

In Formula (1-1), Y ¹ represents an n+2 valent group containing an aromatic hydrocarbon group.

The aromatic hydrocarbon group for Y ¹ is preferably an aromatic hydrocarbon group of 6 to 30 carbon atoms, more preferably an aromatic hydrocarbon group of 6 to 20 carbon atoms, and still more preferably a group obtained by removing two or more hydrogen atoms from the benzene ring. and a group obtained by removing three or more hydrogen atoms from the benzene ring is particularly preferred.

In formula (1-1), it is preferable that all of the bonding sites with two * described in formula (1-1) in Y ¹ are aromatic hydrocarbon groups. That is, it is preferable that the two * described in Formula (1-1) bond directly with the aromatic hydrocarbon ring structure contained in Y ¹ .

Moreover, in formula (1-1), it is preferable that all of the bonding sites with P ¹ in Y ¹ are aromatic hydrocarbon groups. That is, P ¹ is preferably directly bonded to the aromatic hydrocarbon ring structure included in Y ¹ .

Y ¹ preferably contains at least one structure selected from the group consisting of structures represented by the following formulas (A2-1) to (A2-5), and the above formulas (A2-1) to (A2-5) It is more preferable that it is at least 1 sort(s) of structure selected from the group which consists of structures represented by -5).

[Formula 8]

In formulas (A2-1) to (A2-5), R ^A211 to R ^A214 , R ^A221 to R ^A224 , R ^A231 to R ^A238 , R ^A241 to R ^A248 and R ^A251 to R ^A258 are each independently a hydrogen atom , represents an alkyl group, a cyclic alkyl group, an alkoxy group, a hydroxyl group, a cyano group, a halogenated alkyl group, or a halogen atom, and L ^A231 and L ^A241 are each independently a single bond, a carbonyl group, a sulfonyl group, 2 It represents a valent saturated hydrocarbon group, a divalent unsaturated hydrocarbon group, a heteroatom, a heterocyclic group, or a halogenated alkylene group, and at least one of R ^A211 to R ^A214 , at least one of R ^A221 to R ^A224 , R ^A231 to At least one of R ^A238 , at least one of R ^A241 to R ^A248 , and at least one of R ^A251 to R ^A258 may be a binding site to P ¹ in the formula (1-1), and * is each independently Indicates the binding site with the structure.

Among these, from a viewpoint of solvent solubility, it is preferable that Y1 contains the structure represented by any ^of formula (A2-1) - formula (A2-4), and formula (A2-2) or formula (A2-4) It is more preferable to include a structure represented by any of the above.

In formulas (A2-1) to (A2-5), R ^A211 to R ^A214 , R ^A221 to R ^A224 , R ^A231 to R ^A238 , R ^A241 to R ^A248 and R ^A251 to R ^A258 are 1) at least one of R ^A211 to R ^A214 , at least one of R ^A221 to R ^A224 , at least one of R ^A231 to R ^A238 , at least one of R ^A241 to R ^A248 , And at least one of R ^A251 to R ^A258 may be a binding site with P ¹ in the formula (1-1).

In formula (A2-1), when R ^A211 to R ^A214 are not bonding sites to P ¹ , R ^A211 to R ^A214 are each independently a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a cyclic group having 3 to 12 carbon atoms. An alkyl group, an alkoxy group having 1 to 6 carbon atoms, a hydroxy group, a cyano group, a halogenated alkyl group having 1 to 3 carbon atoms, or a halogen atom is preferably represented, and from the viewpoint of solvent solubility, a hydrogen atom or a carbon number 1 An alkyl group of 6 to 6, an alkoxy group of 1 to 6 carbon atoms, and a halogenated alkyl group of 1 to 3 carbon atoms are more preferred, and a hydrogen atom or an alkyl group of 1 to 6 carbon atoms is more preferred.

Examples of the halogen atom in the halogenated alkyl group in R ^A211 to R ^A214 or the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, and the like, and a chlorine atom or a bromine atom is preferred.

In formula (A2-2), R ^A221 to R ^A224 have the same meanings as R ^A211 to R ^A214 in formula (A2-1), and preferred embodiments are also the same.

In formula (A2-3), R ^A231 to R ^A238 are each independently a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a cyclic alkyl group having 3 to 12 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a hydroxyl group, or a cyano group. It is preferable to represent a group, a halogenated alkyl group of 1 to 3 carbon atoms, or a halogen atom, and from the viewpoint of solvent solubility, a hydrogen atom, an alkyl group of 1 to 6 carbon atoms, an alkoxy group of 1 to 6 carbon atoms, or a carbon atom A halogenated alkyl group of 1 to 3 is more preferable, and a hydrogen atom or an alkyl group of 1 to 6 carbon atoms is more preferable.

Examples of the halogen atom or the halogen atom in the halogenated alkyl group for R ^A231 to R ^A238 include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, and the like, and a chlorine atom or a bromine atom is preferred.

In formula (A2-3), L ^A231 is a single bond, a divalent saturated hydrocarbon group having 1 to 6 carbon atoms, a divalent unsaturated hydrocarbon group having 5 to 24 carbon atoms, -O-, -S-, -NR ^N -, a heterocyclic group, or preferably representing a halogenated alkylene group having 1 to 6 carbon atoms, and preferably representing a single bond, a saturated hydrocarbon group having 1 to 6 carbon atoms, -O- or a heterocyclic group, and a single bond or -O- is more preferred.

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

The divalent unsaturated hydrocarbon group may be a divalent aliphatic unsaturated hydrocarbon group or a divalent aromatic hydrocarbon group, but is preferably a divalent aromatic hydrocarbon group.

As the heterocyclic group, for example, a group in which two hydrogen atoms have been removed from an aliphatic or aromatic heterocyclic ring is preferable, and a group in which two hydrogen atoms have been removed from an aliphatic or aromatic heterocyclic ring is preferable, and a pyrrolidine ring, tetrahydrofuran ring, A group obtained by removing two hydrogen atoms from a ring structure such as a tetrahydrothiophene ring, a pyrrole ring, a furan ring, a thiophene ring, a piperidine ring, a tetrahydropyran ring, a pyridine ring, and a morpholine ring is more preferable. These heterocycles may form condensed rings with other heterocycles or hydrocarbon rings.

It is preferable that it is 5-10, and, as for the number of reduction of the said heterocyclic ring, it is more preferable that it is 5 or 6.

Moreover, it is preferable that it is an oxygen atom, a nitrogen atom, or a sulfur atom as a hetero atom in the said heterocyclic group.

As a halogen atom in the said halogenated alkylene group, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc. are mentioned, A chlorine atom or a bromine atom is preferable.

In the formula (A2-4), R ^A241 to R ^A248 and L ^A241 have the same meaning as R ^A231 to R ^A238 and L ^A231 in the formula (A2-3), and the preferred embodiments are also the same.

In formula (A2-5), R ^A251 to R ^A258 have the same meanings as R ^A211 to R ^A214 in formula (A2-1), and preferred embodiments are also the same.

In formula (A2-1), at least one of R ^A211 to R ^A214 is preferably a binding site to P ¹ in formula (1-1), and one of R ^A211 to R ^A214 binds to P ¹ It is more preferably a site, and it is preferable that R ^A213 is a binding site with P ¹ above.

In formula (A2-2), at least one of R ^A221 to R ^A224 is preferably a binding site to P ¹ in formula (1-1), and one of R ^A221 to R ^A224 binds to P ¹ It is more preferably a site, and it is preferable that R ^A223 is a binding site with P ¹ .

In formula (A2-3), at least one of R ^A231 to R ^A238 is preferably a binding site to P ¹ in formula ( ^1-1 ), and two of R ^A231 to R ^A238 are It is more preferably a binding site, and a total of two of one of R ^A231 to R ^A234 and one of R ^A235 to R ^A238 is more preferably a binding site to P ¹ , and two of R ^A231 and R ^A238 , Particularly preferred is a binding site with the aforementioned P ¹ .

In formula (A2-4), at least one of R ^A241 to R ^A248 is preferably a binding site to P ¹ in formula ( ^1-1 ), and two of R ^A241 to R ^A248 are It is more preferably a binding site, and a total of two of one of R ^A241 to R ^A244 and one of R ^A245 to R ^A248 is more preferably a binding site to P ¹ , and two of R ^A241 and R ^A248 , Particularly preferred is a binding site with the aforementioned P ¹ .

In formula (A2-5), at least one of R ^A251 to R ^A258 is preferably a binding site to P ¹ in formula ( ^1-1 ), and two of R ^A251 to R ^A258 are It is more preferably a binding site, and a total of two of one of R ^A251 to R ^A254 and one of R ^A255 to R ^A258 is more preferably a binding site to P ¹ , and two of R ^A253 and R ^A257 , Particularly preferred is a binding site with the aforementioned P ¹ .

In formulas (A2-1) to (A2-5), each of the two * is preferably * in formula (1-1). That is, it is preferable that the two nitrogen atoms to which R ¹¹¹ in Formula (2) bonds are bonded directly to positions indicated by two * in Formulas (A2-1) to (A2-5).

Among these, Y ¹ is preferably a group represented by the following formula (Y-1) or (Y-2).

[Formula 9]

In formula (Y-1), R ^Y11 , R ^Y12 , and R ^Y13 have the same meanings as R ^A211 , R ^A212 and R ^A214 in formula (A2-1), and preferred embodiments are also the same.

In formula (Y-2), R ^Y21 to R ^Y26 each have the same meaning as R ^A242 to R ^A247 in formula (A2-4), and preferred embodiments are also the same.

In formula (Y-1) or formula (Y-2), * represents a bonding site to two nitrogen atoms to which R ¹¹¹ in formula (2) bonds, respectively, and # represents a bonding site to two nitrogen atoms in formula (1-1), respectively. Binding sites to P ¹ are shown respectively.

-P ¹ -

In Formula (1-1), P ¹ represents a group containing a polymerizable group.

As the polymerizable group, a group containing an ethylenically unsaturated group, a cyclic ether group, a methylol group or an alkoxymethyl group is preferable, and a vinyl group, a (meth)allyl group, a (meth)acrylamide group, a (meth)acryloxy group, and a maleimide group. group, vinylphenyl group, epoxy group, oxetanyl group, methylol group or alkoxymethyl group is more preferred, and (meth)acryloxy group, (meth)acrylamide group, epoxy group, methylol group or alkoxymethyl group is more preferred.

The number of polymerizable groups contained in P ¹ is 1 or more, preferably 1 to 15, more preferably 1 to 10, still more preferably 1 to 5, particularly preferably 1 or 2, , most preferably one.

Moreover, it is preferable that P1 is a group represented by the following formula (P- ¹ ).

[Formula 10]

In formula (P-1), L ¹ represents a single bond or an m+1 valent linking group, A ² represents a polymerizable group, m represents an integer greater than or equal to 1, and * represents a bonding site with Y ¹ .

In formula (P-1), L ¹ is preferably a single bond, a hydrocarbon group, an ether bond, a carbonyl group, a thioether bond, a sulfonyl group, -NR ^N -, or a group in which two or more of these are bonded together, provided A bond, or a hydrocarbon group, an ether bond, a carbonyl group, -NR ^N -, or a group in which two or more of these are bonded is more preferable.

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

The hydrocarbon group for L ¹ is preferably a saturated aliphatic hydrocarbon group of 1 to 30 carbon atoms, an aromatic hydrocarbon group of 6 to 30 carbon atoms, or a group represented by a combination thereof, and a saturated carbon atom of 1 to 10 carbon atoms. More preferred is an aliphatic hydrocarbon group, a group in which two or more hydrogen atoms have been removed from the benzene ring, or a group represented by a bond thereof.

In formula (P-1), A ² is a vinyl group, a (meth)allyl group, a (meth)acrylamide group, a (meth)acryloxy group, a maleimide group, a vinylphenyl group, an epoxy group, an oxetanyl group, a methylol group, or An alkoxymethyl group is preferable, and a (meth)acryloxy group, a (meth)acrylamide group, an epoxy group, a methylol group, or an alkoxymethyl group is more preferable.

In formula (P-1), m is preferably an integer of 1 to 15, more preferably an integer of 1 to 10, still more preferably an integer of 1 to 5, particularly preferably 1 or 2, and 1 is most preferable

Moreover, it is preferable that P1 is a group represented by the following formula (P ^- 2) or formula (P-3).

[Formula 11]

In formula (P-2), A ² represents a polymerizable group, and * represents a bonding site with Y ¹ .

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

In formula (P-3), A ² represents a polymerizable group, L ² represents a hydrocarbon group, or a hydrocarbon group, an ether bond, a carbonyl group, a thioether bond, a sulfonyl group, -NR ^N -, or Represents a group in which two or more of these are bonded together, Z ¹ represents an ether bond, an ester bond, a urethane bond, a urea bond, an amide bond, or a carbonate bond, and * represents a bonding site with Y ¹ . R ^N is as described above.

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

In formula (P-3), L ² is preferably a hydrocarbon group, a (poly)alkyleneoxy group, or a group represented by a combination thereof. As the hydrocarbon group, an alkylene group, a divalent aromatic hydrocarbon group, or a group represented by a combination thereof is preferable, and an alkylene group is more preferable.

In this specification, a (poly)alkyleneoxy group means an alkyleneoxy group or a polyalkyleneoxy group. In the present invention, a polyalkyleneoxy group refers to a group in which two or more alkyleneoxy groups are directly bonded. The alkylene groups in the plurality of alkyleneoxy groups contained in the polyalkyleneoxy group may be the same or different. When the polyalkyleneoxy group includes a plurality of types of alkyleneoxy groups from which the alkylene groups differ, the arrangement of the alkyleneoxy groups in the polyalkyleneoxy group may be random arrangement, block arrangement, alternating arrangement, etc. It may be an array having a pattern of

As said alkylene group, a C1-C30 alkylene group is preferable, a C1-C20 alkylene group is more preferable, and a C1-C10 alkylene group is still more preferable.

As the aromatic hydrocarbon group, an aromatic hydrocarbon group having 6 to 30 carbon atoms is preferable, an aromatic hydrocarbon group having 6 to 20 carbon atoms is more preferable, a phenylene group or a naphthylene group is more preferable, and a phenylene group is particularly preferable.

The alkylene group in the (poly)alkyleneoxy group is preferably an alkylene group having 2 to 10 carbon atoms, more preferably an alkylene group having 2 to 4 carbon atoms, more preferably an ethylene group or a propylene group, and even more preferably an ethylene group Do.

The number of alkyleneoxy groups contained in the polyalkyleneoxy group (repeat number of polyalkyleneoxy groups) is preferably from 2 to 20, more preferably from 2 to 10, still more preferably from 2 to 5, and from 2 to 20. 4 is particularly preferred.

In formula (P-3), Z ¹ represents an ether bond, an ester bond, a urethane bond, a urea bond, an amide bond, or a carbonate bond, and an ester bond, a urethane bond, a urea bond, or an amide bond. more preferable than this

In the present invention, when simply described as "ester bond", "urethane bond", "amide bond" or the like, the directions of these bonds are not limited. For example, when Z ¹ is an ester bond, the bonding site with L ² in Z ¹ may be a carbon atom or an oxygen atom in the ester bond.

R ¹¹⁵ in Formula (2) represents a tetravalent organic group. As the tetravalent organic group, a tetravalent organic group containing an aromatic ring is preferable, and a group represented by the following formula (5) or formula (6) is more preferable.

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

[Formula 12]

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

Specific examples of R ¹¹⁵ include tetracarboxylic acid residues remaining after removal of the anhydride group from tetracarboxylic dianhydride. As for tetracarboxylic dianhydride, only 1 type may be used, and 2 or more types may be used.

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

[Formula 13]

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

Specific examples of tetracarboxylic dianhydride include pyromellitic dianhydride (PMDA), 3,3',4,4'-biphenyltetracarboxylic dianhydride, and 3,3',4,4'-diphenylsulfide tetracarboxylic dianhydride. Water, 3,3',4,4'-diphenylsulfotetracarboxylic dianhydride, 3,3',4,4'-benzophenonetetracarboxylic dianhydride, 3,3',4,4'-diphenylmethane Intertetracarboxylic dianhydride, 2,2',3,3'-diphenylmethanetetracarboxylic dianhydride, 2,3,3',4'-biphenyltetracarboxylic dianhydride, 2,3,3',4 '-benzophenonetetracarboxylic dianhydride, 4,4'-oxydiphthalic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 1,4,5,7-naphthalenetetracarboxylic dianhydride, 2, 2-bis(3,4-dicarboxyphenyl)propane dianhydride, 2,2-bis(2,3-dicarboxyphenyl)propane dianhydride, 2,2-bis(3,4-dicarboxyphenyl) Hexafluoropropane dianhydride, 1,3-diphenylhexafluoropropane-3,3,4,4-tetracarboxylic dianhydride, 1,4,5,6-naphthalenetetracarboxylic dianhydride, 2,2 ',3,3'-diphenyltetracarboxylic dianhydride, 3,4,9,10-perylenetetracarboxylic dianhydride, 1,2,4,5-naphthalenetetracarboxylic dianhydride, 1,4,5,8 -Naphthalenetetracarboxylic dianhydride, 1,8,9,10-phenanthrenetetracarboxylic dianhydride, 1,1-bis(2,3-dicarboxyphenyl)ethane dianhydride, 1,1-bis(3,4- dicarboxyphenyl)ethane dianhydride, 1,2,3,4-benzenetetracarboxylic acid dianhydride, and C1-C6 alkyl and C1-C6 alkoxy derivatives thereof.

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

It is also preferable that at least one of R ¹¹¹ and R ¹¹⁵ has an OH group. More specifically, as R ¹¹¹ , residues of bisaminophenol derivatives are exemplified.

R ¹¹³ and R ¹¹⁴ each independently represent a hydrogen atom or a monovalent organic group, and preferably at least one of R ¹¹³ and R ¹¹⁴ contains a polymerizable group, and more preferably both contain a polymerizable group. As the polymerizable group, it is a group capable of undergoing a crosslinking reaction by the action of heat, a radical, or the like, and a radical polymerizable group is preferable. As specific examples of the polymerizable group in specific resin, a group having an ethylenically unsaturated bond, an alkoxymethyl group, a hydroxymethyl group, an acyloxymethyl group, an epoxy group, an oxetanyl group, a benzoxazolyl group, a block isocyanate group, a methylol group , an amino group. As the radical polymerizable group that the polyimide precursor or the like has, a group having an ethylenically unsaturated bond is preferable.

Examples of the group having an ethylenically unsaturated bond include a vinyl group, a (meth)allyl group, and a group represented by the following formula (III), with the group represented by the following formula (III) being preferred.

[Formula 14]

In Formula (III), R ²⁰⁰ represents a hydrogen atom or a methyl group, and is preferably a hydrogen atom.

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 - or a polyalkyleneoxy group.

Examples of suitable R ²⁰¹ include ethylene group, propylene group, trimethylene group, tetramethylene group, 1,2-butanediyl group, 1,3-butanediyl group, pentamethylene group, hexamethylene group, octamethylene group , dodecamethylene group, -CH ₂ CH(OH)CH ₂ -, polyalkyleneoxy group, ethylene group, propylene group, trimethylene group, -CH ₂ CH(OH)CH ₂ -, polyalkylene An oxy group is more preferable, and a polyalkyleneoxy group is still more preferable.

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

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

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

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

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

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

R ¹¹³ and R ¹¹⁴ are each independently a hydrogen atom or a monovalent organic group. Examples of the monovalent organic group include an aromatic group and an aralkyl group having an acidic group bonded to one, two or three, preferably one, of the carbons constituting the aryl group. Specifically, an aromatic group having 6 to 20 carbon atoms having an acidic group and an aralkyl group having 7 to 25 carbon atoms having an acidic group are exemplified. More specifically, a phenyl group having an acidic group and a benzyl group having an acidic group are exemplified. The acidic group is preferably an OH group.

It is more preferable that R ¹¹³ or R ¹¹⁴ is a hydrogen atom, 2-hydroxybenzyl, 3-hydroxybenzyl or 4-hydroxybenzyl.

From the viewpoint of solubility in organic solvents, R ¹¹³ or R ¹¹⁴ is preferably a monovalent organic group. The monovalent organic group preferably includes a straight-chain or branched alkyl group, a cyclic alkyl group, or an aromatic group, and more preferably an alkyl group substituted with an aromatic group.

As for carbon number of an alkyl group, 1-30 are preferable. Alkyl groups may be straight-chain, branched, or cyclic. Examples of the straight-chain or branched alkyl group include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl, tetradecyl, octadecyl, Isopropyl group, isobutyl group, sec-butyl group, t-butyl group, 1-ethylpentyl group, 2-ethylhexyl group, 2-(2-(2-methoxyethoxy)ethoxy)ethoxy group, 2 -(2-(2-ethoxyethoxy)ethoxy)ethoxy)ethoxy group, 2-(2-(2-(2-methoxyethoxy)ethoxy)ethoxy)ethoxy group, and 2-( and a 2-(2-(2-ethoxyethoxy)ethoxy)ethoxy)ethoxy group. The cyclic alkyl group may be a monocyclic cyclic alkyl group or a polycyclic cyclic alkyl group. As a monocyclic cyclic alkyl group, a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a cyclooctyl group are mentioned, for example. Examples of the polycyclic cyclic alkyl group include adamantyl group, norbornyl group, bornyl group, camphenyl group, decahydronaphthyl group, tricyclodecanyl group, tetracyclodecanyl group, camphoroyl group, dicyclohexyl group and pinenyl group. can be heard Among them, a cyclohexyl group is most preferable from the viewpoint of coexistence with high sensitivity. Moreover, as an aromatic group substituted alkyl group, the aromatic group substituted linear alkyl group mentioned later is preferable.

As the aromatic group, specifically, a substituted or unsubstituted benzene ring, naphthalene ring, pentalene ring, indene ring, azulene ring, heptalene ring, indacene ring, perylene ring, pentacene ring, acenaphthene ring, phenanthrene ring, anthracene ring, Naphthacene ring, chrysene ring, triphenylene ring, fluorene ring, biphenyl ring, pyrrole ring, furan ring, thiophene ring, imidazole ring, oxazole ring, thiazole ring, pyridine ring, pyrazine ring, pyrimidine ring, pyr Dajin ring, indolizine ring, indole ring, benzofuran ring, benzothiophene ring, isobenzofuran ring, quinolizine ring, quinoline ring, phthalazine ring, naphthyridine ring, quinoxaline ring, quinoxazoline ring, isoquinoline ring, carbazole ring, phenanthridine ring, acridine ring, phenanthroline ring, cyantrene ring, chromen ring, xanthene ring, phenoxacyine ring, phenothiazine ring or phenazine ring. A benzene ring is most preferred.

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

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

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

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

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

It is preferable that the repeating unit represented by Formula (2) is a repeating unit represented by Formula (2-A). That is, it is preferable that at least 1 sort(s), such as the polyimide precursor used by this invention, is a precursor which has a repeating unit represented by Formula (2-A). By setting it as such a structure, it becomes possible to further expand the width|variety of exposure latitude.

Formula (2-A)

[Formula 15]

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

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

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

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

As an embodiment of the polyimide precursor in the present invention, a polyimide precursor in which 50 mol% or more, furthermore 70 mol% or more, particularly 90 mol% or more of all repeating units is a repeating unit represented by Formula (2) is exemplified. do.

The weight average molecular weight (Mw) of the polyimide precursor is preferably 18,000 to 30,000, more preferably 20,000 to 27,000, still more preferably 22,000 to 25,000. Moreover, the number average molecular weight (Mn) is preferably 7,200 to 14,000, more preferably 8,000 to 12,000, still more preferably 9,200 to 11,200.

The degree of dispersion of the molecular weight of the polyimide precursor is preferably 2.5 or more, more preferably 2.7 or more, and still more preferably 2.8 or more. The upper limit of the degree of dispersion of the molecular weight of the polyimide precursor is not particularly set, but is, for example, preferably 4.5 or less, more preferably 4.0 or less, still more preferably 3.8 or less, still more preferably 3.2 or less, and 3.1 or less. It is even more preferable, 3.0 or less is even more preferable, and 2.95 or less is particularly preferable.

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

[Polyimide]

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

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

Moreover, it is preferable that a polyimide is a polyimide which has a several imide structure in a main chain from a viewpoint of the film|membrane strength and insulating property of the organic film obtained.

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

-Fluorine atom-

From the viewpoint of the film strength of the resulting organic film, it is preferable that the polyimide has a fluorine atom.

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

It is preferable that it is 1-50 mol/g, and, as for the quantity of fluorine atoms with respect to the total mass of polyimide, it is more preferable that it is 5-30 mol/g.

-silicon atom-

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

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

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

It is preferable that it is 0.01-5 mol/g, and, as for the quantity of silicon atoms with respect to the total mass of polyimide, it is more preferable that it is 0.05-1 mol/g.

-ethylenically unsaturated bonds-

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

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

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

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

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

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

[Formula 16]

In Formula (IV), R ²⁰ represents a hydrogen atom or a methyl group, and a methyl group is preferable.

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

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

[Formula 17]

In the formulas (R1) to (R3), L represents a single bond, an alkylene group having 2 to 12 carbon atoms, a (poly)alkyleneoxy group having 2 to 30 carbon atoms, or a group in which two or more of these are bonded together, and X is an oxygen atom or sulfur represents an atom, * represents a bonding site to another structure, and ● represents a bonding site to an oxygen atom to which R ²⁰¹ in formula (III) is bonded.

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

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

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

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

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

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

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

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

It is preferable that it is 0.05-10 mol/g, and, as for the quantity of ethylenically unsaturated bonds with respect to the total mass of polyimide, it is more preferable that it is 0.1-5 mol/g.

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

-Crosslinkable groups other than ethylenically unsaturated bonds-

The polyimide may have a crosslinkable group other than an ethylenically unsaturated bond.

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

A crosslinkable group other than an ethylenically unsaturated bond is preferably included in R ¹³¹ in the repeating unit represented by formula (4) described below, for example.

It is preferable that it is 0.05-10 mol/g, and, as for the quantity of crosslinkable groups other than an ethylenically unsaturated bond with respect to the total mass of polyimide, it is more preferable that it is 0.1-5 mol/g.

From the viewpoint of production aptitude, the amount of crosslinkable groups other than ethylenically unsaturated bonds relative to the total mass of polyimide is preferably 0.0001 to 0.1 mol/g, and more preferably 0.001 to 0.05 mol/g.

-Polar Transducer-

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

-Acid value-

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

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

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

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

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

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

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

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

-Phenolic hydroxyl group-

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

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

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

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

The polyimide used in the present invention is not particularly limited as long as it is a high molecular compound having an imide ring, but preferably contains a repeating unit represented by the following formula (4), including a repeating unit represented by the formula (4), and polymerization It is more preferable that it is a compound with a sexual group.

Equation (4)

[Formula 18]

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

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

Formula (4-1)

[Formula 19]

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

Formula (4-2)

[Formula 20]

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

The polymerizable group has the same meaning as the polymerizable group described as the polymerizable group possessed by the above polyimide precursor or the like.

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

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

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

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

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

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

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

It is also preferable to have an OH group in at least one of R ¹³¹ and R ¹³² . More specifically, as R ¹³¹ , 2,2-bis(3-hydroxy-4-aminophenyl)propane, 2,2-bis(3-hydroxy-4-aminophenyl)hexafluoropropane, 2,2-bis(3-amino-4-hydroxyphenyl)propane, 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane, the above (DA-1) to ( DA-18) can be cited as a preferable example, and as R ¹³² , the above (DAA-1) to (DAA-5) can be cited as more preferable examples.

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

Moreover, polyimide may copolymerize the aliphatic group which has a siloxane structure for the purpose of improving adhesiveness with a board|substrate. Specifically, as a diamine component, bis (3-aminopropyl) tetramethyldisiloxane, bis (p-aminophenyl) octamethylpentasiloxane, etc. are mentioned.

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

-Imidization rate (closing rate)-

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

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

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

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

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

The polyimide may contain repeating structural units of the above formula (4), all of which contain one kind of R ¹³¹ or R ¹³² , and the above formula (4) containing two or more different kinds of R ¹³¹ or R ¹³² ) may be included. Moreover, a polyimide may also contain other types of repeating structural units other than the repeating unit of said Formula (4).

The polyimide can be obtained, for example, by reacting tetracarboxylic dianhydride and diamine compound (partly substituted with a monoamine terminal blocker) at low temperature, or by reacting tetracarboxylic dianhydride (partly acid anhydride or monoacid chloride compound) at low temperature. or a method of reacting a diamine compound) with a diamine compound, obtaining a diester by tetracarboxylic dianhydride and an alcohol, and then condensing with diamine (partially substituted with a monoamine terminal blocker) A method of reacting in the presence of an agent, a method of obtaining a diester by using tetracarboxylic dianhydride and alcohol, then acid chlorideing the remaining dicarboxylic acid, and reacting with diamine (partially substituted with a monoamine terminal blocker), etc. A method of obtaining a polyimide precursor using the method of, and completely imidating this using a known imidation reaction method, or a method of stopping the imidation reaction in the middle and introducing a part of the imide structure, and furthermore , It can be synthesized using a method of introducing a part of the imide structure by blending a completely imidized polymer and the polyimide precursor.

As a commercial item of polyimide, Durimide (registered trademark) 284 (manufactured by Fujifilm Co., Ltd.) and Matrimide 5218 (manufactured by HUNTSMAN Co., Ltd.) are exemplified.

As for the weight average molecular weight (Mw) of polyimide, 4,000-100,000 are mentioned, 5,000-70,000 are preferable, 8,000-50,000 are more preferable, and 10,000-30,000 are more preferable. By setting the weight average molecular weight to 5,000 or more, the bending resistance of the film after curing can be improved. In order to obtain an organic film excellent in mechanical properties, the weight average molecular weight is particularly preferably 20,000 or more. Moreover, when containing 2 or more types of polyimides, it is preferable that the weight average molecular weight of at least 1 type of polyimide is the said range.

[Polybenzoxazole precursor]

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

Equation (3)

[Formula 21]

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

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

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

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

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

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

[Formula 22]

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

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

[Formula 23]

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

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

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

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

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

[Formula 24]

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

[Formula 25]

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

[Formula 26]

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

In the above formula (As), it is considered that having a substituent at the ortho position of the phenolic hydroxyl group, that is, R ₃ also brings the distance between the carbonyl carbon of the amide bond and the hydroxyl group closer, resulting in a high conversion rate when cured at a low temperature. It is particularly preferable in that the effect is further enhanced.

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

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

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

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

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

It is preferable to contain a diamine residue represented by the following formula (SL) as another type of repeating structural unit from the viewpoint of being able to suppress the occurrence of curvature due to ring closure.

[Formula 27]

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

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

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

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

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

[Polybenzoxazole]

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

[Formula 28]

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

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

Formula (X-1)

[Formula 29]

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

Formula (X-2)

[Formula 30]

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

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

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

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

For example, four bonded groups of a tetravalent organic group exemplified as R ¹²² combine with a nitrogen atom and an oxygen atom in the formula (X) to form a condensed ring. For example, when R ¹³⁴ is the following organic group, the following structure is formed.

[Formula 31]

The polybenzoxazole preferably has an oxazolization rate of 85% or more, more preferably 90% or more. When the oxazolization rate is 85% or more, film shrinkage based on ring closure that occurs during oxazolization by heating is reduced, and generation of warping can be more effectively suppressed.

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

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

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

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

[Method for Producing Polyimide Precursors, etc.]

Polyimide precursors and the like are obtained by reacting dicarboxylic acids or dicarboxylic acid derivatives with diamines. Preferably, it is obtained by halogenating a dicarboxylic acid or a dicarboxylic acid derivative using a halogenating agent and then reacting with diamine.

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

Although it can determine suitably according to a raw material as an organic solvent, pyridine, diethylene glycol dimethyl ether (diglyme), N-methylpyrrolidone, and N-ethylpyrrolidone are illustrated.

Polyimide may be manufactured by synthesizing a polyimide precursor and then cyclizing by a method such as thermal imidation or chemical imidation (for example, accelerating the cyclization reaction by activating a catalyst). may be synthesized.

Moreover, it is also preferable to synthesize|combine using a non-halogen type catalyst, without using the said halogenating agent. As the non-halogen catalyst, it is possible to use a known amidation catalyst that does not contain a halogen atom without particular limitation, but examples thereof include boroxine compounds, N-hydroxy compounds, tertiary amines, phosphate esters, Carbodiimide compounds, such as an amine salt and a urea compound, are mentioned. Examples of the carbodiimide compounds include N,N'-diisopropylcarbodiimide and N,N'-dicyclohexylcarbodiimide.

-end sealant-

In order to further improve the storage stability of the composition during production of the polyimide precursor, it is preferable to seal the end of the polyimide precursor or the like with an end capping agent such as an acid anhydride, a monocarboxylic acid, a monoacid chloride compound, or a monoactive ester compound. desirable. As the end capping agent, it is more preferable to use a monoamine, and as a preferable monoamine compound, aniline, 2-ethynylaniline, 3-ethynylaniline, 4-ethynylaniline, 5-amino-8- Hydroxyquinoline, 1-hydroxy-7-aminonaphthalene, 1-hydroxy-6-aminonaphthalene, 1-hydroxy-5-aminonaphthalene, 1-hydroxy-4-aminonaphthalene, 2-hydroxy-7 -Aminonaphthalene, 2-hydroxy-6-aminonaphthalene, 2-hydroxy-5-aminonaphthalene, 1-carboxy-7-aminonaphthalene, 1-carboxy-6-aminonaphthalene, 1-carboxy-5-aminonaphthalene , 2-carboxy-7-aminonaphthalene, 2-carboxy-6-aminonaphthalene, 2-carboxy-5-aminonaphthalene, 2-aminobenzoic acid, 3-aminobenzoic acid, 4-aminobenzoic acid, 4-aminosalicylic acid, 5- Aminosalicylic acid, 6-aminosalicylic acid, 2-aminobenzenesulfonic acid, 3-aminobenzenesulfonic acid, 4-aminobenzenesulfonic acid, 3-amino-4,6-dihydroxypyrimidine, 2-aminophenol, 3- Aminophenol, 4-aminophenol, 2-aminothiophenol, 3-aminothiophenol, 4-aminothiophenol, 4-aminostyrene, etc. are mentioned. Two or more types of these may be used, and a plurality of different terminal groups may be introduced by reacting a plurality of terminal blocking agents.

-solid precipitation-

In the case of manufacture of a polyimide precursor etc., you may include the process of depositing solid. Specifically, solid precipitation can be achieved by precipitating the polyimide precursor or the like in the reaction solution in water and dissolving the polyimide precursor or the like, such as tetrahydrofuran, in a soluble solvent.

After that, the polyimide precursor or the like can be dried to obtain a powdery polyimide precursor or the like.

〔content〕

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

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

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

Specifically, the curable resin composition of the present invention may contain 2 or more types of specific resin and other resins described later in total, or may contain 2 or more types of specific resin, but containing 2 or more types of specific resin desirable.

When the curable resin composition of the present invention contains two or more types of specific resin, it may be, for example, a polyimide precursor, and two or more types of polyisides having different dianhydride-derived structures (R ¹¹⁵ in the above formula (2)) are different. It is preferable to include a mid precursor.

<Other resins>

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

Examples of other resins include polyamideimide, polyamideimide precursors, phenol resins, polyamides, epoxy resins, polysiloxanes, resins containing a siloxane structure, and acrylic resins.

For example, by further adding an acrylic resin, a composition excellent in applicability is obtained, and an organic film excellent in solvent resistance is obtained.

For example, by adding an acrylic resin having a high polymerizable value of 20,000 or less in weight average molecular weight to the composition in place of the crosslinking agent (also referred to as a polymerizable compound) described later or in addition to the polymerizable compound described later, the coating property of the composition is improved. , the solvent resistance of the organic film can be improved.

When the composition of the present invention contains other resins, the content of the other resins is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, and even more preferably 1% by mass or more, based on the total solid content of the composition. , It is more preferably 2% by mass or more, more preferably 5% by mass or more, and still more preferably 10% by mass or more.

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

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

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

<Compound B>

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

[polymerizable group]

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

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

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

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

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

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

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

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

[azole group]

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

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

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

[Formula 32]

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

[Formula 33]

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

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

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

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

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

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

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

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

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

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

[Formula 34]

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

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

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

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

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

The R ^N is as described above.

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

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

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

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

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

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

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

[Low Molecular Compound B]

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

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

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

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

[Formula 35]

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

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

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

The R ^N is as described above.

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

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

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

[Formula 36]

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

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

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

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

The R ^N is as described above.

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

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

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

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

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

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

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

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

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

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

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

[Resin B]

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

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

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

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

[Formula 37]

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

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

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

The R ^N is as described above.

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

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

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

[Formula 38]

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

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

The R ^N is as described above.

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

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

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

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

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

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

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

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

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

[Formula 39]

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

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

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

The R ^N is as described above.

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

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

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

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

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

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

[specific example]

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

〔content〕

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

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

<Compound C>

It is preferable that the curable resin composition of this invention further contains compound C which is a compound which has an azole group without having a polymerizable group from an adhesive viewpoint with the metal of the cured film obtained.

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

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

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

[Formula 40]

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

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

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

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

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

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

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

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

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

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

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

〔Molecular Weight〕

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

[specific example]

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

〔content〕

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

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

<Compound D>

It is preferable that the curable resin composition of this invention further contains compound D which is a silane coupling agent which has a polymeric group different from an alkoxysilyl group and does not have an azole group.

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

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

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

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

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

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

[Formula 41]

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

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

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

The R ^N is as described above.

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

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

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

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

[Low Molecular Compound D]

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

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

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

[Resin D]

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

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

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

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

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

[specific example]

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

〔content〕

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

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

<Compound E>

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

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

Compound E is a compound having no polymerizable group different from the alkoxysilyl group, but the details of the polymerizable group different from the alkoxysilyl group are synonymous with the polymerizable group different from the alkoxysilyl group in the above-mentioned compound D.

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

As an example of compound E, the compound described in Paragraph 0167 of International Publication No. 2015/199219, the compound described in Paragraphs 0062 to 0073 of Unexamined-Japanese-Patent No. 2014-191002, and the compound described in Paragraphs 0063 to 0071 of International Publication No. 2011/080992 Among the compounds described in Paragraphs 0060 to 0061 of Japanese Laid-Open Patent Publication No. 2014-191252, the compounds described in Paragraphs 0045 to 0052 of Unexamined-Japanese-Patent No. 2014-041264, and the compounds described in Paragraph 0055 of International Publication No. 2014/097594, alkoxysilyl Compounds having neither a polymerizable group nor an azole group different from the group are exemplified. Moreover, it is also preferable to use 2 or more types of silane coupling agents different as Paragraph 0050 of Unexamined-Japanese-Patent No. 2011-128358 - 0058 describe.

Moreover, as compound E, it is also preferable to use the following compound. In the formulas below, Et represents an ethyl group.

[Formula 42]

〔content〕

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

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

<Solvent>

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

As esters, for example, ethyl acetate, n-butyl acetate, isobutyl acetate, hexyl acetate, amyl formate, isoamyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, Ethyl lactate, γ-butyrolactone, ε-caprolactone, δ-valerolactone, alkyloxyacetate (e.g. methyl alkyloxyacetate, ethyl alkyloxyacetate, butyl alkyloxyacetate (e.g. methoxy methyl acetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, etc.), 3-alkyloxypropionate alkyl esters (e.g., 3-alkyloxymethylpropionate, 3-alkyloxy Ethyl propionate and the like (eg, 3-methoxymethylpropionate, 3-methoxyethylpropionate, 3-ethoxymethylpropionate, 3-ethoxyethylpropionate, etc.), 2-alkyloxypropionate alkyl esters (eg For example, 2-alkyloxymethylpropionate, 2-alkyloxyethylpropionate, 2-alkyloxypropylpropionate, etc. (e.g., 2-methoxymethylpropionate, 2-methoxyethylpropionate, 2-methoxypropylpropionate, 2 -methyl ethoxypropionate, ethyl 2-ethoxypropionate)), 2-alkyloxy-2-methylmethylpropionate and 2-alkyloxy-2-methylethylpropionate (e.g. 2-methoxy-2-methylpropionate) methyl, 2-ethoxy-2-methylethylpropionate, etc.), methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutanoate, ethyl 2-oxobutanoate, etc., ethyl hexanoate , ethyl heptanoate, dimethyl malonate and diethyl malonate are mentioned as suitable ones.

As ethers, for example, diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve Acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate , Propylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether, ethylene glycol monobutyl ether acetate, diethylene glycol ethyl methyl ether, propylene glycol monopropyl ether acetate, etc. can be cited as suitable.

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

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

As the sulfoxides, for example, dimethyl sulfoxide can be cited as a suitable one.

As amides, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide, N,N-dimethylisobutyl Amide, 3-methoxy-N,N-dimethylpropionamide, 3-butoxy-N,N-dimethylpropionamide, N-formylmorpholine, N-acetylmorpholine, etc. are mentioned as suitable ones.

Examples of ureas include N,N,N',N'-tetramethylurea, 1,3-dimethyl-2-imidazolidinone, and the like as suitable ones.

As alcohols, methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 1-pentanol, 1-hexanol, benzyl alcohol, ethylene glycol monomethyl ether, 1-methoxy-2- Propanol, 2-ethoxyethanol, diethylene glycol monoethyl ether, diethylene glycol monohexyl ether, triethylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol Colmonomethyl ether, polyethylene glycol monomethyl ether, polypropylene glycol, tetraethylene glycol, ethylene glycol monobutyl ether, ethylene glycol monobenzyl ether, ethylene glycol mono Phenyl ether, methylphenyl carbinol, n-amyl alcohol, methyl amyl alcohol, diacetone alcohol, etc. are mentioned.

As for the solvent, a form in which two or more types are mixed is also preferable from the viewpoint of improving the properties of the coated surface.

In the present invention, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, methyl 3-methoxypropionate, 2-heptane one, cyclohexanone, cyclopentanone, γ-butyrolactone, dimethyl sulfoxide, ethyl carbitol acetate, butyl carbitol acetate, N-methyl-2-pyrrolidone, propylene glycol methyl ether, and 1 type of solvent chosen from propylene glycol methyl ether acetate, or the mixed solvent comprised of 2 or more types is preferable. Combination use of dimethyl sulfoxide and γ-butyrolactone is particularly preferred. Also preferred are combinations of N-methyl-2-pyrrolidone and ethyl lactate, N-methyl-2-pyrrolidone and ethyl lactate, diacetone alcohol and ethyl lactate, and cyclopentanone and γ-butyrolactone.

Among these, the curable resin composition of the present invention preferably contains esters, and more preferably contains a lactone solvent.

The lactone solvent refers to a solvent containing a lactone structure, and examples thereof include γ-butyrolactone, ε-caprolactone, and δ-valerolactone.

The content of the lactone solvent relative to the total mass of the solvent is not particularly limited, but is preferably 30 to 100% by mass, more preferably 40 to 95% by mass, and still more preferably 50 to 90% by mass.

The content of the solvent is preferably an amount such that the total solid concentration of the curable resin composition of the present invention is 5 to 80% by mass, and more preferably 5 to 75% by mass, from the viewpoint of applicability, It is more preferable to set it as 10-70 mass %, and it is still more preferable to set it as 40-70 mass %. What is necessary is just to adjust solvent content according to the desired thickness of a coating film, and a coating method.

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

<Photosensitizer>

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

As the photosensitizer, a photopolymerization initiator is preferable.

[Photoinitiator]

It is preferable that the composition of this invention contains a photoinitiator as a photosensitizer.

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

Moreover, as said radical photopolymerization initiator, the oxime compound mentioned later is preferable.

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

As an optical radical polymerization initiator, a known compound can be used arbitrarily. For example, acylphosphine compounds such as halogenated hydrocarbon derivatives (for example, compounds having a triazine skeleton, compounds having an oxadiazole skeleton, compounds having a trihalomethyl group, etc.) and acylphosphine oxides. , hexaarylbiimidazole, oxime compounds such as oxime derivatives, organic peroxides, thio compounds, ketone compounds, aromatic onium salts, ketoxime ethers, aminoacetophenone compounds, hydroxyacetophenones, azo compounds, azide compounds , metallocene compounds, organic boron compounds, iron arene complexes, and the like. About these details, Paragraph 0165 of Unexamined-Japanese-Patent No. 2016-027357 - 0182 and Paragraph 0138 of International Publication No. 2015/199219 - description of 0151 can be considered into consideration, and this content is integrated in this specification.

As a ketone compound, the compound of Paragraph 0087 of Unexamined-Japanese-Patent No. 2015-087611 is illustrated, for example, This content is integrated in this specification. In commercial products, Kaya Cure DETX (manufactured by Nippon Kayaku Co., Ltd.) is also suitably used.

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

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

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

As an aminoacetophenone system initiator, the compound of Unexamined-Japanese-Patent No. 2009-191179 in which absorption maximum wavelength was matched with wavelength light sources, such as 365 nm or 405 nm, can also be used.

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

As a metallocene compound, IRGACURE-784, IRGACURE-784EG (both BASF Corporation make), etc. are illustrated.

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

As a specific example of an oxime compound, the compound of Unexamined-Japanese-Patent No. 2001-233842, the compound of Unexamined-Japanese-Patent No. 2000-080068, and the compound of Unexamined-Japanese-Patent No. 2006-342166 can be used.

Preferable examples of the oxime compound include compounds having the following structures, 3-benzoyloxyiminobutan-2-one, 3-acetoxyiminobutan-2-one, 3-propionyloxyiminobutan-2-one, 2-acetoxyiminopentan-3-one, 2-acetoxyimino-1-phenylpropan-1-one, 2-benzoyloxyimino-1-phenylpropan-1-one, 3-(4-toluenesulfonyloxy ) iminobutan-2-one, and 2-ethoxycarbonyloxyimino-1-phenylpropan-1-one. In the composition of this invention, it is preferable to use an oxime compound (oxime type photoinitiator) especially as a photoradical polymerization initiator. An oxime-based photopolymerization initiator has a linking group of >C=N-O-C(=O)- in its molecule.

[Formula 43]

Commercially available products include IRGACURE OXE 01, IRGACURE OXE 02, IRGACURE OXE 03, IRGACURE OXE 04 (above, manufactured by BASF), Adeka Optomer N-1919 (manufactured by ADEKA Co., Ltd., an optical radical described in Japanese Laid-Open Patent Publication No. 2012-014052 The polymerization initiator 2) is also suitably used. In addition, TR-PBG-304 (Changzhou Trolly New Electronic Materials Co., Ltd.), Adeka Arcles NCI-831 and Adeka Arcles NCI-930 (Co., Ltd.) ADEKA) can also be used. Also, DFI-091 (manufactured by Daito Chemicals Co., Ltd.) can be used. Moreover, the oxime compound of the following structure can also be used.

[Formula 44]

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

As the photopolymerization initiator, an oxime compound having a skeleton in which at least one benzene ring of a carbazole ring is a naphthalene ring can also be used. As a specific example of such an oxime compound, the compound of international publication 2013/083505 is mentioned.

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

As the most preferable oxime compound, the oxime compound which has a specific substituent shown in Unexamined-Japanese-Patent No. 2007-269779, the oxime compound which has a thioaryl group shown in Unexamined-Japanese-Patent No. 2009-191061, etc. are mentioned.

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

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

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

[Formula 45]

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

[Formula 46]

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

Moreover, as an optical radical polymerization initiator, Paragraph 0048 of International Publication No. 2015/125469 - the compound of 0055 can also be used.

When a photopolymerization initiator is included, the content thereof is preferably 0.1 to 30% by mass, more preferably 0.1 to 20% by mass, still more preferably 0.5 to 15% by mass, based on the total solid content of the composition of the present invention. and more preferably 1.0 to 10% by mass. The photoinitiator may contain only 1 type, and may contain 2 or more types. When containing 2 or more types of photoinitiators, it is preferable that the total amount is the said range.

[mine generator]

Moreover, it is also preferable that the composition of this invention contains a photo-acid generator as a photosensitizer.

By containing a photoacid generator, for example, acid is generated in the exposed portion of the composition layer, the solubility of the exposed portion in the developing solution (eg, aqueous alkali solution) is increased, and the exposed portion is removed by the developing solution. pattern can be obtained.

In addition, when the composition contains a photoacid generator and a polymerizable compound other than a radical polymerizable compound described later, a crosslinking reaction of the polymerizable compound is promoted by an acid generated in the exposed portion, for example, and the exposed portion is exposed to the acid. It can also be set as an aspect in which it is more difficult to be removed by the developer than by the miner. According to such an aspect, a negative pattern can be obtained.

The photoacid generator is not particularly limited as long as it generates an acid by exposure, but onium salt compounds such as quinonediazide compounds, diazonium salts, phosphonium salts, sulfonium salts and iodonium salts, imide sulfonates, oximes and sulfonate compounds such as sulfonate, diazodisulfone, disulfone, and o-nitrobenzylsulfonate.

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

In the present invention, both 5-naphthoquinonediazide sulfonyl group and 4-naphthoquinonediazide sulfonyl group are preferably used as quinonediazide. The 4-naphthoquinone diazide sulfonyl ester compound has absorption in the i-line region of a mercury lamp, and is suitable for i-line exposure. The 5-naphthoquinone diazide sulfonyl ester compound has absorption extending to the g-line region of a mercury lamp, and is suitable for g-line exposure. In this invention, it is preferable to select a 4-naphthoquinone diazide sulfonyl ester compound and a 5-naphthoquinone diazide sulfonyl ester compound according to the exposure wavelength. Alternatively, a naphthoquinonediazidesulfonyl ester compound having a 4-naphthoquinonediazidesulfonyl group or a 5-naphthoquinonediazidesulfonyl group may be contained in the same molecule, and 4-naphthoquinonediazidesulfonylester You may contain a compound and a 5-naphthoquinone diazide sulfonyl ester compound.

The naphthoquinonediazide compound can be synthesized by an esterification reaction between a compound having a phenolic hydroxyl group and a quinonediazide sulfonic acid compound, and can be synthesized by a known method. By using these naphthoquinone diazide compounds, the resolution, sensitivity, and remaining film rate are further improved.

Examples of the naphthoquinonediazide compound include 1,2-naphthoquinone-2-diazide-5-sulfonic acid or 1,2-naphthoquinone-2-diazide-4-sulfonic acid, these A salt or ester compound of a compound, etc. are mentioned.

As an onium salt compound or a sulfonate compound, Paragraph 0064 of Unexamined-Japanese-Patent No. 2008-013646 - the compound of 0122, etc. are mentioned.

It is also preferable that the photoacid generator is a compound containing an oxime sulfonate group (hereinafter, simply referred to as "oxime sulfonate compound").

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

[Formula 47]

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

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

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

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

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

[Formula 48]

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

In formulas (OS-103) to (OS-105), an alkyl group (preferably 1 to 30 carbon atoms), an aryl group (preferably 6 to 30 carbon atoms), or a heteroaryl group (preferably 4 to 30 carbon atoms) represented by R ^s1 This is preferable) may have a substituent T.

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

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

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

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

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

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

[Formula 49]

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

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

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

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

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

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

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

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

[Formula 50]

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

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

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

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

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

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

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

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

In addition, you may use a commercial item as a photo-acid generator. As commercial products, WPAG-145, WPAG-149, WPAG-170, WPAG-199, WPAG-336, WPAG-367, WPAG-370, WPAG-443, WPAG-469, WPAG-638, WPAG-699 (all Fujifilm Wako Junyaku Co., Ltd.), Omnicat 250, Omnicat 270 (all made by IGM Resins B.V.), Irgacure 250, Irgacure 270, Irgacure 290 (all made by BASF), MBZ-101 (made by Midori Chemical Co., Ltd.), etc. can be heard

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

[Formula 51]

As a photoacid generator, an organic halogenated compound can also be applied. Specifically, as an organic halogenated compound, Wakabayashi et al. "Bull Chem. Soc Japan" 42, 2924 (1969), US Patent Publication No. 3,905,815 Specification, Japanese Patent Publication No. 46-4605, Japanese Unexamined Patent Publication Japanese Laid-Open Patent Publication No. 48-36281, Japanese Laid-Open Patent Publication 55-32070, Japanese Laid-Open Patent Publication 60-239736, Japanese Laid-Open Patent Publication 61-169835, Japanese Laid-Open Patent Publication 61-169837, Japanese Laid-Open Patent Publication 62-58241, Japanese Laid-Open Patent Publication 62-212401, 63-70243, 63-298339, M. P. Hutt "Jurnal of Heterocyclic Chemistry" 1 (No3), ( 1970) and the like, and in particular, an oxazole compound in which a trihalomethyl group is substituted: an S-triazine compound.

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

As a photoacid generator, organic borate compounds are also applicable. As an organic borate compound, Unexamined-Japanese-Patent No. 62-143044, Unexamined-Japanese-Patent No. 62-150242, Unexamined-Japanese-Patent No. 9-188685, Unexamined-Japanese-Patent No. 9-188686, Japan, for example Japanese Patent Laid-open No. 9-188710, Japanese Laid-open Patent No. 2000-131837, Japanese Laid-Open Patent No. 2002-107916, Japanese Patent No. 2764769, Japanese Patent Application No. 2000-310808, and Kunz, Martin Organic borates described in "Rad Tech '98. Proceeding April 19-22, 1998, Chicago", etc., Japanese Unexamined Patent Publication No. Hei 6-157623, Japanese Unexamined Patent Publication No. Hei 6-175564, Japanese Unexamined Patent Publication No. Hei 6-175561 The organic boron sulfonium complex or organoboron oxo sulfonium complex described in Japanese Patent Laid-Open No. 6-175554, the organoboron iodonium complex described in Japanese Unexamined Patent Publication No. Hei 6-175553, Japanese Patent Laid-Open No. Hei 9 Organoboron phosphonium complexes described in No. -188710, Japanese Unexamined Patent Publication No. 6-348011, Japanese Unexamined Patent Publication No. Hei 7-128785, Japanese Unexamined Patent Publication No. Hei 7-140589, Japanese Unexamined Patent Publication No. Hei 7-306527 , organoboron transition metal coordination complexes, such as Japanese Unexamined Patent Publication No. 7-292014, etc. are mentioned as a specific example.

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

As the onium salt compound, for example, S. I. Schlesinger, Photogr. Sci. Eng., 18,387 (1974), T. S. Bal et al, Polymer, 21,423 (1980) diazonium salts, US Patent Publication No. 4,069,055, ammonium salts described in Japanese Unexamined Patent Publication No. Hei 4-365049, US Patent Publication No. 4,069,055 and 4,069,056 phosphonium salts, European Patent No. 104,143, US Patent No. 339,049 and 410,201, Japanese Unexamined Patent Publication No. 2-150848, Japanese Unexamined Patent Publication No. Hei Iodonium salts described in 2-296514, European Patent Nos. 370,693, 390,214, 233,567, 297,443, 297,442, US Patent Nos. 4,933,377, 161,811, 410,201, 339,049 J. V. Crivello et al, Macromolecules, 10(6), 1307 (1977) ), J. V. Crivello et al, J. Polymer Sci., Polymer Chem. Ed., 17, 1047 (1979) selenium salts, C. S. Wen et al, Teh, Proc. Conf. Rad. and onium salts such as arsonium salts and pyridinium salts described in Curing ASIA, p478 Tokyo, Oct (1988).

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

[Formula 52]

In formula (RI-I), Ar11 represents an aryl group having 20 or less carbon atoms which may have 1 to 6 substituents, and preferred substituents include an alkyl group of 1 to 12 carbon atoms, an alkenyl group of 1 to 12 carbon atoms, and an alkane group of 1 to 12 carbon atoms. Phosphorus group, aryl group of 1 to 12 carbon atoms, alkoxy group of 1 to 12 carbon atoms, aryloxy group of 1 to 12 carbon atoms, halogen atom, alkylamino group of 1 to 12 carbon atoms, dialkylamino group of 1 to 12 carbon atoms, and an alkylamide group of 1 to 12, an arylamide group, a carbonyl group, a carboxyl group, a cyano group, a sulfonyl group, a thioalkyl group of 1 to 12 carbon atoms, and a thioaryl group of 1 to 12 carbon atoms. Z11 ^- represents a monovalent anion, and is a halogen ion, a perchlorate ion, a hexafluorophosphate ion, a tetrafluoroborate ion, a sulfonate ion, a sulfinate ion, a thiosulfonate ion, a sulfate ion, and in terms of stability, perchloric acid ions, hexafluorophosphate ions, tetrafluoroborate ions, sulfonic acid ions, and sulfinic acid ions are preferred. In formula (RI-II), Ar21 and Ar22 each independently represent an aryl group having 20 or less carbon atoms which may have 1 to 6 substituents, and preferred substituents include an alkyl group of 1 to 12 carbon atoms, an alkenyl group of 1 to 12 carbon atoms, and Alkynyl group of 1 to 12 carbon atoms, aryl group of 1 to 12 carbon atoms, alkoxy group of 1 to 12 carbon atoms, aryloxy group of 1 to 12 carbon atoms, halogen atom, alkylamino group of 1 to 12 carbon atoms, A dialkylamino group, an alkylamide group or arylamide group having 1 to 12 carbon atoms, a carbonyl group, a carboxyl group, a cyano group, a sulfonyl group, a thioalkyl group having 1 to 12 carbon atoms, or a thioaryl group having 1 to 12 carbon atoms. there is. Z21 ^- represents a monovalent anion, and is a halogen ion, a perchlorate ion, a hexafluorophosphate ion, a tetrafluoroborate ion, a sulfonate ion, a sulfinate ion, a thiosulfonate ion, a sulfate ion, and stability and reactivity In , perchlorate ion, hexafluorophosphate ion, tetrafluoroborate ion, sulfonic acid ion, sulfinic acid ion, and carboxylic acid ion are preferred. In formula (RI-III), R31, R32 and R33 each independently represent an aryl group or an alkyl group having 20 or less carbon atoms, which may have 1 to 6 substituents, an alkenyl group, or an alkynyl group, and is preferably reactive and stable. In terms of aspect, it is preferable that it is an aryl group. Preferred substituents include an alkyl group of 1 to 12 carbon atoms, an alkenyl group of 1 to 12 carbon atoms, an alkynyl group of 1 to 12 carbon atoms, an aryl group of 1 to 12 carbon atoms, an alkoxy group of 1 to 12 carbon atoms, and an aryloxy group of 1 to 12 carbon atoms. Group, halogen atom, C1-12 alkylamino group, C1-12 dialkylamino group, C1-12 alkylamide or arylamide group, carbonyl group, carboxyl group, cyano group, sulfonyl group, carbon number A thioalkyl group of 1-12 and a thioaryl group of 1-12 carbon atoms are mentioned. Z31 ^- represents a monovalent anion and is a halogen ion, a perchlorate ion, a hexafluorophosphate ion, a tetrafluoroborate ion, a sulfonate ion, a sulfinate ion, a thiosulfonate ion, a sulfate ion, and stability and reactivity In , perchlorate ion, hexafluorophosphate ion, tetrafluoroborate ion, sulfonic acid ion, sulfinic acid ion, and carboxylic acid ion are preferred.

As a specific example, the following are mentioned.

[Formula 53]

[Formula 54]

[Formula 55]

[Formula 56]

When a photoacid generator is included, the content thereof is preferably 0.1 to 30% by mass, more preferably 0.1 to 20% by mass, and still more preferably 2 to 15% by mass, based on the total solid content of the composition of the present invention. desirable. A photoacid generator may contain only 1 type, and may contain 2 or more types. When two or more types of photoacid generators are contained, it is preferable that the total is within the above range.

[photobase generator]

Curable resin composition of this invention may also contain a photobase generator as a photosensitizer.

When the curable resin composition contains a photobase generator and a crosslinking agent to be described later, for example, cyclization of a specific resin is promoted by a base generated in an exposed area or a crosslinking reaction of a crosslinking agent is promoted. It is also possible to make the exposed portion more difficult to remove with the developing solution than the non-exposed portion. According to such an aspect, a negative relief pattern can be obtained.

The photobase generator is not particularly limited as long as it generates a base by exposure, and a known one can be used.

For example, M. Shirai, and M. Tsunooka, Prog. Polym. Sci., 21, 1 (1996); Masahiro Tsunooka, Polymer Processing, 46, 2 (1997); C. Kutal, Coord. Chem. Rev., 211, 353 (2001); Y. Kaneko, A. Sarker, and D. Neckers, Chem. Mater., 11, 170 (1999); H. Tachi, M. Shirai, and M. Tsunooka, J. Photopolym. Sci. Technol., 13, 153 (2000); M. Winkle, and K. Graziano, J. Photopolym. Sci. Technol., 3, 419 (1990); M. Tsunooka, H. Tachi, and S. Yoshitaka, J. Photopolym. Sci. Technol., 9, 13 (1996); K. Suyama, H. Araki, M. Shirai, J. Photopolym. Sci. As described in Technol., 19, 81 (2006), a transition metal compound complex, one having a structure such as an ammonium salt, or an amidine moiety that is latent by forming a salt with a carboxylic acid, a basic component forms a salt. An ionic compound neutralized by formation and a nonionic compound in which a basic component is latent by urethane bonds or oxime bonds such as carbamate derivatives, oxime ester derivatives, and acyl compounds are exemplified.

In the present invention, more preferable examples of the photobase generator include carbamate derivatives, amide derivatives, imide derivatives, α-cobalt complexes, imidazole derivatives, cinnamic acid amide derivatives, and oxime derivatives.

The basic substance generated from the photobase generator is not particularly limited, but includes compounds having an amino group, particularly polyamines such as monoamines and diamines, and amidines.

From the viewpoint of the imidation rate, it is preferable that the basic substance has a large pKa in DMSO (dimethyl sulfoxide) as a conjugate acid. As for the said pKa, it is preferable that it is 1 or more, and it is more preferable that it is 3 or more. Although the upper limit of the said pKa is not specifically limited, It is preferable that it is 20 or less.

Here, the pKa represents the logarithm of the reciprocal of the first dissociation constant of an acid, Determination of Organic Structures by Physical Methods (author: Brown, H. C., McDaniel, D. H., Hafliger, O., Nachod, F. C.; Compilation: Braude , E. A., Nachod, F. C.; Academic Press, New York, 1955) or Data for Biochemical Research (authors: Dawson, R.M.C. et al; Oxford, Clarendon Press, 1959). For compounds not described in these literatures, the value calculated from the structural formula using ACD/pKa (manufactured by ACD/Labs) software is used as pKa.

From the viewpoint of the storage stability of the curable resin composition, the photobase generator is preferably a photobase generator that does not contain a salt in the structure, and a photobase generator that does not have an electric charge on the nitrogen atom of the base moiety generated in the photobase generator desirable. As the photobase generator, it is preferable that the base to be generated is latent using a covalent bond, and the mechanism for generating the base is that the covalent bond between the nitrogen atom and the adjacent atom of the base part to be generated is cleaved to form a base. It is desirable that it occurs. Since the photobase generator can be made neutral if it is a photobase generator which does not contain a salt in a structure, solvent solubility is more favorable and a pot life improves. For this reason, the amine generated from the photobase generator used in the present invention is preferably a primary amine or a secondary amine.

Moreover, from a viewpoint of the chemical-resistance of a pattern, as a photobase generator, it is preferable that it is a photobase generator containing a salt in a structure.

In addition, for the above reason, as a photobase generator, it is preferable that the base generated as described above is latent using a covalent bond, and the generated base uses an amide bond, a carbamate bond, or an oxime bond. It is desirable to be latent.

As the photobase generator according to the present invention, for example, a photobase generator having a cinnamic acid amide structure as disclosed in Japanese Unexamined Patent Publication No. 2009-080452 and International Publication No. 2009/123122, Japanese Unexamined Patent Publication 2006 Photobase generators having a carbamate structure as disclosed in Japanese Patent Application Laid-Open No. 2008-247747 and oxime structure as disclosed in Japanese Patent Laid-Open No. 2007-249013 and Japanese Laid-Open Patent Publication No. 2008-003581 Although the photobase generator etc. which have an oxime structure are mentioned, It is not limited to these, In addition, the structure of a well-known photobase generator can be used.

In addition, as a photobase generator, the compound of Paragraph No. 0185-0188, 0199-0200, and 0202 of Unexamined-Japanese-Patent No. 2012-093746, the compound of Paragraph No. 0022-0069 of Unexamined-Japanese-Patent No. 2013-194205, Japan The compound of Paragraph No. 0026 of Unexamined-Japanese-Patent No. 2013-204019 - 0074, and the compound of Paragraph No. 0052 of International Publication No. 2010/064631 are mentioned as an example.

In addition, you may use a commercial item as a photobase generator. As commercial products, WPBG-266, WPBG-300, WPGB-345, WPGB-140, WPBG-165, WPBG-027, WPBG-018, WPGB-015, WPBG-041, WPGB-172, WPGB-174, WPBG-166 , WPGB-158, WPGB-025, WPGB-168, WPGB-167, WPBG-082 (all manufactured by Fujifilm Wako Junyaku Co., Ltd.), A2502, B5085, N0528, N1052, O0396, O0447, O0448 (Tokyo Kasei High School) Co., Ltd.) and the like.

When a photobase generator is included, the content thereof is preferably 0.1 to 30% by mass, more preferably 0.1 to 20% by mass, and 2 to 15% by mass, based on the total solid content of the curable resin composition of the present invention. It is more preferable to be The photobase generator may contain only 1 type, or may contain 2 or more types. When 2 or more types of photobase generators are contained, it is preferable that the sum total is the said range.

<Thermal polymerization initiator>

The composition of the present invention may contain a thermal polymerization initiator, and particularly may contain a thermal radical polymerization initiator. A thermal radical polymerization initiator is a compound that generates radicals by thermal energy to initiate or accelerate a polymerization reaction of a polymerizable compound. Since the polymerization reaction of resin and a polymeric compound can also advance in the heating process mentioned later by adding a thermal radical polymerization initiator, solvent resistance can be improved more.

As a thermal radical polymerization initiator, specifically, the compound described in Paragraph 0074 of Unexamined-Japanese-Patent No. 2008-063554 - 0118 is mentioned.

When a thermal polymerization initiator is included, the content thereof is preferably 0.1 to 30% by mass, more preferably 0.1 to 20% by mass, and even more preferably 5 to 15% by mass based on the total solid content of the composition of the present invention. %to be. The thermal polymerization initiator may contain only 1 type, and may contain 2 or more types. When containing 2 or more types of thermal polymerization initiators, it is preferable that the total amount is the said range.

<Thermal acid generator>

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

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

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

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

As a device used when measuring the thermal decomposition start temperature, Q2000 (manufactured by TA Instruments) and the like are exemplified.

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

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

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

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

<Onium Salt>

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

In particular, when the curable resin composition of the present invention contains a polyimide precursor or a polybenzoxazole precursor as a specific resin, it is preferable to contain an onium salt.

Although the type of onium salt is not particularly determined, ammonium salts, iminium salts, sulfonium salts, iodonium salts, or phosphonium salts are preferred.

Among these, an ammonium salt or an iminium salt is preferable from a viewpoint of high thermal stability, and a sulfonium salt, an iodonium salt, or a phosphonium salt is preferable from a compatibility viewpoint with a polymer.

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

That is, the onium salt may be an intramolecular salt having a cation moiety and an anion moiety in the same molecular structure, or may be an intermolecular salt in which a cation molecule and an anion molecule, which are separate molecules, are ionically bonded, but an intermolecular salt is preferable. Further, in the curable resin composition of the present invention, the cation moiety or cation molecule and the anion moiety or anion molecule may be bonded by ionic bonding or may be dissociated.

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

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

A thermal base generator refers to a compound that generates a base when heated, and includes, for example, a compound that generates a base when heated to 40°C or higher.

As an onium salt, Paragraph 0122 of International Publication No. 2018/043262 - the onium salt of 0138, etc. are mentioned, for example. In addition, it is possible to use onium salts used in the field of polyimide precursors without particular limitation.

When the curable resin composition of the present invention contains an onium salt, the content of the onium salt is preferably 0.1 to 50% by mass with respect to the total solid content of the curable resin composition of the present invention. The lower limit is more preferably 0.5% by mass or more, more preferably 0.85% by mass or more, and still more preferably 1% by mass or more. The upper limit is more preferably 30% by mass or less, more preferably 20% by mass or less, still more preferably 10% by mass or less, and may be 5% by mass or less, or may be 4% by mass or less.

1 type or 2 or more types can be used for an onium salt. When using 2 or more types, it is preferable that the total amount is the said range.

<thermal base generator>

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

In particular, when the curable resin composition of the present invention contains a polyimide precursor or a polybenzoxazole precursor as a specific resin, it is preferable to include a heat base generator.

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

Examples of thermal base generators other than the onium salts described above include nonionic thermal base generators.

As a nonionic heat base generator, the compound represented by Formula (B1) or Formula (B2) is mentioned.

[Formula 57]

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

In formulas (B1) and (B2), as for Rb ¹ , Rb ² and Rb ³ , it is preferable that at least one of these includes a cyclic structure, and it is more preferable that at least two of these include a cyclic structure. As the cyclic structure, either a monocycle or a condensed ring may be used, and a monocycle or a condensed ring in which two monocycles are condensed is preferable. A 5-membered ring or a 6-membered ring is preferable, and, as for a monocyclic ring, a 6-membered ring is preferable. As for a monocyclic ring, a cyclohexane ring and a benzene ring are preferable, and a cyclohexane ring is more preferable.

More specifically, Rb ¹ and Rb ² are a hydrogen atom, an alkyl group (preferably 1 to 24 carbon atoms, more preferably 2 to 18 carbon atoms, still more preferably 3 to 12 carbon atoms), an alkenyl group (preferably 2 to 24 carbon atoms, , 2 to 18 are more preferred, 3 to 12 are more preferred), an aryl group (6 to 22 carbon atoms are preferred, 6 to 18 are more preferred, and 6 to 10 are more preferred), or an arylalkyl group ( It is preferably 7 to 25 carbon atoms, more preferably 7 to 19, more preferably 7 to 12). These groups may have a substituent within the range of exhibiting the effect of the present invention. Rb ¹ and Rb ² may be bonded to each other to form a ring. As the ring formed, a 4- to 7-membered nitrogen-containing heterocycle is preferable. Rb ¹ and Rb ² are particularly preferably a straight-chain, branched, or cyclic alkyl group which may have a substituent (preferably 1 to 24 carbon atoms, more preferably 2 to 18, and even more preferably 3 to 12). , It is more preferably a cycloalkyl group (preferably 3 to 24 carbon atoms, more preferably 3 to 18, and still more preferably 3 to 12) which may have a substituent, and a cyclohexyl group that may have a substituent is more preferable Do.

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

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

[Formula 58]

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

Rb ¹³ is an alkyl group (preferably 1 to 24 carbon atoms, more preferably 2 to 18 carbon atoms, and still more preferably 3 to 12 carbon atoms), an alkenyl group (preferably 2 to 24 carbon atoms, more preferably 2 to 18 carbon atoms, and 3 -12 is more preferable), aryl group (C6-22 is preferable, 6-18 are more preferable, 6-12 are still more preferable), arylalkyl group (C7-23 is preferable, 7-19 is more preferable, and 7 to 12 are more preferable), and may have a substituent within the range showing the effect of the present invention. Among them, Rb ¹³ is preferably an arylalkyl group.

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

Rb ³⁵ is an alkyl group (preferably 1 to 24 carbon atoms, more preferably 1 to 12, more preferably 3 to 8 carbon atoms), an alkenyl group (preferably 2 to 12 carbon atoms, more preferably 2 to 10 carbon atoms, 3-8 are more preferable), aryl group (C6-22 are preferable, 6-18 are more preferable, 6-12 are more preferable), arylalkyl group (C7-23 are preferable, 7-18 are more preferable) 19 is more preferable, and 7 to 12 are more preferable), and an aryl group is preferable.

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

[Formula 59]

Rb ¹¹ and Rb ^{12 have the same meaning as Rb 11 and Rb 12 in Formula} (B1-1).

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

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

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

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

[Formula 60]

[Formula 61]

[Formula 62]

The content of the other heat base generator is preferably 0.1 to 50% by mass with respect to the total solid content of the curable resin composition of the present invention. The lower limit is more preferably 0.5% by mass or more, and more preferably 1% by mass or more. As for an upper limit, 30 mass % or less is more preferable, and 20 mass % or less is still more preferable. 1 type or 2 or more types can be used for a heat base generator. When using 2 or more types, it is preferable that the total amount is the said range.

<Crosslinking agent>

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

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

<Radical crosslinking agent>

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

A radical crosslinking agent is a compound having a radical polymerizable group. As the radical polymerizable group, a group containing an ethylenically unsaturated bond is preferable. As a group containing the said ethylenically unsaturated bond, group which has an ethylenically unsaturated bond, such as a vinyl group, an allyl group, a vinylphenyl group, and a (meth)acryloyl group, is mentioned.

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

The radical crosslinking agent may be a compound having one or more ethylenically unsaturated bonds, but more preferably a compound having two or more.

It is preferable that the compound which has two ethylenically unsaturated bonds is a compound which has two groups containing the said ethylenically unsaturated bond.

Moreover, from a viewpoint of the film|membrane strength of the pattern (cured film) obtained, it is preferable that the curable resin composition of this invention contains the compound which has 3 or more ethylenically unsaturated bonds as a radical crosslinking agent. As the compound having 3 or more ethylenically unsaturated bonds, compounds having 3 to 15 ethylenically unsaturated bonds are preferable, compounds having 3 to 10 ethylenically unsaturated bonds are more preferable, and compounds having 3 to 6 this is more preferable

In addition, the compound having 3 or more ethylenically unsaturated bonds is preferably a compound having 3 or more groups containing the ethylenically unsaturated bonds, more preferably a compound having 3 to 15, and 3 to 10 It is more preferable that it is a compound having, and it is particularly preferable that it is a compound having 3 to 6.

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

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

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

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

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

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

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

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

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

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

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

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

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

A preferable acid value of the radical crosslinking agent having an acid group is 0.1 to 40 mgKOH/g, and particularly preferably 5 to 30 mgKOH/g. When the acid value of the radical crosslinking agent is in the above range, the handleability in production is excellent, and furthermore, the developability is excellent. Moreover, polymerizability is good. On the other hand, from the viewpoint of the development rate in the case of alkaline development, the radical crosslinking agent having an acid group has a preferable acid value of 0.1 to 300 mgKOH/g, particularly preferably 1 to 100 mgKOH/g. The said acid value is measured based on description of JISK0070:1992.

In the curable resin composition of the present invention, it is preferable to use a bifunctional methacrylate or acrylate from the viewpoint of pattern resolution and film stretchability. Specific compounds include triethylene glycol diacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, tetraethylene glycol diacrylate, PEG200 diacrylate, and PEG200 dimethacrylate. Acrylate, PEG600 Diacrylate, PEG600 Dimethacrylate, Polytetraethylene Glycol Diacrylate, Polytetraethylene Glycol Dimethacrylate, Neopentyl Glycol Diacrylate, Neopentyl Glycol Diacrylate Methacrylate, 3-methyl-1,5-pentanedioldiacrylate, 1,6-hexanedioldiacrylate, 1,6-hexanedioldimethacrylate, dimethylol-tri Cyclodecane diacrylate, dimethylol-tricyclodecane dimethacrylate, EO adduct diacrylate of bisphenol A, EO adduct dimethacrylate of bisphenol A, PO adduct diacrylate of bisphenol A , PO adduct dimethacrylate of bisphenol A, 2-hydroxy-3-acryloyloxypropyl methacrylate, isocyanuric acid EO modified diacrylate, isocyanuric acid modified dimethacrylate, In addition, bifunctional acrylate having a urethane bond and bifunctional methacrylate having a urethane bond can be used. These can mix and use 2 or more types as needed.

Moreover, as a radical crosslinking agent, a monofunctional radical crosslinking agent can be preferably used from a viewpoint of curvature suppression by control of the modulus of elasticity of a pattern (cured film). As a monofunctional radical crosslinking agent, n-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, butoxyethyl (meth) acrylate, carbitol (meth) Acrylate, cyclohexyl (meth)acrylate, benzyl (meth)acrylate, phenoxyethyl (meth)acrylate, N-methylol (meth)acrylamide, glycidyl (meth)acrylate, polyethylene glycol (meth)acrylic acid derivatives such as mono(meth)acrylate and polypropylene glycol mono(meth)acrylate, N-vinyl compounds such as N-vinylpyrrolidone and N-vinylcaprolactam, allylglycidyl Allyl compounds, such as ether, diallyl phthalate, and triallyl trimellitate, etc. are used preferably. As the monofunctional radical crosslinking agent, in order to suppress volatilization before exposure, a compound having a boiling point of 100°C or higher under normal pressure is also preferable.

When containing a radical crosslinking agent, it is preferable that the content is more than 0 mass % and 60 mass % or less with respect to the total solids of curable resin composition of this invention. As for a lower limit, 5 mass % or more is more preferable. As for an upper limit, it is more preferable that it is 50 mass % or less, and it is still more preferable that it is 30 mass % or less.

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

<Other crosslinking agents>

Curable resin composition of this invention also preferably contains another crosslinking agent different from the radical crosslinking agent mentioned above.

In the present invention, the other crosslinking agent refers to a crosslinking agent other than the above-mentioned radical crosslinking agent, and a group that promotes a reaction of forming a covalent bond between other compounds in the composition or a reaction product thereof by photosensitization of the above-mentioned photosensitizer is a molecule. A compound having a plurality of groups within the molecule is preferable, and a compound having a plurality of groups in the molecule in which a reaction for forming a covalent bond with other compounds in the composition or reaction products thereof is promoted by the action of an acid or base is preferable.

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

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

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

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

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

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

Specific examples of the urea-based crosslinking agent include monohydroxymethylation glycoluril, dihydroxymethylation glycoluril, trihydroxymethylation glycoluril, tetrahydroxymethylation glycoluril, and monomethoxymethylation. Glycoluril, dimethoxymethylated glycoluril, trimethoxymethylated glycoluril, tetramethoxymethylated glycoluril, monomethoxymethylated glycoluril, dimethoxymethylated glycoluril, Trimethoxymethylated Glycoluril, Tetraethoxymethylated Glycoluril, Monopropoxymethylated Glycoluril, Dipropoxymethylated Glycoluril, Tripropoxymethylated Glycoluril, Tetrapropoxymethylated Glycoluril glycoluril type crosslinking agents such as lycoluril, monobutoxymethylation glycoluril, dibutoxymethylation glycoluril, tributoxymethylation glycoluril, or tetrabutoxymethylation glycoluril;

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

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

monohydroxymethylated propylene urea, dihydroxymethylated propylene urea, monomethoxymethylated propylene urea, dimethoxymethylated propylene urea, monodiethoxymethylated propylene urea, diethoxymethylated propylene urea, monopropoxymethylated propylene urea, propylene urea-based crosslinking agents such as dipropoxymethylated propylene urea, monobutoxymethylated propylene urea, or dibutoxymethylated propylene urea;

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

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

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

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

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

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

[Epoxy compound (compound having an epoxy group)]

As an epoxy compound, it is preferable that it is a compound which has 2 or more epoxy groups in 1 molecule. The epoxy group undergoes a crosslinking reaction at 200°C or less, and since the dehydration reaction resulting from the crosslinking does not occur, film shrinkage is unlikely to occur. For this reason, containing an epoxy compound is effective for low-temperature curing of curable resin composition and suppression of curvature.

It is preferable that the epoxy compound contains a polyethylene oxide group. Thereby, the modulus of elasticity is lowered and the warpage can be suppressed. A polyethylene oxide group means that the number of repeating units of ethylene oxide is 2 or more, and it is preferable that the number of repeating units is 2-15.

As an example of an epoxy compound, it is bisphenol-A epoxy resin; bisphenol F-type epoxy resin; Propylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, ethylene glycol diglycidyl ether, butylene glycol diglycidyl ether, hexamethylene glycol alkylene glycol type epoxy resins or polyhydric alcohol hydrocarbon type epoxy resins such as diglycidyl ether and trimethylolpropane triglycidyl ether; polyalkylene glycol type epoxy resins such as polypropylene glycol diglycidyl ether; Epoxy group-containing silicones, such as polymethyl (glycidyloxypropyl) siloxane, etc. are mentioned, but are not limited to these. Specifically, Epiclon (registered trademark) 850-S, Epiclon (registered trademark) HP-4032, Epiclon (registered trademark) HP-7200, Epiclon (registered trademark) HP-820, Epiclon (registered trademark) HP-4700, Epiclon (registered trademark) EXA-4710, Epiclon (registered trademark) HP-4770, Epiclon (registered trademark) EXA-859CRP, Epiclon (registered trademark) EXA-1514, Epiclon (registered trademark) EXA-4880, Epiclon (registered trademark) EXA-4850-150, Epiclon (registered trademark) EXA-4850-1000, Epiclon (registered trademark) EXA-4816, Epiclon (registered trademark) EXA-4822, Epiclon (registered trademark) EXA-830LVP, Epiclon (registered trademark) EXA-8183, Epiclon (registered trademark) EXA-8169, Epiclon (registered trademark) N-660, Epiclon (registered trademark) N-665-EXP-S, Epiclon (registered trademark) (registered trademark) N-740, Rika Resin (registered trademark) BEO-20E (above product names, manufactured by DIC Co., Ltd.), Rika Resin (registered trademark) BEO-60E, Rika Resin (registered trademark) HBE-100, Rika Resin (registered trademark) DME-100, Rika Resin (registered trademark) L-200 (trade name, New Nippon Rica Co., Ltd.), EP-4003S, EP-4000S, EP-4088S, EP-3950S (above product names, Co., Ltd.) ADEKA), Celloxide 2021P, 2081, 2000, 3000, EHPE3150, Epolide GT400, Cellvenus B0134, B0177 (above trade names, manufactured by Daicel Co., Ltd.), NC-3000, NC-3000-L, NC-3000 -H, NC-3000-FH-75M, NC-3100, CER-3000-L, NC-2000-L, XD-1000, NC-7000L, NC-7300L, EPPN-501H, EPPN-501HY, EPPN-502H , EOCN-1020, EOCN-102S, EOCN-103S, EOCN-104S, CER-1020, EPPN-201, BREN-S, BREN-10S (above brand name, Nippon Kayaku Co., Ltd. product), etc. are mentioned.

[Oxetane compound (compound having an oxetanyl group)]

As the oxetane compound, a compound having two or more oxetane rings in one molecule, 3-ethyl-3-hydroxymethyloxetane, 1,4-bis{[(3-ethyl-3-oxetanyl)methoxy ]methyl}benzene, 3-ethyl-3-(2-ethylhexylmethyl)oxetane, 1,4-benzenedicarboxylic acid-bis[(3-ethyl-3-oxetanyl)methyl] ester, and the like. . As a specific example, Aronoxetane series (for example, OXT-121, OXT-221, OXT-191, OXT-223) manufactured by Toagosei Co., Ltd. can be suitably used, and these can be used singly or in combination of two or more. You may mix.

[benzoxazine compound (compound having a benzoxazolyl group)]

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

Preferred examples of the benzoxazine compound include B-a-type benzoxazine, B-m-type benzoxazine, P-d-type benzoxazine, F-a-type benzoxazine (above, trade name, manufactured by Shikoku Kasei Kogyo Co., Ltd.), and polyhydroxystyrene resin benzene. oxazine adducts and phenol novolak-type dihydrobenzoxazine compounds. These may be used independently or may mix 2 or more types.

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

<Compound having a sulfonamide structure, compound having a thiourea structure>

From the viewpoint of improving the adhesion of the obtained pattern (cured film) to the substrate, the curable resin composition of the present invention contains at least one compound selected from the group consisting of a compound having a sulfonamide structure and a compound having a thiourea structure. It is preferable to include more.

[Compound having a sulfonamide structure]

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

[Formula 63]

In formula (S-1), R represents a hydrogen atom or an organic group, R may combine with another structure to form a ring structure, and * each independently represents a bonding site with another structure.

It is preferable that said R is the same group as R2 in the following formula (S- ² ).

The compound having a sulfonamide structure may be a compound having two or more sulfonamide structures, but is preferably a compound having one sulfonamide structure.

It is preferable that the compound which has a sulfonamide structure is a compound represented by following formula (S-2).

[Formula 64]

In formula (S-2), R ¹ , R ² and R ³ each independently represent a hydrogen atom or a monovalent organic group, and two or more of R ¹ , R ² and R ³ bond to each other to form a ring structure. You can do it.

It is preferable that each of R ¹ , R ² and R ³ independently represents a monovalent organic group.

Examples of R ¹ , R ² and R ³ include a hydrogen atom, an alkyl group, a cycloalkyl group, an alkoxy group, an alkyl ether group, an alkylsilyl group, an alkoxysilyl group, an aryl group, an aryl ether group, a carboxy group, a carbonyl group, and an allyl group. group, a vinyl group, a heterocyclic group, or a group in which two or more of these are combined.

As said alkyl group, a C1-C10 alkyl group is preferable, and a C1-C6 alkyl group is more preferable. As said alkyl group, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, an isopropyl group, 2-ethylhexyl group etc. are mentioned, for example.

As said cycloalkyl group, a C5-C10 cycloalkyl group is preferable, and a C6-C10 cycloalkyl group is more preferable. As said cycloalkyl group, a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, etc. are mentioned, for example.

As said alkoxy group, a C1-C10 alkoxy group is preferable, and a C1-C5 alkoxy group is more preferable. As said alkoxy group, a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentoxy group, etc. are mentioned.

As said alkoxysilyl group, a C1-C10 alkoxysilyl group is preferable, and a C1-C4 alkoxysilyl group is more preferable. As said alkoxysilyl group, a methoxysilyl group, an ethoxysilyl group, a propoxysilyl group, a butoxysilyl group, etc. are mentioned.

As said aryl group, a C6-C20 aryl group is preferable, and a C6-C12 aryl group is more preferable. The said aryl group may have substituents, such as an alkyl group. As said aryl group, a phenyl group, a tolyl group, a xylyl group, a naphthyl group, etc. are mentioned.

Examples of the heterocyclic group include a triazole ring, a pyrrole ring, a furan ring, a thiophene ring, an imidazole ring, an oxazole ring, a thiazole ring, a pyrazole ring, an isoxazole ring, an isothiazole ring, a tetrazole ring, a pyridine ring, and a pyridine ring. One hydrogen atom from a heterocyclic structure such as a multijin ring, a pyrimidine ring, a pyrazine ring, a piperidine ring, a piperidine ring, a piperazine ring, a morpholine ring, a dihydropyran ring, a tetrahydropyran group, and a triazine ring. Removed group etc. are mentioned.

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

Examples of the compound having a sulfonamide structure include benzenesulfonamide, dimethylbenzenesulfonamide, N-butylbenzenesulfonamide, sulfanylamide, o-toluenesulfonamide, p-toluenesulfonamide, hydroxynaphthalenesulfonamide, naphthalene- 1-sulfonamide, naphthalene-2-sulfonamide, m-nitrobenzenesulfonamide, p-chlorobenzenesulfonamide, methanesulfonamide, N,N-dimethylmethanesulfonamide, N,N-dimethylethane Sulfonamide, N,N-diethylmethanesulfonamide, N-methoxymethanesulfonamide, N-dodecylmethanesulfonamide, N-cyclohexyl-1-butanesulfonamide, 2-aminoethanesulfonamide etc. can be mentioned.

[Compound having a thiourea structure]

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

[Formula 65]

In formula (T-1), R ⁴ and R ⁵ each independently represent a hydrogen atom or a monovalent organic group, R ⁴ and R ⁵ may be bonded to form a ring structure, and R ⁴ is another group to which * is bonded. A ring structure may be formed by combining with a structure, R ⁵ may combine with another structure to which * is bonded to form a ring structure, and * each independently represents a binding site with another structure.

It is preferable that each of R ⁴ and R ⁵ independently represents a hydrogen atom.

Examples of R ⁴ and R ⁵ include a hydrogen atom, an alkyl group, a cycloalkyl group, an alkoxy group, an alkyl ether group, an alkylsilyl group, an alkoxysilyl group, an aryl group, an aryl ether group, a carboxy group, a carbonyl group, an allyl group, and a vinyl group. group, a heterocyclic group, or a group in which two or more of these are combined.

As said alkyl group, a C1-C10 alkyl group is preferable, and a C1-C6 alkyl group is more preferable. As said alkyl group, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, an isopropyl group, 2-ethylhexyl group etc. are mentioned, for example.

As said cycloalkyl group, a C5-C10 cycloalkyl group is preferable, and a C6-C10 cycloalkyl group is more preferable. As said cycloalkyl group, a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, etc. are mentioned, for example.

As said alkoxy group, a C1-C10 alkoxy group is preferable, and a C1-C5 alkoxy group is more preferable. As said alkoxy group, a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentoxy group, etc. are mentioned.

As said alkoxysilyl group, a C1-C10 alkoxysilyl group is preferable, and a C1-C4 alkoxysilyl group is more preferable. As said alkoxysilyl group, a methoxysilyl group, an ethoxysilyl group, a propoxysilyl group, a butoxysilyl group, etc. are mentioned.

As said aryl group, a C6-C20 aryl group is preferable, and a C6-C12 aryl group is more preferable. The said aryl group may have substituents, such as an alkyl group. As said aryl group, a phenyl group, a tolyl group, a xylyl group, a naphthyl group, etc. are mentioned.

Examples of the heterocyclic group include a triazole ring, a pyrrole ring, a furan ring, a thiophene ring, an imidazole ring, an oxazole ring, a thiazole ring, a pyrazole ring, an isoxazole ring, an isothiazole ring, a tetrazole ring, a pyridine ring, and a pyridine ring. One hydrogen atom from a heterocyclic structure such as a multijin ring, a pyrimidine ring, a pyrazine ring, a piperidine ring, a piperidine ring, a piperazine ring, a morpholine ring, a dihydropyran ring, a tetrahydropyran group, and a triazine ring. Removed group etc. are mentioned.

The compound having a thiourea structure may be a compound having two or more thiourea structures, but is preferably a compound having one thiourea structure.

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

[Formula 66]

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

In formula (T-2), R ⁴ and R ⁵ have the same meanings as R ⁴ and R ⁵ in formula (T-1), and preferred embodiments are also the same.

In formula (T-2), it is preferable that each of R ⁶ and R ⁷ independently represents a monovalent organic group.

In the formula (T-2), preferred embodiments of the monovalent organic group for R ⁶ and R ⁷ are the same as preferred embodiments of the monovalent organic group for R ⁴ and R ⁵ in the formula (T-1). .

Examples of compounds having a thiourea structure include N-acetylthiourea, N-allylthiourea, N-allyl-N'-(2-hydroxyethyl)thiourea, and 1-adamantylthiourea. , N-benzoylthiourea, N,N'-diphenylthiourea, 1-benzyl-phenylthiourea, 1,3-dibutylthiourea, 1,3-diisopropylthiourea, 1 ,3-dicyclohexylthiourea, 1-(3-(trimethoxysilyl)propyl)-3-methylthiourea, trimethylthiourea, tetramethylthiourea, N,N-diphenylthio Ourea, ethylenethiourea (2-imidazoline thione), carbimazole, 1,3-dimethyl-2-thiohydantoin, etc. are mentioned.

〔content〕

The total content of the compound having a sulfonamide structure and the compound having a thiourea structure with respect to the total mass of the curable resin composition of the present invention is preferably 0.05 to 10% by mass, and more preferably 0.1 to 5% by mass. And, it is more preferably 0.2 to 3% by mass.

The curable resin composition of the present invention may contain only one or two or more compounds selected from the group consisting of compounds having a sulfonamide structure and compounds having a thiourea structure. When containing only 1 type, when content of the compound contains 2 or more types, it is preferable that the total amount becomes said range.

<Polymerization inhibitor>

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

Examples of the polymerization inhibitor include hydroquinone, o-methoxyphenol, methoxyhydroquinone, p-methoxyphenol, di-tert-butyl-p-cresol, pyrogallol, and p-tert-butylcatechol. (t-butylcatechol), 1,4-benzoquinone, diphenyl-p-benzoquinone, 4,4'-thiobis(3-methyl-6-tert-butylphenol), 2,2'-methylenebis (4-methyl-6-tert-butylphenol), N-nitroso-N-phenylhydroxyamine aluminum salt, phenothiazine, N-nitrosodiphenylamine, N-phenylnaphthylamine, ethylenediamine Tetraacetic acid, 1,2-cyclohexanediamine tetraacetic acid, glycoletherdiamine tetraacetic acid, 2,6-di-tert-butyl-4-methylphenol, 5-nitroso-8-hydroxyquinoline , 1-nitroso-2-naphthol, 2-nitroso-1-naphthol, 2-nitroso-5-(N-ethyl-N-sulfopropylamino)phenol, N-nitrosophenylhydroxy Amine monobasic cerium salt, N-nitroso-N-(1-naphthyl)hydroxyamine ammonium salt, bis(4-hydroxy-3,5-tert-butyl)phenylmethane, N,N'-di Phenyl-p-phenylenediamine, 2,4-di-tert-butylphenol, di-t-butylhydroxytoluene, 1,4-naphthoquinone, 1,3,5-tris(4-t-butyl -3-hydroxy-2,6-dimethylbenzyl) -1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 4-hydroxy-2,2, 6,6-tetramethylpiperidine 1-oxyl free radical, phenothiazine, 1,1-diphenyl-2-picrylhydrazyl, dibutyldithiocarbanate copper(II), nitrobenzene, N - Nitroso-N-phenylhydroxylamine aluminum salt, N-nitroso-N-phenylhydroxylamine ammonium salt, etc. are used suitably. Moreover, the polymerization inhibitor of Paragraph 0060 of Unexamined-Japanese-Patent No. 2015-127817, and Paragraph 0031 of International Publication No. 2015/125469 - the compound of 0046 can also be used.

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

[Formula 67]

When curable resin composition of this invention has a polymerization inhibitor, content of polymerization inhibitor is 0.01-20.0 mass % with respect to the total solids of curable resin composition of this invention, and it is 0.01-5 mass % It is preferable, it is more preferable that it is 0.02-3 mass %, and it is still more preferable that it is 0.05-2.5 mass %.

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

<Metal Adhesion Improver>

The curable resin composition of the present invention preferably contains a metal adhesion improving agent for improving adhesion to metal materials used for electrodes, wiring, and the like. Examples of the metal adhesion improving agent include aluminum-based adhesive aids, titanium-based adhesive aids, compounds having a sulfonamide structure, compounds having a thiourea structure, phosphoric acid derivative compounds, β-ketoester compounds, amino compounds, and the like. there is.

[Aluminum-based adhesive aid]

Examples of aluminum-based adhesive aids include aluminum tris (ethylacetoacetate), aluminum tris (acetylacetonate), and ethylacetoacetate aluminum diisopropylate.

As a metal adhesion improver, the compound of Paragraph 0046 of Unexamined-Japanese-Patent No. 2014-186186 - 0049, and the sulfide type compound of Paragraph 0032 of Unexamined-Japanese-Patent No. 2013-072935 - 0043 can be used.

The content of the metal adhesion improving agent is preferably 0.1 to 30 parts by mass, more preferably 0.5 to 15 parts by mass, and still more preferably 0.5 to 5 parts by mass, based on 100 parts by mass of the specific resin. By using the above lower limit or more, the adhesion between the pattern and the metal layer becomes good, and by using the above upper limit or less, the heat resistance and mechanical properties of the pattern become good. The metal adhesion improver may be one type or two or more types. When using 2 or more types, it is preferable that the sum total is the said range.

<Other additives>

Curable resin composition of the present invention, as necessary, various additives such as sensitizers, chain transfer agents, surfactants, higher fatty acid derivatives, inorganic particles, curing agents, curing catalysts, fillers, as necessary, within the range where the effects of the present invention are obtained. , antioxidants, ultraviolet absorbers, anti-aggregation agents and the like can be blended. When blending these additives, the total blending amount is preferably 3% by mass or less of the solid content of the curable resin composition.

[sensitizer]

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

Examples of the sensitizer include Michler's ketone, 4,4'-bis(diethylamino)benzophenone, 2,5-bis(4'-diethylaminobenzal)cyclopentane, 2,6-bis( 4'-diethylaminobenzal)cyclohexanone, 2,6-bis(4'-diethylaminobenzal)-4-methylcyclohexanone, 4,4'-bis(dimethylamino)chalcone, 4,4 '-bis(diethylamino)chalcone, p-dimethylaminocinnamylideneindanone, p-dimethylaminobenzylideneindanone, 2-(p-dimethylaminophenylbiphenylene)-benzothiazole, 2 -(p-dimethylaminophenylvinylene)benzothiazole, 2-(p-dimethylaminophenylvinylene)isonaphthothiazole, 1,3-bis(4'-dimethylaminobenzal)acetone, 1 ,3-bis(4'-diethylaminobenzal)acetone, 3,3'-carbonyl-bis(7-diethylaminocoumarin), 3-acetyl-7-dimethylaminocoumarin, 3-ethoxycarbonyl -7-dimethylaminocoumarin, 3-benzyloxycarbonyl-7-dimethylaminocoumarin, 3-methoxycarbonyl-7-diethylaminocoumarin, 3-ethoxycarbonyl-7-diethylaminocoumarin, N-phenyl-N'-ethylethanolamine, N-phenyldiethanolamine, N-p-tolyldiethanolamine, N-phenylethanolamine, 4-morpholinobenzophenone, dimethylaminobenzoic acid isoamyl, diethylaminobenzoic acid Isoamyl, 2-mercaptobenzimidazole, 1-phenyl-5-mercaptotetrazole, 2-mercaptobenzothiazole, 2-(p-dimethylaminostyryl)benzoxazole, 2-(p- Dimethylaminostyryl) benzothiazole, 2-(p-dimethylaminostyryl)naphtho(1,2-d)thiazole, 2-(p-dimethylaminobenzoyl)styrene, diphenylacetamide , benzanilide, N-methylacetanilide, 3',4'-dimethylacetanilide, and the like.

As a sensitizer, you may use a sensitizing dye.

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

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

[Chain transfer agent]

Curable resin composition of this invention may contain a chain transfer agent. The chain transfer agent is defined, for example, on pages 683-684 of the Polymer Dictionary, 3rd edition (ed., 2005). As the chain transfer agent, for example, a group of compounds having SH, PH, SiH, and GeH in the molecule are used. These can generate radicals by donating hydrogen to radicals with low activity to generate radicals, or by deprotonating after being oxidized. In particular, a thiol compound can be preferably used.

Moreover, as a chain transfer agent, Paragraph 0152 of International Publication No. 2015/199219 - the compound of 0153 can also be used.

When the curable resin composition of the present invention has a chain transfer agent, the content of the chain transfer agent is preferably 0.01 to 20 parts by mass, more preferably 1 to 10 parts by mass, based on 100 parts by mass of the total solids of the curable resin composition of the present invention. , 1 to 5 parts by mass are more preferable. 1 type of chain transfer agent may be sufficient as it, and 2 or more types may be sufficient as it. When there are 2 or more types of chain transfer agents, it is preferable that the sum total is the said range.

〔Surfactants〕

You may add surfactant to curable resin composition of this invention from a viewpoint of further improving applicability. As surfactant, each kind of surfactant, such as a fluorochemical surfactant, a nonionic surfactant, a cationic surfactant, anionic surfactant, and a silicone type surfactant, can be used. Moreover, the following surfactants are also preferable. In the following formula, parentheses indicating the repeating unit of the main chain indicate the content (mol%) of each repeating unit, and parentheses indicating the repeating unit of the side chain indicate the repeating number of each repeating unit.

[Formula 68]

Moreover, Paragraph 0159 of International Publication No. 2015/199219 - the compound of 0165 can also be used for surfactant.

As the fluorochemical surfactant, a fluoropolymer having an ethylenically unsaturated group in the side chain may be used as the fluorochemical surfactant. Specific examples include the compounds described in paragraphs 0050 to 0090 and paragraphs 0289 to 0295 of JP-A-2010-164965, for example, DIC Co., Ltd. Megafac RS-101, RS-102, RS-718K, etc. there is.

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

As the silicone surfactant, for example, Toray Silicone DC3PA, Toray Silicone SH7PA, Toray Silicone DC11PA, Toray Silicone SH21PA, Toray Silicone SH28PA, Toray Silicone SH29PA, Toray Silicone SH30PA, Toray Silicone SH8400 (above, Toray Dow Corning Co., Ltd.) product), TSF-4440, TSF-4300, TSF-4445, TSF-4460, TSF-4452 (above, manufactured by Momentive Performance Materials Co., Ltd.), KP341, KF6001, KF6002 (above, manufactured by Shin-Etsu Silicone Co., Ltd.) ), BYK307, BYK323, BYK330 (above, manufactured by Big Chemie Co., Ltd.), and the like.

Examples of hydrocarbon-based surfactants include Pionin A-76, Newcalzen FS-3PG, Pionin B-709, Pionin B-811-N, Pionin D-1004, Pionin D-3104, Pionin Pionin D-3605, Pionin D-6112, Pionin D-2104-D, Pionin D-212, Pionin D-931, Pionin D-941, Pionin D-951, Pionin E-5310, Pionin Pionin P-1050-B, Pionin P-1028-P, Pionin P-4050-T (above, Takemoto Yushi Co., Ltd.), etc. are mentioned.

Examples of nonionic surfactants include glycerol, trimethylolpropane, trimethylolethane and their ethoxylates and propoxylates (for example, glycerol propoxylate and glycerol ethoxylate), polyoxyethylene lauryl Ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate , Sorbitan fatty acid ester, Pluronic L10, L31, L61, L62, 10R5, 17R2, 25R2 (manufactured by BASF), Tetronic 304, 701, 704, 901, 904, 150R1 (manufactured by BASF), Solsperse 20000 (Nippon) Lubrizol Co., Ltd.), NCW-101, NCW-1001, NCW-1002 (Wako Junyaku Kogyo Co., Ltd.), Pionein D-6112, D-6112-W, D-6315 (Takemoto Yushi ( Co., Ltd.), Olfin E1010, Surfynol 104, 400, 440 (Nisshin Chemical Industry Co., Ltd.), etc. are mentioned.

Specifically, as the cationic surfactant, organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Industry Co., Ltd.), (meth)acrylic acid-based (co)polymer Polyflow No. 75, no. 77, no. 90, no. 95 (made by Kyoeisha Chemical Co., Ltd.), W001 (made by Yusho Co., Ltd.), etc. are mentioned.

Specifically as anionic surfactant, W004, W005, W017 (made by Yusho Co., Ltd.), Sandet BL (made by Sanyo Kasei Co., Ltd.), etc. are mentioned.

When the curable resin composition of the present invention has a surfactant, the content of the surfactant is preferably 0.001 to 2.0% by mass, more preferably 0.005 to 1.0% by mass with respect to the total solid content of the curable resin composition of the present invention. to be. 1 type of surfactant may be sufficient as it, and 2 or more types may be sufficient as it. When there are 2 or more types of surfactants, it is preferable that the sum total is the said range.

[Higher Fatty Acid Derivatives]

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

Moreover, the compound of Paragraph 0155 of International Publication No. 2015/199219 can also be used for a higher fatty acid derivative.

When the curable 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 curable resin composition of the present invention. 1 type of higher fatty acid derivative may be sufficient as it, and 2 or more types may be sufficient as it. When two or more types of higher fatty acid derivatives are used, it is preferable that the total is within the above range.

[Thermal polymerization initiator]

The resin composition of the present invention may contain a thermal polymerization initiator, and particularly may contain a thermal radical polymerization initiator. A thermal radical polymerization initiator is a compound that generates radicals by thermal energy to initiate or accelerate a polymerization reaction of a polymerizable compound. Since the polymerization reaction of resin and a polymeric compound can also advance by adding a thermal radical polymerization initiator, solvent resistance can be improved more.

As a thermal radical polymerization initiator, specifically, the compound described in Paragraph 0074 of Unexamined-Japanese-Patent No. 2008-063554 - 0118 is mentioned.

When a thermal polymerization initiator is included, the content thereof is preferably 0.1 to 30% by mass, more preferably 0.1 to 20% by mass, and further preferably 0.5 to 15% by mass with respect to the total solid content of the resin composition of the present invention. is mass %. The thermal polymerization initiator may contain only 1 type, and may contain 2 or more types. When containing 2 or more types of thermal polymerization initiators, it is preferable that the total amount is the said range.

[Inorganic Particles]

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

The average particle diameter of the inorganic particles is preferably 0.01 to 2.0 μm, more preferably 0.02 to 1.5 μm, still more preferably 0.03 to 1.0 μm, and particularly preferably 0.04 to 0.5 μm.

By containing the inorganic particles having the above-mentioned average particle size, the mechanical properties of the cured film and scattering suppression of exposure light can be made compatible.

[Ultraviolet rays absorber]

The composition of the present invention may contain a ultraviolet absorber. As the ultraviolet absorber, ultraviolet absorbers such as salicylate type, benzophenone type, benzotriazole type, substituted acrylonitrile type, and triazine type can be used.

Examples of salicylate-based ultraviolet absorbers include phenyl salicylate, p-octylphenyl salicylate, and p-t-butylphenyl salicylate. Examples of benzophenone-based ultraviolet absorbers include 2,2'-dihydride Roxy-4-methoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2,2',4,4'-tetrahydroxybenzophenone, 2-hydroxy- 4-methoxy benzophenone, 2,4-dihydroxy benzophenone, 2-hydroxy-4-octoxy benzophenone, etc. are mentioned. In addition, examples of benzotriazole-based ultraviolet absorbers include 2-(2'-hydroxy-3',5'-di-tert-butylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy- 3'-tert-butyl-5'-methylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-3'-tert-amyl-5'-isobutylphenyl)-5-chlorobenzotriazole , 2-(2'-hydroxy-3'-isobutyl-5'-methylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-3'-isobutyl-5'-propylphenyl) -5-chlorobenzotriazole, 2-(2'-hydroxy-3',5'-di-tert-butylphenyl)benzotriazole, 2-(2'-hydroxy-5'-methylphenyl)benzotriazole azoles, 2-[2'-hydroxy-5'-(1,1,3,3-tetramethyl)phenyl]benzotriazole, and the like.

Examples of the substituted acrylonitrile-based ultraviolet absorber include ethyl 2-cyano-3,3-diphenyl acrylate, 2-ethylhexyl 2-cyano-3,3-diphenyl acrylate and the like. Further, as an example of the triazine-based ultraviolet absorber, 2-[4-[(2-hydroxy-3-dodecyloxypropyl)oxy]-2-hydroxyphenyl]-4,6-bis(2,4-di Methylphenyl) -1,3,5-triazine, 2-[4-[(2-hydroxy-3-tridecyloxypropyl)oxy]-2-hydroxyphenyl]-4,6-bis(2,4 -Dimethylphenyl)-1,3,5-triazine, 2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, etc. Mono (hydroxyphenyl) triazine compounds of; 2,4-bis(2-hydroxy-4-propyloxyphenyl)-6-(2,4-dimethylphenyl)-1,3,5-triazine, 2,4-bis(2-hydroxy-3 -Methyl-4-propyloxyphenyl)-6-(4-methylphenyl)-1,3,5-triazine, 2,4-bis(2-hydroxy-3-methyl-4-hexyloxyphenyl)-6 bis(hydroxyphenyl)triazine compounds such as -(2,4-dimethylphenyl)-1,3,5-triazine; 2,4-bis(2-hydroxy-4-butoxyphenyl)-6-(2,4-dibutoxyphenyl)-1,3,5-triazine, 2,4,6-tris(2- Hydroxy-4-octyloxyphenyl)-1,3,5-triazine, 2,4,6-tris[2-hydroxy-4-(3-butoxy-2-hydroxypropyloxy)phenyl]- and tris(hydroxyphenyl)triazine compounds such as 1,3,5-triazine.

In this invention, the said various ultraviolet absorbers may be used individually by 1 type, and may be used in combination of 2 or more types.

The composition of the present invention may or may not contain a ultraviolet absorber, but when it is included, the content of the ultraviolet absorber is preferably 0.001% by mass or more and 1% by mass or less with respect to the total solid mass of the composition of the present invention, It is more preferable that it is 0.01 mass % or more and 0.1 mass % or less.

[organic titanium compound]

The resin composition of the present embodiment may contain an organic titanium compound. By containing the organic titanium compound in the resin composition, a resin layer having excellent chemical resistance can be formed even when cured at a low temperature.

Examples of usable organic titanium compounds include those in which an organic group is bonded to a titanium atom through a covalent bond or an ionic bond.

Specific examples of the organic titanium compound are shown in the following I) to VII):

I) Titanium chelate compound: Especially, the titanium chelate compound which has 2 or more alkoxy groups is more preferable at the point which is excellent in the storage stability of a negative photosensitive resin composition, and a favorable curing pattern is obtained. Specific examples include titanium bis(triethanolamine) diisopropoxide, titanium di(n-butoxide)bis(2,4-pentanedionate), titanium diisopropoxide bis(2,4-phen theindionate), titanium diisopropoxide bis(tetramethylheptanedionate), titanium diisopropoxide bis(ethylacetoacetate), and the like.

II) Tetraalkoxytitanium compounds: For example, titanium tetra(n-butoxide), titanium tetraethoxide, titanium tetra(2-ethylhexoxide), titanium tetraisobutoxide, titanium tetraisopropoxide, titanium Tetramethoxide, titanium tetramethoxypropoxide, titanium tetramethylphenoxide, titanium tetra(n-nonyloxide), titanium tetra(n-propoxide), titanium tetrastearyl oxide, titanium tetrakis[bis{2] ,2-(aryloxymethyl)butoxide}] and the like.

III) titanocene compounds: eg pentamethylcyclopentadienyltitanium trimethoxide, bis(η5-2,4-cyclopentadien-1-yl)bis(2,6-difluorophenyl ) titanium, bis(η5-2,4-cyclopentadien-1-yl)bis(2,6-difluoro-3-(1H-pyrrol-1-yl)phenyl)titanium, and the like.

IV) Monoalkoxy titanium compounds: For example, titanium tris (dioctyl phosphate) isopropoxide, titanium tris (dodecylbenzenesulfonate) isopropoxide and the like.

V) Titanium oxide compounds: For example, titanium oxide bis(pentanedionate), titanium oxide bis(tetramethylheptanedionate), phthalocyanine titanium oxide and the like.

VI) Titanium tetraacetylacetonate compounds: For example, titanium tetraacetylacetonate and the like.

VII) Titanate coupling agent: For example, isopropyl tridodecylbenzenesulfonyl titanate and the like.

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

When blending the organotitanium compound, the compounding amount is preferably 0.05 to 10 parts by mass, more preferably 0.1 to 2 parts by mass, based on 100 parts by mass of the precursor of the cyclized resin. When the compounding amount is 0.05 parts by mass or more, good heat resistance and chemical resistance are exhibited in the resulting cured pattern, while when it is 10 parts by mass or less, the storage stability of the composition is excellent.

[Antioxidant]

The composition of the present invention may contain an antioxidant. By containing an antioxidant as an additive, elongation characteristics of the film after curing and adhesion to a metal material can be improved. As an antioxidant, a phenol compound, a phosphite compound, a thioether compound, etc. are mentioned. As the phenolic compound, any phenolic compound known as a phenolic antioxidant can be used. As a preferable phenol compound, a hindered phenol compound is mentioned. A compound having a substituent at a site adjacent to the phenolic hydroxy group (ortho position) is preferred. As the substituent described above, a substituted or unsubstituted alkyl group having 1 to 22 carbon atoms is preferable. Further, the antioxidant is also preferably a compound having a phenol group and a phosphite ester group in the same molecule. Moreover, a phosphorus antioxidant can also be used suitably as an antioxidant. As the phosphorus antioxidant, tris[2-[[2,4,8,10-tetrakis(1,1-dimethylethyl)dibenzo[d,f][1,3,2]dioxaphosphepine-6- yl]oxy]ethyl]amine, tris[2-[(4,6,9,11-tetra-tert-butyldibenzo[d,f][1,3,2]dioxaphosphepin-2-yl) oxy]ethyl]amine, phosphorous acid ethylbis(2,4-di-tert-butyl-6-methylphenyl), and the like. As a commercial item of an antioxidant, Adeka Stab AO-20, Adeka Stab AO-30, Adeka Stab AO-40, Adeka Stab AO-50, Adeka Stab AO-50F, for example, Adeka Stab AO-60, Adeka Stab AO-60G, Adeka Stab AO-80, Adeka Stab AO-330 (above, made by ADEKA Co., Ltd.), etc. are mentioned. Moreover, the compound of Paragraph No. 0023 - 0048 of Unexamined-Japanese-Patent No. 6268967 can also be used as an antioxidant. Moreover, the composition of this invention may contain a latent antioxidant as needed. As the latent antioxidant, the site functioning as an antioxidant is a compound protected by a protecting group, and the protecting group is released by heating at 100 to 250° C. or heating at 80 to 200° C. in the presence of an acid/base catalyst to function as an antioxidant. compounds can be mentioned. Examples of the latent antioxidant include compounds described in International Publication No. 2014/021023, International Publication No. 2017/030005, and Japanese Unexamined Patent Publication No. 2017-008219. As a commercial item of a latent antioxidant, Adeka Akles GPA-5001 (made by ADEKA Corporation) etc. are mentioned. Examples of preferable antioxidants include compounds represented by 2,2-thiobis(4-methyl-6-t-butylphenol), 2,6-di-t-butylphenol, and General Formula (3).

[Formula 69]

In general formula (3), R5 represents a hydrogen atom or a C2 or more alkyl group, and R6 represents a C2 or more alkylene group. R7 represents a monovalent to tetravalent organic group containing at least any one of an alkylene group having 2 or more carbon atoms, an O atom, and an N atom. k represents an integer from 1 to 4;

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

Since it can act simultaneously on the resin and the metal material, k is more preferably an integer of 2 to 4. As R7, an alkyl group, a cycloalkyl group, an alkoxy group, an alkyl ether group, an alkylsilyl group, an alkoxysilyl group, an aryl group, an aryl ether group, a carboxyl group, a carbonyl group, an allyl group, a vinyl group, a heterocyclic group, -O-, - NH-, -NHNH-, what combined them, etc. are mentioned, You may have a substituent further. Among these, from the viewpoint of solubility in a developing solution and metal adhesion, those having alkyl ether and -NH- are preferable, and -NH- is more preferable from the viewpoint of interaction with resin and metal adhesion due to metal complexation. .

Although the following are mentioned as an example of the compound represented by following General formula (3), It is not limited to the following structure.

[Formula 70]

[Formula 71]

[Formula 72]

[Formula 73]

The addition amount of the antioxidant is preferably 0.1 to 10 parts by mass, more preferably 0.5 to 5 parts by mass, based on the resin. When the addition amount is less than 0.1 parts by mass, it is difficult to obtain the effect of improving elongation characteristics after reliability and adhesion to metal materials, and when it is more than 10 parts by mass, the sensitivity of the resin composition decreases due to interaction with the photosensitizer. may cause Antioxidant may use only 1 type, and may use 2 or more types. When using 2 or more types, it is preferable that those total amounts become the said range.

<Restrictions on other substances contained>

The water content of the curable resin composition of the present invention is preferably less than 5% by mass, more preferably less than 1% by mass, and even more preferably less than 0.6% by mass, from the viewpoint of coated surface properties. As a method of maintaining the water content, humidity adjustment in storage conditions, reduction of the porosity of the storage container, and the like are exemplified.

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

In addition, as a method for reducing metal impurities unintentionally contained in the curable resin composition of the present invention, a raw material having a low metal content is selected as a raw material constituting the curable resin composition of the present invention, or the curable resin composition of the present invention is constituted A method of filtering the raw material to be treated, lining the inside of the apparatus with polytetrafluoroethylene or the like, and distilling under conditions in which contamination is suppressed as much as possible can be cited.

In the curable resin composition of the present invention, considering the use as a semiconductor material, the content of halogen atoms is preferably less than 500 ppm by mass, more preferably less than 300 ppm by mass, and less than 200 ppm by mass, from the viewpoint of wiring corrosiveness. this is more preferable Especially, as for what exists in the state of a halogen ion, less than 5 mass ppm is preferable, less than 1 mass ppm is more preferable, and less than 0.5 mass ppm is still more preferable. As a halogen atom, a chlorine atom and a bromine atom are mentioned. It is preferable that the sum of chlorine atoms and bromine atoms, or chlorine ions and bromine ions, respectively is within the above range.

As a method of adjusting the content of halogen atoms, ion exchange treatment or the like is preferably used.

A conventionally well-known container can be used as a container for the curable resin composition of the present invention. In addition, as the storage container, a multi-layered bottle in which the inner wall of the container is composed of 6 types of 6-layered resins or a bottle in which 6 types of resins are used in a 7-layer structure is used for the purpose of suppressing the mixing of impurities into the raw materials and curable resin composition. It is also desirable to As such a container, the container of Unexamined-Japanese-Patent No. 2015-123351 is mentioned, for example.

<Use of Curable Resin Composition>

The curable resin composition of the present invention is preferably used for forming an interlayer insulating film for a redistribution layer.

In addition, it can also be used for forming an insulating film of a semiconductor device or forming a stress buffer film.

<Preparation of Curable Resin Composition>

Curable resin composition of this invention can be prepared by mixing each said component. The mixing method is not particularly limited, and a conventionally known method can be used.

Moreover, it is preferable to perform filtration using a filter for the purpose of removing foreign substances such as dust and fine particles in the curable resin composition. The filter hole diameter is preferably 1 μm or less, more preferably 0.5 μm or less, and still more preferably 0.1 μm or less. On the other hand, from the viewpoint of productivity, it is preferably 5 μm or less, more preferably 3 μm or less, and even more preferably 1 μm or less. The material of the filter is preferably polytetrafluoroethylene, polyethylene or nylon. As the filter, one previously washed with an organic solvent may be used. In the filter filtration process, you may connect and use multiple types of filters in series or parallel. In the case of using a plurality of types of filters, filters having different pore diameters or materials may be used in combination. Moreover, you may filter various materials multiple times. When filtering multiple times, circulation filtration may be sufficient. Moreover, you may perform filtration by pressurizing. When filtration is performed by pressurization, the pressurized pressure is preferably 0.05 MPa or more and 0.3 MPa or less. On the other hand, from the viewpoint of productivity, 0.01 MPa or more and 1.0 MPa or less are preferable, 0.03 MPa or more and 0.9 MPa or less are more preferable, and 0.05 MPa or more and 0.7 MPa or less are still more preferable.

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

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

Next, a resin film, a cured film, a laminate, a semiconductor device, and their manufacturing method are described.

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

It is good also as a laminated body by laminating the cured film of this invention in 2 or more layers, and also 3-7 layers. It is preferable that the layered product of the present invention includes two or more layers of cured films and includes a metal layer between any one of the cured films. For example, a laminated body containing at least a layered structure in which three layers of a first cured film, a metal layer, and a second cured film are laminated in this order is mentioned as a preferable one. The first cured film and the second cured film are both cured films of the present invention, and, for example, both the first cured film and the second cured film are films obtained by curing the curable resin composition of the present invention. can be mentioned as a preferable thing. The curable resin composition of the present invention used for forming the first cured film and the curable resin composition of the present invention used for forming the second cured film may be compositions having the same composition or different compositions. The metal layer in the laminate of the present invention is preferably used as metal wiring such as a redistribution layer.

Examples of applicable fields of the cured film of the present invention include insulating films for semiconductor devices, interlayer insulating films for redistribution layers, and stress buffer films. In addition, pattern formation of a sealing film, a substrate material (a base film or cover lay of a flexible printed circuit board, an interlayer insulating film), or an insulating film for mounting use as described above by etching may be used. Regarding their applications, for example, Science & Technology Co., Ltd. "Highly functional polyimide and application technology" April 2008, Masaaki Kakimoto/Supervisor, CMC Technical Library "Fundamentals and development of polyimide materials" 2011 Published in November, Japanese Polyimide and Aromatic Polymer Research Association/edition "Latest Polyimide Basics and Applications" N.T.S, August 2010, etc. can be referenced.

In addition, the cured film in the present invention can also be used for the production of a plate surface such as an offset plate surface or a screen plate surface, use for etching of molded parts, manufacture of protective lacquer and dielectric layer in electronics, particularly microelectronics.

The method for producing a cured film of the present invention (hereinafter also simply referred to as "the production method of the present invention") includes a film formation step of forming a film (resin film) by applying the curable resin composition of the present invention to a substrate. desirable.

It is preferable that the manufacturing method of the cured film of this invention includes the said film formation process, the exposure process of exposing the said film, and the developing process of developing the said film.

Moreover, it is more preferable that the manufacturing method of the cured film of this invention includes the said film formation process and the said developing process as needed, and also includes the heating process of heating the said film at 50-450 degreeC.

Specifically, it is also preferable to include the following steps (a) to (d).

(a) film formation step of forming a film (curable resin composition layer) by applying a curable resin composition to a substrate

(b) exposure step of exposing the film to light after the film formation step

(c) a developing step of developing the exposed film

(d) a heating step of heating the developed film at 50 to 450 ° C.

By heating in the said heating process, the resin layer hardened by exposure can be further hardened. In this heating step, for example, the heat base generator described above is decomposed, and sufficient curability is obtained.

The method for producing a laminate according to a preferred embodiment of the present invention includes the method for producing a cured film of the present invention. The manufacturing method of the laminated body of this embodiment, after forming a cured film according to the manufacturing method of the said cured film, the process of (a) again, or the process of (a) - (c), or (a) - The process of (d) is further performed. In particular, it is preferable to perform each of the above steps in order, plural times, for example, 2 to 5 times (ie, 3 to 6 times in total). By laminating the cured film in this way, it can be set as a laminated body. In this invention, it is preferable to provide a metal layer especially on the part where the cured film was provided, or between cured films, or both. In addition, in the manufacture of the laminate, it is not necessary to repeat all of the steps (a) to (d), and as described above, at least (a), preferably (a) to (c) or (a) to A layered product of a cured film can be obtained by performing the process of (d) a plurality of times.

<Film formation process (layer formation process)>

A manufacturing method according to a preferred embodiment of the present invention includes a film formation step (layer formation step) in which the curable resin composition is applied to a base material to form a film (layer form).

The type of base material can be appropriately determined depending on the application, but semiconductor manufacturing base materials such as silicon, silicon nitride, polysilicon, silicon oxide, and amorphous silicon, quartz, glass, optical films, ceramic materials, vapor deposition films, magnetic films, A reflective film, a metal substrate such as Ni, Cu, Cr, Fe, paper, SOG (Spin On Glass), a TFT (Thin Film Transistor) array substrate, an electrode plate of a plasma display panel (PDP), and the like are not particularly limited. Moreover, layers, such as an adhesive layer and an oxide layer, may be provided on the surface of these base materials. In the present invention, semiconductor fabrication substrates are particularly preferred, and silicon substrates, Cu substrates, and mold substrates are more preferred.

In addition, layers such as an adhesion layer or an oxide layer by hexamethyldisilazane (HMDS) or the like may be provided on the surface of these substrates.

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

The shape of the substrate is not particularly limited, and may be circular or rectangular, but a rectangular shape is preferred.

As for the size of the substrate, if it is circular, the diameter is, for example, 100 to 450 mm, preferably 200 to 450 mm. If it is a rectangular shape, the length of a short side is 100-1000 mm, for example, Preferably it is 200-700 mm.

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

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

Specifically, as applied means, dip coating method, air knife coating method, curtain coating method, wire bar coating method, gravure coating method, extrusion coating method, spray coating method, spin coating method, slit coating method, and An inkjet method etc. are illustrated. From the viewpoint of the uniformity of the thickness of the curable resin composition layer, spin coating method, slit coating method, spray coating method, and inkjet method are more preferable. A resin layer having a desired thickness can be obtained by appropriately adjusting the solid content concentration and application conditions according to the method. In addition, the coating method can be appropriately selected depending on the shape of the substrate. For circular substrates such as wafers, spin coating, spray coating, or ink jetting are preferable, and for rectangular substrates, slit coating, spray coating, or inkjet methods are preferred. etc. are preferred. In the case of spin coating, it can be applied for about 10 seconds to 1 minute at a rotational speed of 500 to 2,000 rpm, for example.

Moreover, it is also preferable to apply for 10 to 180 second at the rotation speed of 300-3,500 rpm depending on the viscosity of the photosensitive resin composition or the film thickness to set. Moreover, in order to obtain uniformity of film thickness, it is also possible to apply by combining a plurality of rotation speeds.

In addition, a method of transferring a coating film formed by applying on a temporary support in advance according to the above application method onto a base material can also be applied.

Regarding the transfer method, the production methods described in paragraphs 0023 and 0036 to 0051 of JP2006-023696 and paragraphs 0096 to 0108 of JP2006-047592 can be suitably used in the present invention.

Moreover, you may perform the process of removing an excess film|membrane at the edge part of a base material. Examples of such a process include edge bead rinse (EBR), air knife, bag rinse, and the like.

Alternatively, a pre-wet process may be employed in which various solvents are applied to the substrate before the resin composition is applied to the substrate to improve wettability of the substrate, and then the resin composition is applied.

<Drying process>

The manufacturing method of this invention may include the process of drying in order to remove a solvent after a film formation process (layer formation process). A preferred drying temperature is 50 to 150°C, more preferably 70°C to 130°C, still more preferably 90°C to 110°C. As drying time, 30 seconds - 20 minutes are illustrated, 1 minute - 10 minutes are preferable, and 3 minutes - 7 minutes are more preferable.

<Exposure process>

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

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

Regarding the exposure wavelength, in relation to the light source, (1) semiconductor laser (wavelength 830 nm, 532 nm, 488 nm, 405 nm etc.), (2) metal halide lamp, (3) high pressure mercury lamp, g-ray (wavelength 436 nm), h ray (wavelength 405nm), i-ray (wavelength 365nm), broad (three wavelengths of g, h, i-ray), (4) excimer laser, KrF excimer laser (wavelength 248nm), ArF excimer laser (wavelength 193nm), F2 excimer laser (wavelength 157 nm), (5) extreme ultraviolet; EUV (wavelength: 13.6 nm), (6) electron beam, (7) YAG laser second harmonic 532 nm, third harmonic 355 nm, and the like. Regarding the curable resin composition of the present invention, exposure by a high-pressure mercury lamp is particularly preferred, and exposure by i-line is particularly preferred. In this way, a particularly high exposure sensitivity can be obtained.

Further, from the viewpoint of handling and productivity, a high-pressure mercury lamp's broad (three wavelengths of g, h, and i lines) light sources or semiconductor lasers of 405 nm are also suitable.

<Development process>

The manufacturing method of the present invention may also include a developing step of performing development (developing the film) on the exposed film (curable resin composition layer). By developing, the unexposed part (unexposed part) is removed. The developing method is not particularly limited as long as a desired pattern can be formed, and examples thereof include ejection of a developing solution from a nozzle, spray spraying, and immersion of a substrate in a developing solution, and ejection from a nozzle is preferably used. As the developing step, a step in which the developing solution is continuously supplied to the substrate, a step in which the developing solution is maintained in a substantially stationary state on the substrate, a step in which the developing solution is vibrated by ultrasonic waves or the like, and a step in which they are combined are employable.

Development is performed using a developing solution.

The developing solution is not particularly limited and a known developer can be used, but a developing solution containing an organic solvent or an aqueous alkali solution can be used.

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

When the developer is a developer containing an organic solvent, the organic solvent is esters, 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, alkyloxyacetate alkyl (e.g., alkyloxymethyl methyl acetate, alkyloxyacetate ethyl, alkyl butyl oxyacetate (e.g. methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, etc.), 3-alkyloxypropionic acid alkyl esters (e.g. 3-alkyl Methyl oxypropionate, 3-alkyloxyethylpropionate, etc. (e.g., 3-methoxymethylpropionate, 3-methoxyethylpropionate, 3-ethoxymethylpropionate, 3-ethoxyethylpropionate, etc.), 2-alkyl Alkyl oxypropionate (e.g., 2-alkyloxymethylpropionate, 2-alkyloxyethylpropionate, 2-alkyloxypropyl oxypropionate, etc. (e.g., 2-methoxymethylpropionate, 2-methoxyethylpropionate, 2- Propyl methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate)), 2-alkyloxy-2-methylmethylpropionate and 2-alkyloxy-2-methylethylpropionate (e.g. 2-methylpropionate) Toxy-2-methylmethylpropionate, 2-ethoxy-2-methylethylpropionate, etc.), methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutanoate, 2-oxobutanoic acid Ethyl, etc., and as ethers, for example, diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate , ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol Monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, etc., and ketones As the class, for example, methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, N-methyl-2-pyrrolidone, etc., and as cyclic hydrocarbons, for example For example, toluene, xylene, anisole, limonene, etc. As sulfoxides, dimethyl sulfoxide is suitably mentioned, Moreover, the mixture of these organic solvents is also mentioned suitably.

When the developing solution is a developing solution containing an organic solvent, in the present invention, cyclopentanone and γ-butyrolactone are particularly preferred, and cyclopentanone is more preferred. Moreover, when a developing solution contains an organic solvent, organic solvent can also be used 1 type or in mixture of 2 or more types.

When the developer is a developer containing an organic solvent, the developer preferably contains 50% by mass or more of an organic solvent, more preferably 70% by mass or more of an organic solvent, and still more preferably 90% by mass or more of an organic solvent. Do. Moreover, 100 mass % of a developing solution may be an organic solvent.

The developing solution may further contain other components.

As another component, a well-known surfactant, a well-known antifoaming agent, etc. are mentioned, for example.

When the developing solution is an aqueous alkali solution, basic compounds that can be contained in the aqueous alkali solution include TMAH (tetramethylammonium hydroxide), KOH (potassium hydroxide), sodium carbonate, and the like, and TMAH is preferable. The content of the basic compound in the developing solution is preferably 0.01 to 10% by mass, more preferably 0.1 to 5% by mass, and even more preferably 0.3 to 3% by mass, based on the total mass of the developing solution, for example, when TMAH is used. .

[Supply Method of Developer]

The method of supplying the developer is not particularly limited as long as a desired pattern can be formed, and there are a method of immersing the substrate in the developer, a puddle phenomenon of supplying the developer onto the substrate using a nozzle, or a method of continuously supplying the developer. . The type of nozzle is not particularly limited, and examples thereof include straight nozzles, shower nozzles, and spray nozzles.

From the viewpoints of penetrability of the developer, removability of the non-image portion, and manufacturing efficiency, a method of supplying the developer through a straight nozzle or a method of continuously supplying the developer through a spray nozzle is preferable, and from the viewpoint of penetrability of the developer into the image portion, the spray The method of supplying with a nozzle is more preferable.

Alternatively, after continuously supplying the developing solution with a straight nozzle, the base material is spun to remove the developing solution from the base material, and after spin drying, a step of continuously supplying the developing solution with the straight nozzle again and then spinning the base material to remove the developing solution from the base material may be employed. , You may repeat this process multiple times.

Further, as a method of supplying the developing solution in the developing step, a step in which the developing solution is continuously supplied to the substrate, a step in which the developing solution is maintained on the substrate in a substantially stationary state, a step in which the developing solution is vibrated on the substrate with ultrasonic waves or the like, and a process in which they are combined. etc. can be employed.

As development time, 5 seconds - 10 minutes are preferable, and 10 seconds - 5 minutes are more preferable. The temperature of the developing solution at the time of development is not particularly determined, but is usually 10 to 45°C, preferably 20 to 40°C.

You may further rinse after the process using a developing solution. Moreover, you may employ|adopt the method of supplying a rinse liquid before the developing solution which touches on a pattern is completely dried. It is preferable to rinse with a solvent different from the developing solution. For example, it can rinse using the solvent contained in curable resin composition.

When the developing solution is a developing solution containing an organic solvent, examples of the rinsing solution include PGMEA (propylene glycol monoethyl ether acetate) and IPA (isopropanol), and PGMEA is preferable. Moreover, as a rinse liquid for image development with a developing solution containing an aqueous alkali solution, water is preferable.

The rinse time is preferably 10 seconds to 10 minutes, more preferably 20 seconds to 5 minutes, and still more preferably 5 seconds to 1 minute. 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.

Examples of the organic solvent in case the rinse liquid contains an organic solvent include esters such as ethyl acetate, n-butyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, Ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, γ-butyrolactone, ε-caprolactone, δ-valerolactone, alkyloxyacetate (e.g., methyl alkyloxyacetate, ethyl alkyloxyacetate, alkyloxy butyl acetate (e.g. methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, etc.), 3-alkyloxypropionic acid alkyl esters (e.g. 3-alkyloxy Methyl propionate, 3-alkyloxyethylpropionate, etc. (eg, 3-methoxymethylpropionate, 3-methoxyethylpropionate, 3-ethoxymethylpropionate, 3-ethoxyethylpropionate, etc.), 2-alkyloxy Alkyl esters of propionic acid (e.g., 2-alkyloxymethylpropionate, 2-alkyloxyethylpropionate, 2-alkyloxypropylpropionate, etc. (e.g., 2-methoxymethylpropionate, 2-methoxyethylpropionate, 2-methoxypropionate, Propyl oxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate)), 2-alkyloxy-2-methylmethylpropionate and 2-alkyloxy-2-methylethylpropionate (e.g. 2-methoxy -2-methylmethylpropionate, 2-ethoxy-2-methylethylpropionate, etc.), methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutanoate, ethyl 2-oxobutanoate etc., and, as ethers, for example, diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, Ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether (PGME), propylene glycol Lycol Monomethyl Ether Acetate (PGMEA), Propylene Glycol Monoethyl Ether Acetate, Propylene Glycol Monopropyl Ether Acetate etc., and as ketones, for example, methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, N-methyl-2-pyrrolidone, etc., and aromatic hydrocarbons As a small group, for example, toluene, xylene, anisole, limonene, etc., as sulfoxides, dimethyl sulfoxide, and as alcohols, methanol, ethanol, propanol, isopropanol, butanol, pentanol, octanol, Diethylene glycol, propylene glycol, methyl isobutyl carbinol, triethylene glycol, etc., and as amides, N-methylpyrrolidone, N-ethylpyrrolidone, dimethylformamide, etc. are suitable. can hear

When the rinse liquid contains an organic solvent, the organic solvent can be used alone or in combination of two or more. In the present invention, cyclopentanone, γ-butyrolactone, dimethylsulfoxide, N-methylpyrrolidone, cyclohexanone, PGMEA, and PGME are particularly preferred, and cyclopentanone, γ-butyrolactone, dimethylsulfoxide Side, PGMEA, and PGME are more preferable, and cyclohexanone and PGMEA are still more preferable.

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

The rinse liquid may further contain other components.

As another component, a well-known surfactant, a well-known antifoaming agent, etc. are mentioned, for example.

[How to supply rinse liquid]

The method of supplying the rinsing liquid is not particularly limited as long as a desired pattern can be formed, and a method of immersing the substrate in the rinsing liquid, a method of supplying the rinsing liquid onto the substrate by a liquid rise, and supplying the rinsing liquid to the substrate by showering There is a method of continuously supplying the rinsing liquid onto the substrate by means such as a straight nozzle.

From the viewpoint of permeability of the rinse liquid, removability of the non-image area, and manufacturing efficiency, there is a method of supplying the rinse liquid to a shower nozzle, a straight nozzle, a spray nozzle, etc., and a method of continuously supplying the rinse liquid to the spray nozzle is preferable, and the image area From the viewpoint of permeability of the rinsing liquid to the water, a method of supplying through a spray nozzle is more preferable. The type of nozzle is not particularly limited, and examples thereof include straight nozzles, shower nozzles, and spray nozzles.

That is, the rinsing step is preferably a step of supplying a rinsing liquid to the film after exposure through a straight nozzle or continuously supplying the rinsing liquid to the film after exposure, and more preferably a process of supplying the rinsing liquid through a spray nozzle.

Further, as a method of supplying the rinsing liquid in the rinsing step, a process in which the rinsing liquid is continuously supplied to the substrate, a process in which the rinsing liquid is maintained on the substrate in a substantially stationary state, a process in which the rinsing liquid is vibrated on the substrate with ultrasonic waves, and A process or the like combining them is employable.

<Heating process>

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

The heating process is preferably included after the film formation process (layer formation process), the drying process, and the developing process. In the heating step, a base is generated by decomposition of the above-mentioned thermal base generator, for example, and the cyclization reaction of the precursor, which is a specific resin, proceeds. Further, the curable resin composition of the present invention may contain radical polymerizable compounds other than specific resin precursors, but curing of unreacted radical polymerizable compounds other than specific resin precursors can also proceed in this step. The heating temperature (maximum heating temperature) of the layer in the heating step is preferably 50°C or higher, more preferably 80°C or higher, still more preferably 140°C or higher, still more preferably 150°C or higher, and 160°C or higher It is more preferable, and it is still more preferable that it is 170 degreeC or more. The upper limit is preferably 500°C or less, more preferably 450°C or less, still more preferably 350°C or less, still more preferably 250°C or less, and even more preferably 220°C or less.

Heating is preferably carried out at a heating rate of 1 to 12°C/minute from the temperature at the start of heating to the highest heating temperature, more preferably 2 to 10°C/minute, and still more preferably 3 to 10°C/minute. By setting the temperature increase rate to 1 ° C./min or more, excessive volatilization of amine can be prevented while securing productivity, and by setting the temperature increase rate to 12 ° C./min or less, the residual stress of the cured film can be relaxed. Further, in the case of an oven capable of rapid heating, heating is performed at a heating rate of 1 to 8°C/sec from the temperature at the start of heating to the maximum heating temperature, more preferably 2 to 7°C/sec, and even more preferably 3 to 6°C/sec. desirable.

The temperature at the start of heating is preferably 20°C to 150°C, more preferably 20°C to 130°C, still more preferably 25°C to 120°C. The temperature at the start of heating refers to the temperature at the time of starting the process of heating to the highest heating temperature. For example, when drying after applying curable resin composition on a base material, it is the temperature of the film (layer) after this drying, for example, the temperature 30-200 degreeC lower than the boiling point of the solvent contained in curable resin composition. It is preferable to gradually increase the temperature from there.

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

In particular, in the case of forming a multi-layered laminate, the heating temperature is preferably from 180°C to 320°C, more preferably from 180°C to 260°C, from the viewpoint of the interlayer adhesion of the cured film. Although the reason is not clear, it is thought that it is because the crosslinking reaction between the ethynyl groups of the specific resin between layers is advancing by setting it as this temperature.

Heating may be performed stepwise. For example, a pretreatment step such as raising the temperature from 25 ° C to 180 ° C at 3 ° C / min and holding at 180 ° C for 60 minutes, raising the temperature from 180 ° C to 200 ° C at 2 ° C / min and holding at 200 ° C for 120 minutes You can do it. The heating temperature as a pretreatment step is preferably 100 to 200°C, more preferably 110 to 190°C, and still more preferably 120 to 185°C. In this pretreatment process, it is also preferable to process while irradiating ultraviolet rays as described in US Patent Publication No. 9159547. It is possible to improve the properties of the film by such a pretreatment process. The pretreatment step is preferably performed in a short time of about 10 seconds to 2 hours, and more preferably 15 seconds to 30 minutes. The pretreatment may be carried out in two or more steps, for example, the pretreatment step 1 may be performed in the range of 100 to 150°C, and then the pretreatment step 2 may be performed in the range of 150 to 200°C.

Moreover, you may cool after heating, and as a cooling rate in this case, it is preferable that it is 1-5 degrees C/min.

The heating step is preferably performed in an atmosphere with a low oxygen concentration by flowing an inert gas such as nitrogen, helium, or argon to prevent decomposition of the specific resin. The oxygen concentration is preferably 50 ppm (volume ratio) or less, and more preferably 20 ppm (volume ratio) or less.

Although it does not specifically limit as a heating means, For example, a hot plate, an infrared furnace, an electrothermal type oven, a hot air type oven, etc. are mentioned.

<Metal layer formation process>

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

As the metal layer, without particular limitation, existing metal species can be used, and copper, aluminum, nickel, vanadium, titanium, chromium, cobalt, gold, and tungsten are exemplified, and copper, aluminum, and these metals are included. alloys are more preferred, and copper is more preferred.

The method of forming the metal layer is not particularly limited, and an existing method can be applied. For example, the method described in Unexamined-Japanese-Patent No. 2007-157879, Unexamined-Japanese-Patent No. 2001-521288, Unexamined-Japanese-Patent No. 2004-214501, and Unexamined-Japanese-Patent No. 2004-101850 can be used. For example, photolithography, lift-off, electrolytic plating, electroless plating, etching, printing, and methods combining these may be considered. More specifically, a patterning method in which sputtering, photolithography and etching are combined, and a patterning method in which photolithography and electrolytic plating are combined are exemplified.

The thickness of the metal layer is preferably 0.01 μm to 100 μm, more preferably 0.1 μm to 50 μm, and still more preferably 1 μm to 10 μm in the thickest part.

<Laminating process>

It is preferable that the manufacturing method of this invention further includes a lamination process.

The lamination process is, again, (a) film formation process (layer formation process), (b) exposure process, (c) development process, (d) heating process on the surface of the cured film (resin layer) or metal layer. It is a series of steps that involve performing in sequence. However, the aspect which repeats only the film formation process of (a) may be sufficient. Further, (d) the heating step may be performed collectively at the end or in the middle of the lamination. That is, it is good also as an aspect in which the laminated curable resin composition layer is collectively cured by repeating the steps (a) to (c) a predetermined number of times and then heating in (d). Further, after the (c) developing step, the metal layer forming step (e) may be included, and the heating in (d) may be performed at each time, or the heating in (d) may be performed collectively after laminating a predetermined number of times. It goes without saying that the lamination process may further include the aforementioned drying process, heating process, and the like as appropriate.

When the lamination process is further performed after the lamination process, a surface activation treatment process may be further performed after the heating process, the exposure process, or the metal layer forming process. As the surface activation treatment, plasma treatment is exemplified.

The lamination step is preferably performed 2 to 20 times, more preferably 2 to 5 times, and even more preferably 3 to 5 times.

In addition, each layer in the lamination process may be a layer having the same composition, shape, film thickness, and the like, or may be a layer different from each other.

For example, a resin layer/metal layer/resin layer/metal layer/resin layer/metal layer is preferably composed of 3 or more layers and 7 or less layers, more preferably 3 or more and 5 layers or less.

In this invention, after providing a metal layer especially, the aspect of forming the cured film (resin layer) of the said curable resin composition so that the said metal layer may be further covered is preferable. Specifically, (a) film formation process, (b) exposure process, (c) development process, (e) metal layer formation process, and (d) heating process are repeated in this order, or (a) film formation process , (b) exposure process, (c) development process, and (e) metal layer formation process are repeated in this order, and an aspect in which (d) heating process is provided collectively at the end or in the middle is exemplified. By alternately performing the lamination step of laminating the curable resin composition layer (resin layer) and the metal layer forming step, the curable resin composition layer (resin layer) and the metal layer can be alternately laminated.

(Surface activation treatment process)

The method for producing a laminate of the present invention may also include a surface activation treatment step of subjecting at least a part of the metal layer and the photosensitive resin composition layer to a surface activation treatment.

Although the surface activation treatment step is usually performed after the metal layer formation step, the metal layer formation step may be performed after performing the surface activation treatment step on the photosensitive resin composition layer after the above exposure and development step.

The surface activation treatment may be performed on at least a portion of the metal layer, at least a portion of the photosensitive resin composition layer after exposure, or at least a portion of both the metal layer and the photosensitive resin composition layer after exposure. 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 a region in which the photosensitive resin composition layer is formed on the surface of the metal layer. In this way, by performing surface activation treatment on the surface of the metal layer, adhesion to the resin layer provided on the surface can be improved.

In addition, it is preferable to perform surface activation treatment also on a part or all of the photosensitive resin composition layer (resin layer) after exposure. In this way, by subjecting the surface of the photosensitive resin composition layer to surface activation treatment, adhesion to the metal layer or resin layer provided on the surface of the surface activation treatment can be improved.

As the surface activation treatment, specifically, plasma treatment of various source gases (oxygen, hydrogen, argon, nitrogen, nitrogen/hydrogen mixture gas, argon/oxygen mixture gas, etc.), corona discharge treatment, CF ₄ /O ₂ , NF ₃ /O ₂ , SF ₆ , NF ₃ , NF ₃ After etching treatment by /O ₂ , surface treatment by ultraviolet (UV) ozone method, and immersion in an aqueous hydrochloric acid solution to remove the oxide film, having at least one amino group and thiol group It is selected from an immersion treatment for an organic surface treatment agent containing a compound and a mechanical roughening treatment using a brush, and a plasma treatment is preferred, and an oxygen plasma treatment using oxygen as a raw material gas is particularly preferred. In the case of corona discharge treatment, the energy is preferably 500 to 200,000 J/m ² , more preferably 1000 to 100,000 J/m ² , and most preferably 10,000 to 50,000 J/m ² .

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

Example

The present invention will be described in more detail by way of examples below. The materials, usage amount, ratio, processing content, processing procedure, etc. shown in the following examples can be appropriately changed as long as they do not deviate from the spirit of the present invention. Therefore, the scope of the present invention is not limited to the specific examples shown below. "Part" and "%" are based on mass unless otherwise specified.

<Synthesis Example B-1: Synthesis of Compound B-1>

In a flask equipped with a stirrer and a condenser, 7.25 g (105 mmol) of 1,2,4-triazole (manufactured by Tokyo Kasei Kogyo Co., Ltd.) and 15.52 g (100 mmol) of Karenz MOI (manufactured by Showa Denko Co., Ltd.) ) and Neostan U-600 (manufactured by Nitto Kasei Co., Ltd.) 0.01 g was dissolved in 70 mL of tetrahydrofuran (manufactured by Tokyo Kasei Kogyo Co., Ltd.), and stirred at 25°C for 1 hour. Then, after stirring at 45°C for 2 hours, it was dissolved in 600 mL of ethyl acetate and transferred to a separatory funnel. Subsequently, this was washed twice with 100 mL of water and twice with 150 mL of saturated brine, and dried over sodium sulfate. It was transferred to a one-necked flask, filtering this with filter paper, and the solvent was removed with an evaporator to obtain 18 g of B-1. The structure of B-1 is presumed to be a structure represented by the following formula (B-1). It was confirmed from the ¹ H-NMR spectrum that it was B-1.

¹ H-NMR data are shown below.

¹ H-NMR data: (heavy dimethyl sulfoxide, 400 MHz, internal standard: tetramethylsilane) δ (ppm) = 1.85 (s, 3H), 3.54 to 3.58 (q, 2H), 4.24 to 4.26 (t, 2H), 5.66(s, 1H), 6.03(s, 1H), 8.27(s, 1H), 8.86~8.90(t, 1H), 9.16(s, 1H)

[Formula 74]

<Synthesis Example B-2: Synthesis of Compound B-2>

In a flask equipped with a stirrer and a condenser, 15.2 g (0.22 mol) of 1,2,4-triazole was mixed with 150 mL of methylene chloride and cooled to 10°C or lower. Subsequently, 10.5 g (0.1 mol) of methacrylic acid chloride was added dropwise over 1 hour, and the temperature was raised to 20 to 25°C. After stirring at 20 to 25°C for 3 hours, 200 mL of methylene chloride was added, the generated salt was filtered with filter paper, and the filtrate was collected. The filtrate was transferred to a separatory funnel, washed twice with 50 mL of water and twice with 150 mL of saturated brine, and dried over sodium sulfate. It was transferred to a one-necked flask while filtering this with a filter paper, and the solvent was removed with an evaporator to obtain 12 g of B-2. The structure of B-2 is presumed to be a structure represented by the following formula (B-2). It was confirmed from the ¹ H-NMR spectrum that it was B-2.

¹ H-NMR data are shown below.

¹ H-NMR data: (deuterated chloroform, 400 MHz, internal standard: tetramethylsilane)

δ (ppm) = 2.17 (s, 3H), 6.09 (s, 1H), 6.44 (s, 1H), 8.06 (s, 1H), 8.95 (s, 1H)

[Formula 75]

<Synthesis Example B-3: Synthesis of Compound B-3>

In a flask equipped with a stirrer and a condenser, 7.25 g (105 mmol) of 1,2,4-triazole (manufactured by Tokyo Kasei Kogyo Co., Ltd.), 3-(triethoxysilyl)propyl isocyanate (Tokyo Kasei Kogyo Co., Ltd.) Co., Ltd.) 24.7 g (100 mmol), Neostan U-600 (manufactured by Nitto Kasei Co., Ltd.) 0.02 g was dissolved in 100 mL of tetrahydrofuran (manufactured by Tokyo Kasei Kogyo Co., Ltd.), stirred at 25 ° C. for 1 hour did. Subsequently, after stirring at 45°C for 2 hours, the mixture was dissolved in 800 mL of ethyl acetate and transferred to a separatory funnel. Subsequently, this was washed twice with 100 mL of water and twice with 150 mL of saturated brine, and dried over sodium sulfate. It was transferred to a one-necked flask, filtering this with a filter paper, and the solvent was removed with an evaporator to obtain 26 g of B-3. The structure of B-3 is presumed to be a structure represented by the following formula (B-3). It was confirmed from the ¹ H-NMR spectrum that it was B-3.

¹ H-NMR data are shown below.

¹ H-NMR data: (deuterated chloroform, 400 MHz, internal standard: tetramethylsilane)

δ (ppm) = 0.67 to 0.72 (t, 2H), 1.21 to 1.25 (t, 9H), 1.74 to 1.82 (M, 2H), 3.43 to 3.48 (q, 2H), 3.81 to 3.86 (q, 6H), 7.19(s, 1H), 7.97(s, 1H), 8.86(s, 1H)

[Formula 76]

<Synthesis Examples B-4 to B-10: Synthesis of Compounds B-4 to B-10>

The following B-4 to B-10 were synthesized in the same manner as in Synthesis Examples B-1 to B-3.

Structures B-4 to B-10 are estimated are shown in the following formulas (B-4) to formulas (B-10), respectively.

[Formula 77]

<Synthesis Example AP-1: Synthesis of Compound AP-1>

15 g of propylene glycol monomethyl ether was added to the flask, and the temperature was raised to 80°C and stirred while passing nitrogen.

Next, to an Erlenmeyer flask, 14.52 g (50 mmol) of 3-(triethoxysilyl)propyl methacrylate (manufactured by Tokyo Kasei Kogyo Co., Ltd.), 6.16 g (50 mmol) of the above-mentioned B-4, propylene glycol 50 g of colmonomethyl ether and 0.46 g of polymerization initiator V-601 (manufactured by Fujifilm Wako Co., Ltd.) were added, dissolved, and added dropwise to the flask over 3 hours. Then, after raising the temperature to 85°C and stirring for 3 hours, the mixture was cooled to room temperature to obtain an AP-1 solution. The solid content concentration (solid content/total mass of solution × 100) of the AP-1 solution was 24.1% by mass, and the weight average molecular weight (Mw) of AP-1 was 12,500.

[Formula 78]

<Synthesis Examples AP-2 to AP-4: Synthesis of Compounds AP-2 to AP-4>

Compounds AP-2 to AP-4 were synthesized in the same manner as in Synthesis Example AP-1.

Structures in which AP-2 to AP-4 are estimated are shown in the following formulas (AP-2) to (AP-4), respectively. In each structure, subscripts in parentheses indicate the molar ratio of each repeating unit.

The Mw of AP-2 was 15,800, the Mw of AP-3 was 25,000, and the Mw of AP-4 was 8,500.

[Formula 79]

<Synthesis Examples BP-1 to BP-2: Synthesis of Compounds BP-1 to BP-2>

Compounds BP-1 to BP-2 were synthesized in the same manner as in Synthesis Example AP-1.

Structures in which BP-1 to BP-2 are estimated are shown in the following formulas (BP-1) to (BP-2), respectively. In each structure, subscripts in parentheses indicate the molar ratio of each repeating unit.

The Mw of BP-1 was 19,100 and the Mw of BP-2 was 32,800.

[Formula 80]

<Synthesis Examples CP-1 to CP-3: Synthesis of Compounds CP-1 to CP-3>

Compounds CP-1 to CP-3 were synthesized in the same manner as in Synthesis Example AP-1.

Structures in which CP-1 to CP-3 are estimated are shown in the following formulas (CP-1) to (CP-3), respectively. In each structure, subscripts in parentheses indicate the molar ratio of each repeating unit.

The Mw of CP-1 was 15,300, the Mw of CP-2 was 20,600, and the Mw of CP-3 was 28,700.

[Formula 81]

<Synthesis Example A-1: of polybenzoxazole precursor A-1 from 2,2'-bis(3-amino-4-hydroxyphenyl)hexafluoropropane, 4,4'-oxydibenzoyl chloride synthesis>

28.0 g (76.4 mmol) of 2,2'-bis(3-amino-4-hydroxyphenyl)hexafluoropropane was stirred and dissolved in 200 g of N-methylpyrrolidone. Subsequently, 12.1 g (153 mmol) of pyridine was added, and 20.7 g (70.1 mmol) of 4,4'-oxydibenzoyl chloride was dissolved in 75 g of N-methylpyrrolidone while maintaining the temperature at -10 to 0 ° C. The solution was dripped over 1 hour. After stirring for 30 minutes, 1.00 g (12.7 mmol) of acetyl chloride was added, followed by stirring for another 60 minutes. Then, the polybenzoxazole precursor resin was precipitated in 6 liters of water, and the water-polybenzoxazole precursor resin mixture was stirred at a speed of 500 rpm for 15 minutes. The polybenzoxazole precursor resin was removed by filtration, stirred again for 30 minutes in 6 liters of water, and filtered again. Next, the obtained polybenzoxazole precursor resin was dried under reduced pressure at 45°C for 3 days to obtain polybenzoxazole precursor A-1. This polybenzoxazole precursor A-1 was Mw=21500 and Mn=9500.

The structure of the polybenzoxazole precursor A-1 is estimated to be a structure represented by the following formula (A-1).

[Formula 82]

<Synthesis Example A-2: Polyimide precursor from pyromellitic dianhydride, 4,4'-diaminodiphenyl ether and 2-hydroxyethyl methacrylate (A-2: polyi having a radical polymerizable group) Synthesis of Mead Precursor)>

14.06 g (64.5 mmol) of pyromellitic dianhydride (dried at 140 ° C for 12 hours), 16.8 g (129 mmol) of 2-hydroxyethyl methacrylate, 0.05 g of hydroquinone, 20.4 g of (258 mmol) of pyridine and 100 g of diglyme (diethylene glycol dimethyl ether) were mixed and stirred at a temperature of 60 ° C. for 18 hours to obtain pyromellitic acid and 2-hydroxyethyl methacrylate. of diesters were prepared. Subsequently, the resulting diester was chlorinated with SOCl ₂ , and then converted into a polyimide precursor with 4,4′-diaminodiphenyl ether in the same manner as in Synthesis Example A-5, followed by the same method as in Synthesis Example A-5. As a result, polyimide precursor A-2 was obtained. The weight average molecular weight of this polyimide precursor A-2 was 21,000.

The structure of the polyimide precursor A-2 is estimated to be a structure represented by the following formula (A-2).

[Formula 83]

<Synthesis Example A-3: Polyimide precursor from 4,4'-oxydiphthalic dianhydride, 4,4'-diaminodiphenyl ether and 2-hydroxyethyl methacrylate (A-3: radical polymerization Synthesis of Polyimide Precursor with Sexual Groups>

20.0 g (64.5 mmol) of 4,4'-oxydiphthalic dianhydride (dried at 140 ° C for 12 hours), 16.8 g (129 mmol) of 2-hydroxyethyl methacrylate, and 0.05 g of hydroquinone Rice paddy, 20.4 g (258 mmol) of pyridine, and 100 g of diglyme were mixed, and stirred at a temperature of 60 ° C. for 18 hours to obtain dihydrogenation of 4,4'-oxydiphthalic acid and 2-hydroxyethyl methacrylate. Esters were prepared. Subsequently, the resulting diester was chlorinated with SOCl ₂ , and then converted into a polyimide precursor with 4,4′-diaminodiphenyl ether in the same manner as in Synthesis Example A-5, followed by the same method as in Synthesis Example A-5. As a result, polyimide precursor A-3 was obtained. The weight average molecular weight of this polyimide precursor A-3 was 19,600.

The structure of the polyimide precursor A-3 is estimated to be a structure represented by the following formula (A-3).

[Formula 84]

<Synthesis Example A-4: from 4,4'-oxydiphthalic dianhydride, 4,4'-diamino-2,2'-dimethylbiphenyl (orthotolidine) and 2-hydroxyethyl methacrylate Synthesis of polyimide precursor (A-4: polyimide precursor having a radical polymerizable group) of

20.0 g (64.5 mmol) of 4,4'-oxydiphthalic dianhydride (dried at 140 ° C for 12 hours), 16.8 g (129 mmol) of 2-hydroxyethyl methacrylate, 0.05 g of hydroquinone Rice paddy, 20.4 g (258 mmol) of pyridine, and 100 g of diglyme were mixed and stirred at a temperature of 60 ° C. for 18 hours to obtain dihydrogenation of 4,4'-oxydiphthalic acid and 2-hydroxyethyl methacrylate. Esters were prepared. Subsequently, after chlorination of the obtained diester with SOCl ₂ , it was converted into a polyimide precursor with 4,4'-diamino-2,2'-dimethylbiphenyl in the same manner as Synthesis Example A-5, and Synthesis Example A polyimide precursor A-4 was obtained in the same manner as in A-5. The weight average molecular weight of this polyimide precursor A-4 was 23,500.

The structure of the polyimide precursor A-4 is estimated to be a structure represented by the following formula (A-4).

[Formula 85]

<Synthesis Example A-5: Polyimide precursor resin A- from oxydiphthalic dianhydride, 4,4'-biphthalic anhydride, 2-hydroxyethyl methacrylate and 4,4'-diaminodiphenyl ether Synthesis of 5>

9.49 g (32.25 mmol) of 4,4'-biphthalic anhydride and 10.0 g (32.25 mmol) of oxydiphthalic dianhydride were removed while removing water in a drying reactor equipped with a flat bottom joint equipped with an agitator, condenser and internal thermometer. ) was suspended in 140 mL of diglyme. 16.8 g (129 mmol) of 2-hydroxyethyl methacrylate, 0.05 g of hydroquinone, 0.05 g of pure water, and 10.7 g (135 mmol) of pyridine were successively added, and the mixture was stirred at a temperature of 60°C for 18 hours. Then, after cooling the mixture to -20°C, 16.1 g (135.5 mmol) of thionyl chloride was added dropwise over 90 minutes. A white precipitate of pyridinium hydrochloride was obtained. Then, after warming the mixture to room temperature and stirring for 2 hours, 9.7 g (123 mmol) of pyridine and 25 mL of N-methylpyrrolidone (NMP) were added to obtain a clear solution. Subsequently, a solution of 11.8 g (58.7 mmol) of 4,4'-diaminodiphenyl ether in 100 mL of NMP was added dropwise over 1 hour to the resulting transparent solution. Next, 5.6 g (17.5 mmol) of methanol and 0.05 g of 3,5-di-tert-butyl-4-hydroxytoluene were added, and the mixture was stirred for 2 hours. Then, the polyimide precursor resin was precipitated in 4 liters of water, and the water-polyimide precursor resin mixture was stirred at a speed of 500 rpm for 15 minutes. The polyimide precursor resin was obtained by filtration, stirred again in 4 liters of water for 30 minutes, and filtered again. Next, the obtained polyimide precursor resin was dried at 45°C for 3 days under reduced pressure to obtain polyimide precursor A-5. The weight average molecular weight of the obtained polyimide precursor A-5 was 23,800, and the number average molecular weight was 10,400.

The structure of the polyimide precursor A-5 is estimated to be a structure represented by the following formula (A-5).

[Formula 86]

<Synthesis Example A-6: Synthesis of Polyimide Precursor A-6 from 4,4'-oxydiphthalic dianhydride, 4,4'-diaminodiphenyl ether, and 2-hydroxyethyl methacrylate>

155.1 g of 4,4'-oxydiphthalic dianhydride (ODPA) was placed in a separable flask, and 134.0 g of 2-hydroxyethyl methacrylate (HEMA) and 400 mL of γ-butyrolactone were added. A reaction mixture was obtained by adding 79.1 g of pyridine while stirring at room temperature. After completion of heat generation by the reaction, the mixture was allowed to cool to room temperature and left still for further 16 hours.

Next, under ice-cooling, a solution obtained by dissolving 206.3 g of dicyclohexylcarbodiimide (DCC) in 180 mL of γ-butyrolactone was added to the reaction mixture over 40 minutes while stirring. Subsequently, a suspension obtained by suspending 93.0 g of 4,4'-diaminodiphenyl ether in 350 mL of γ-butyrolactone was added over 60 minutes while stirring. After stirring at room temperature for another 2 hours, 30 mL of ethyl alcohol was added and stirred for 1 hour. After that, 400 mL of γ-butyrolactone was added. A precipitate generated in the reaction mixture was removed by filtration to obtain a reaction liquid.

The obtained reaction liquid was added to 3 liters of ethyl alcohol to produce a precipitate composed of a crude polymer. The resulting crude polymer was collected by filtration and dissolved in 1.5 liters of tetrahydrofuran to obtain a crude polymer solution. The obtained crude polymer solution was dropped into 28 liters of water to precipitate the polymer, and the obtained precipitate was collected by filtration and vacuum dried to obtain a powdery polyimide precursor A-6. It was 24,000 as a result of measuring the weight average molecular weight (Mw) of this polyimide precursor A-6.

<Synthesis Example A-7: Polyimide precursor from 3,3',4,4'-biphenyltetracarboxylic dianhydride, 4,4'-diaminodiphenyl ether, and 2-hydroxyethyl methacrylate Synthesis of A-7>

In Synthesis Example 6, the method described in Synthesis Example 6 except for using 147.1 g of 3,3',4,4'-biphenyltetracarboxylic dianhydride instead of 155.1 g of 4,4'-oxydiphthalic dianhydride. Polymer A-7 was obtained by reacting in the same manner as above. It was 22,900 as a result of measuring the weight average molecular weight (Mw) of this polymer A-7.

<Synthesis Example PBI-1: Synthesis of Polyimide PBI-1>

In a flask equipped with a condenser and a stirrer, 22.2 g (50 mmol) of 4,4'-(hexafluoroisopropylidene)diphthalic anhydride (manufactured by Tokyo Kasei Kogyo Co., Ltd.), 2,2, 0.02 g of 6,6-tetramethylpiperidine 1-oxyl free radical (manufactured by Tokyo Kaseihin Kogyo Co., Ltd.) was dissolved in 100.0 g of N-methylpyrrolidone (NMP). Subsequently, 11.9 g (45 mmol) of diamine (AA-1) described later was added, and the mixture was stirred at 25°C for 3 hours and stirred at 45°C for another 3 hours. Subsequently, 15.8 g (200 mmol) of pyridine, 12.8 g (125 mmol) of acetic anhydride, and 50 g of N-methylpyrrolidone (NMP) were added, stirred at 80 ° C. for 3 hours, and N-methylpyrrolidone (NMP ) 50 g was added and diluted.

This reaction liquid was precipitated in 1 liter of methanol and stirred for 15 minutes at a speed of 3000 rpm. The resin was removed by filtration, stirred again for 30 minutes in 1 liter of methanol, and filtered again. The obtained resin was dried under reduced pressure at 40°C for one day to obtain polyimide PBI-1. The molecular weight of PBI-1 was Mw = 19,000 and Mn = 8,100.

It is estimated that the structure of polyimide PBI-1 is a structure represented by the following formula (PBI-1).

[Formula 87]

<Synthesis Example AA-1: Synthesis of Diamine AA-1>

In a flask equipped with a condenser and a stirrer, 26.0 g (0.2 mol) of 2-hydroxyethyl methacrylate (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) and 17.4 g of dehydrated pyridine (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) (0.22 mol) was dissolved in 78 g of ethyl acetate and cooled to 5°C or less. Then, 48.4 g (0.21 mol) of 3,5-dinitrobenzoyl chloride (manufactured by Tokyo Kasei Kogyo Co., Ltd.) was dissolved in 145 g of ethyl acetate, and this solution was added dropwise into the flask for 1 hour using a dropping funnel. did. After completion of the dropping, the mixture was stirred at 10°C or less for 30 minutes, heated to 25°C, and stirred for 3 hours. Then, the reaction solution was diluted with 600 mL of ethyl acetate (CH ₃ COOEt), transferred to a separatory funnel, and washed with 300 mL of water, 300 mL of saturated sodium bicarbonate water, 300 mL of dilute hydrochloric acid, and 300 mL of saturated brine in this order. After liquid separation and washing, drying with 30 g of magnesium sulfate, concentration using an evaporator and vacuum drying were carried out to obtain 61.0 g of a dinitro body (A-1).

In a flask equipped with a condenser and stirrer, 27.9 g (500 mmol) of reduced iron (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), 5.9 g (110 mmol) of ammonium chloride (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), acetic acid (Fujifilm Wako Junyaku Co., Ltd.) 3.0 g (50 mmol) and 2,2,6,6-tetramethylpiperidine 1-oxyl free radical (Tokyo Kasei Kogyo Co., Ltd.) 0.03 g were weighed, , 200 mL of isopropyl alcohol (IPA) and 30 mL of pure water were added and stirred.

Subsequently, 16.2 g of the dinitro body (A-1) was added in small portions over 1 hour, followed by stirring for 30 minutes. Next, the external temperature was raised to 85°C, stirred for 2 hours, cooled to 25°C or lower, and filtered using Celite (registered trademark). The filtrate was concentrated with a rotary evaporator and dissolved in 800 mL of ethyl acetate. This was transferred to a separatory funnel and washed twice with 300 mL of saturated sodium bicarbonate, followed by washing with 300 mL of water and 300 mL of saturated saline in that order. After liquid separation and washing, drying with 30 g of magnesium sulfate, concentration and vacuum drying were performed using an evaporator to obtain 11.0 g of diamine (AA-1).

[Formula 88]

<Examples and Comparative Examples>

In each Example, each curable resin composition was obtained by mixing the components described in the table below, respectively. Moreover, in each comparative example, each component for comparison was obtained by mixing the components described in the table below, respectively.

Specifically, the contents of components other than the solvents described in the tables were set to the amounts (parts by mass) described in each "additional amount" column in the tables.

In addition, for AP-1 to AP-4, BP-1 to BP-2, and CP-1 to CP-3, the solid content in the solution was added so as to be the amount (part by mass) described in each "addition amount" in the table.

The obtained curable resin composition and the comparative composition were filtered under pressure through a polytetrafluoroethylene filter having a fine pore width of 0.8 μm.

In addition, in the table|surface, description of "-" shows that the composition does not contain the component concerned.

[Table 1]

[Table 2]

The detail of each component described in the table|surface is as follows.

〔Suzy〕

A-1 to A-7, PBI-1: polybenzoxazole precursors A-1 synthesized in the above-described synthesis examples, polyimide precursors A-2 to A-7, polyimide PBI-1

[Compound B]

B-1 to B-10: B-1 to B-10 synthesized in the synthesis example described above

AP-1 to AP-4: AP-1 to AP-4 synthesized in the synthesis example described above

CP-1 to CP-3: CP-1 to CP-3 synthesized in the above-described synthesis example

B-1 to B-10 are compounds corresponding to the low molecular weight compound B described above.

AP-1 to AP-4 and CP-1 to CP-3 are compounds corresponding to Resin B described above.

[Compound C]

C-1 to C-7: Compounds represented by the following formulas (C-1) to (C-7)

[Formula 89]

[Compound D]

D-1 to D-6: Compounds represented by the following formulas (D-1) to (D-6)

BP-1 to BP-2: BP-1 to BP-2 synthesized in the synthesis example described above

D-1 to D-6 are compounds corresponding to the low molecular weight compound D described above.

BP-1 to BP-2 are compounds corresponding to Resin D described above.

[Formula 90]

[Compound E]

E-1 to E-3: Compounds represented by the following formulas (E-1) to (E-3)

[Formula 91]

[Photoinitiator (all brand names)]

・OXE-01: IRGACURE OXE 01 (manufactured by BASF)

・OXE-02: IRGACURE OXE 02 (manufactured by BASF)

[Polymerizable compound (all brand names)]

SR-209: SR-209 (manufactured by Sartomer)

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

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

A-DPH: dipentaerythritol hexaacrylate (manufactured by Shin-Nakamura Chemical Industry Co., Ltd.)

[Polymerization inhibitor]

F-1: 1,4-benzoquinone

F-2: 4-methoxyphenol

F-3: 1,4-dihydroxybenzene

F-4: a compound having the following structure

[Formula 92]

[base generator]

I-1 to I-3: Compounds with the following structures

・I-4: WPBG-27 (Fujifilm Wako Junyaku Co., Ltd.)

[Formula 93]

〔additive〕

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

〔solvent〕

DMSO: dimethyl sulfoxide

GBL: γ-butyrolactone

NMP: N-methylpyrrolidone

In the table, the description of "DMSO/GBL" indicates that a mixture of DMSO and GBL at a mixing ratio (mass ratio) of 80:20 was used.

<evaluation>

[Evaluation of Copper Adhesion]

Each of the curable resin compositions or comparative compositions after the filtration was applied in layers on a copper substrate by a spin coating method to form a curable resin composition layer. The copper substrate to which the obtained curable resin composition layer was applied was dried on a hot plate at 100°C for 5 minutes to obtain a uniform curable resin composition layer having a thickness of 20 µm on the copper substrate. The curable resin composition layer on the copper substrate was exposed to light using a stepper (Nikon NSR 2005 i9C) at an exposure energy of 500 mJ/cm ² using a photomask having a square-shaped non-mask portion having a side of 100 μm, and then cyclopentane. It was developed for 60 seconds by heating to obtain a square resin layer with a side of 100 µm. Further, in a nitrogen atmosphere, the temperature was raised at a heating rate of 10 ° C./min to reach the temperature described in the “curing temperature (° C.)” column in the table, and then maintained at this temperature for 3 hours to obtain a resin film 2.

However, in the case of using I-4 as the base generator, after reaching the temperature described in the above “curing temperature (°C)” column, the entire pattern was cured at an exposure amount of 500 mJ/cm ² while maintaining this temperature for 3 hours. i-line exposure was performed on the surface.

The shear force was measured for the square resin film 2 having a side of 100 μm on a copper substrate in an environment of 25° C. and 65% relative humidity (RH) using a bond tester (manufactured by XYZTEC, CondorSigma). The greater the shear force, the greater the adhesion, and it can be said that the adhesion between the metal and the cured film is excellent, resulting in a preferable result.

Evaluation was performed according to the following evaluation criteria, and the evaluation results were described in the "copper adhesion" column in the table.

-Evaluation standard-

A: The shear force exceeded 40 gf

B: Shear force greater than 35 gf and less than 40 gf

C: Shear force greater than 30 gf and less than 35 gf

D: Shear force greater than 25 gf and less than 30 gf

E: Shear force less than 25gf

1gf is 9.80665×10 ^-3 N.

[Evaluation of adhesion during multi-layer lamination]

-Manufacture of laminated body-

Each curable resin composition or comparative composition was applied layer by layer on a silicon wafer by spin coating, and dried at 100° C. for 5 minutes using a hot plate to form a curable resin composition layer. Next, the curable resin composition layer was exposed with exposure energy of 500 mJ/cm ² using a stepper (Nikon NSR 2005 i9C) through a photomask having a circular non-exposed portion having a diameter of 10 μm. Next, the curable resin composition layer after exposure was developed for 60 seconds using cyclopentanone to form a hole with a diameter of 10 μm. Next, a resin layer (pattern) was formed by heating in a nitrogen atmosphere at the temperature described in the "curing temperature (°C)" column in the table for 3 hours. However, in the case of using I-4 as the base generator, after reaching the temperature described in the above “curing temperature (°C)” column, the entire pattern was cured at an exposure amount of 500 mJ/cm ² while maintaining this temperature for 3 hours. i-line exposure was performed on the surface. Next, the resin layer (pattern) after heating was cooled to room temperature, copper plating was performed, a copper thin film having a thickness of 5 μm was formed on the resin layer, and laminate 1 was formed.

Next, after irradiating oxygen plasma to the copper thin film of layered product 1, application of curable resin composition, exposure, development, and heating are performed again, followed by copper plating treatment, and copper having a thickness of 5 μm on the resin layer. A thin film was formed to obtain laminate 2.

Next, after irradiating oxygen plasma to the copper thin film of layered product 2, application of curable resin composition, exposure, development, and heating are performed again, followed by copper plating treatment, and copper having a thickness of 5 μm on the resin layer. A thin film was formed to obtain laminate 3.

-Evaluation of Peeling Defects-

The layered product 3 was cut in the vertical direction, and a cross section having a width of 5 mm was observed, and the presence or absence of peeling between resin layers/resin layers and between copper/resin layers and the number of pieces were confirmed. The smaller the occurrence of peeling, the more excellent adhesion is exhibited during multilayer lamination, resulting in a preferable result.

Evaluation was performed according to the following evaluation criteria, and the evaluation results were described in the "adhesiveness at the time of multilayer lamination" column in the table.

-Evaluation standard-

A: No occurrence of peeling

B: 1 to 2 occurrences of peeling

C: 3 to 5 occurrences of peeling

D: 6 or more occurrences of peeling

<Example 101>

The curable resin composition used in Example 1 was applied layer by layer to the surface of a thin copper layer of a resin base material having a thin copper layer formed thereon by a spin coating method, dried at 100°C for 4 minutes, and curable resin composition having a film thickness of 20 μm. After forming the layer, it was exposed using a stepper (manufactured by Nikon Corporation, NSR1505i6). Exposure was performed at a wavelength of 365 nm through a mask (a binary mask with a 1:1 line-and-space pattern and a line width of 10 μm). After exposure, it heated at 100 degreeC for 4 minutes. After the heating, development was carried out with cyclohexanone for 2 minutes and rinsed with PGMEA for 30 seconds to obtain a layer pattern.

Then, in a nitrogen atmosphere, the temperature was raised at a heating rate of 10°C/min to reach 230°C, and then maintained at 230°C for 3 hours to form an interlayer insulating film for a redistribution layer. This interlayer insulating film for the redistribution layer was excellent in insulating properties.

In addition, as a result of manufacturing semiconductor devices using these interlayer insulating films for redistribution layers, it was confirmed that they operated without problems.

Claims (19)

At least one resin selected from the group consisting of polyimide precursors, polybenzoxazole precursors, polyimides, and polybenzoxazoles, and
A curable resin composition comprising compound B, which is a compound having a polymerizable group and an azole group. The method of claim 1,
Curable resin composition in which the said compound B has at least 1 sort(s) of group selected from the group which consists of an amide group, a urethane group, and a urea group. According to claim 1 or claim 2,
Curable resin composition in which the said compound B contains at least 1 sort(s) of group selected from the group which consists of a radical polymerizable group and an alkoxysilyl group as said polymeric group. The method according to any one of claims 1 to 3,
curable resin composition in which the azole group in the compound B is a group represented by the following formula (B-1) or the following formula (B-2);
[Formula 1]

In formula (B-1), R ^B1 represents a bonding site with a structure having a polymerizable group, a hydrogen atom, or a monovalent organic group having no polymerizable group, and Z ^B1 to Z ^B4 are each independently =CR ^B7 - or represents a nitrogen atom, R ^B7 represents a bonding site to a structure having a polymerizable group, a hydrogen atom or a monovalent organic group having no polymerizable group, and at least one of R ^B1 and R ^B7 contained in formula (B-1) represents a bonding site with a structure having a polymerizable group;
In formula (B-2), R ^B2 to R ^B6 each independently represent a bonding site to a structure having a polymerizable group, a hydrogen atom, or a monovalent organic group having no polymerizable group, and Z ^B5 and Z ^B6 are each independently where =CR ^B8 - or represents a nitrogen atom, R ^B8 represents a bonding site to a structure having a polymerizable group, a hydrogen atom, or a monovalent organic group having no polymerizable group, and is included in the formula (B-2) Among R ^B2 to R ^B6 and R ^B8 , at least one represents a bonding site with a structure having a polymerizable group. The method according to any one of claims 1 to 4,
A curable resin composition comprising a compound B having a molecular weight of less than 2,000 as the compound B. The method according to any one of claims 1 to 5,
Curable resin composition containing compound B which is a resin as said compound B. The method according to any one of claims 1 to 6,
A curable resin composition further comprising compound C, which is a compound having an azole group without having a polymerizable group. The method of claim 7,
Curable resin composition in which the said compound C is a compound represented by following formula (C-1) or following formula (C-2);
[Formula 2]

In formula (C-1), each of Z ¹ to Z ⁴ independently represents =CR ⁷ - or a nitrogen atom, R ¹ represents a hydrogen atom or a monovalent organic group, and R ⁷ represents a hydrogen atom or a monovalent organic group. and does not contain a polymerizable group in the structure represented by formula (C-1);
In formula (C-2), Z ⁵ to Z ⁶ each independently represent =CR ⁸ - or a nitrogen atom, R ² to R ⁶ each independently represent a hydrogen atom or a monovalent organic group, and R ⁸ is It represents a hydrogen atom or a monovalent organic group, and a polymerizable group is not included in the structure represented by formula (C-2). The method according to any one of claims 1 to 8,
A curable resin composition wherein at least one resin selected from the group consisting of the polyimide precursor, polybenzoxazole precursor, polyimide, and polybenzoxazole has a polymerizable group in the compound B and a polymerizable group capable of polymerization. The method according to any one of claims 1 to 9,
A curable resin composition further comprising Compound D, which is a silane coupling agent having a polymerizable group different from an alkoxysilyl group and not having an azole group. The method of claim 10,
A curable resin composition wherein at least one resin selected from the group consisting of the polyimide precursor, polybenzoxazole precursor, polyimide, and polybenzoxazole has a polymerizable group in the compound D and a polymerizable group capable of polymerization. According to any one of claims 1 to 11,
A curable resin composition further comprising a compound E which is a silane coupling agent having neither a polymerizable group nor an azole group different from an alkoxysilyl group. According to any one of claims 1 to 12,
A curable resin composition used for forming an interlayer insulating film for a redistribution layer. A cured film formed by curing the curable resin composition according to any one of claims 1 to 13. A laminate comprising two or more layers of the cured film according to claim 14 and including a metal layer between any of the cured films. A method for producing a cured film including a film formation step of applying the curable resin composition according to any one of claims 1 to 13 to a substrate to form a film. The method of claim 16
A method for producing a cured film comprising an exposure step of exposing the film and a developing step of developing the film. According to claim 16 or claim 17,
The manufacturing method of the cured film including the heating process of heating the said film at 50-450 degreeC. A semiconductor device comprising the cured film according to claim 14 or the laminate according to claim 15.