KR20230110589A - Resin composition, cured product, laminate, method for producing cured product, and semiconductor device - Google Patents

Abstract

A cyclized resin or a precursor thereof, a radical polymerization initiator, and a radical polymerizable compound, wherein the radical polymerizable compound includes a compound A having a urea bond and not having an axis of symmetry, wherein the compound A satisfies at least one of the following conditions 1 and 2; a cured product obtained by curing the resin composition; a laminate containing the cured product; a method for producing the cured product;
Condition 1: Compound A has two or more radical polymerizable groups;
Condition 2: Compound A has at least one selected from the group consisting of a hydroxy group, an alkyleneoxy group, an amide group and a cyano group.

Description

Resin composition, cured product, laminate, method for producing cured product, and semiconductor device

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

Since cyclization resins, such as polyimide, are excellent in heat resistance, insulating property, etc., they are 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, a cyclized resin such as polyimide is used in the form of a resin composition containing at least one of a cyclized resin such as polyimide and a precursor of the cyclized resin.

A cured product can be formed on the substrate by applying such a resin composition to a substrate by, for example, coating to form a photosensitive film, and then performing exposure, development, heating, or the like as necessary.

The precursors of the said cyclized resin, such as a polyimide precursor, are cyclized by heating, for example, and become a cyclized resin, such as polyimide, in hardened|cured material.

Since the resin composition can be applied by a known coating method or the like, it can be said to have excellent manufacturing adaptability, such as a high degree of freedom in designing, for example, the shape, size, application position, etc. at the time of application of the resin composition to be applied. In addition to the high performance possessed by cyclization resins such as polyimide, from the standpoint of such excellent adaptability in manufacturing, development of industrial applications of the above-described resin composition is increasingly expected.

For example, Patent Document 1 describes a photosensitive polyimide precursor composition characterized by containing (a) a polymer (A) containing a specific structural unit as a main component, (b) a compound (B) having a specific structure, and (c) a photoinitiator and/or a sensitizer and/or a photoreactive monomer.

Patent Document 2 describes a negative photosensitive resin composition containing (A) a polyimide precursor having a specific structural unit: 100 parts by mass, (B) a photopolymerization initiator: 1 to 20 parts by mass, and (C) a compound represented by a specific structure, or a polymer thereof and a compound represented by a specific structure, or at least one compound selected from the group consisting of the polymer, or a polymer thereof: 0.1 to 30 parts by mass.

Patent Document 1: Japanese Unexamined Patent Publication No. 6-332178 Patent Document 2: Japanese Unexamined Patent Publication No. 2011-059656

In a resin composition containing at least one of a cyclized resin such as polyimide and a precursor of the cyclized resin, it is required that the cured product obtained be excellent in chemical resistance.

An object of the present invention is to provide a resin composition from which a cured product having excellent chemical resistance can be obtained, a cured product formed by curing the resin composition, a laminate containing the cured product, a method for producing the cured product, and a semiconductor device containing the cured product or the laminate.

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

<1> A cyclized resin or a precursor thereof;

a radical polymerization initiator, and

Contains a radically polymerizable compound;

The radically polymerizable compound includes compound A having a urea bond and not having an axis of symmetry,

The compound A is a resin composition that satisfies at least one of condition 1 and condition 2 below;

Condition 1: Compound A has two or more radical polymerizable groups;

Condition 2: Compound A has at least one selected from the group consisting of a hydroxy group, an alkyleneoxy group, an amide group and a cyano group.

<2> The resin composition according to <1>, wherein the cyclized resin or precursor thereof is at least one resin selected from the group consisting of polyimide, polyimide precursor, polybenzoxazole, polybenzoxazole precursor, polyamideimide, and polyamideimide precursor.

<3> The resin composition according to <1> or <2>, wherein the cyclization resin or the precursor thereof has an acid value of 0 mmol/g to 1.2 mmol/g.

<4> The resin composition according to any one of <1> to <3>, wherein the compound A contains an aromatic group.

<5> The resin composition according to any one of <1> to <4>, further comprising a compound different from the compound A as the radically polymerizable compound.

<6> The resin composition according to any one of <1> to <5>, wherein the compound A is a compound represented by the following formula (1-1) or formula (1-2).

[Formula 1]

In formula (1-1), R ^P1 and R ^P2 each independently represent a group containing at least one radical polymerizable group;

In Formula (1-2), R ^P1 represents a group containing at least one radical polymerizable group, and L ³ represents a divalent linking group.

<7> The resin composition according to any one of <1> to <5>, which is used for forming an interlayer insulating film for a redistribution layer.

<8> A cured product formed by curing the resin composition according to any one of <1> to <7>.

<9> A laminate comprising two or more layers of layers made of the cured material according to <8>, and including a metal layer between any one of the layers made of the cured material.

<10> A method for producing a cured product, including a film formation step of applying the resin composition according to any one of <1> to <7> onto a substrate to form a film.

<11> The method for producing a cured product according to <10>, including an exposure step of selectively exposing the film and a developing step of forming a pattern by developing the film using a developing solution.

<12> The method for producing a cured product according to <10> or <11>, including a heating step of heating the film at 50 to 450°C.

<13> A semiconductor device comprising the cured product according to <8> or the laminate according to <9>.

According to the present invention, a resin composition from which a cured product having excellent chemical resistance can be obtained, a cured product formed by curing the resin composition, a laminate containing the cured product, a method for producing the cured product, and a semiconductor device including the cured product or the laminate.

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”, “(meth)acryl” means either or both of “acryl” and “methacryl”, and “(meth)acryloyl” means either or both of “acryloyl” and “methacryloyl”.

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

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

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

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

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

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

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

(resin composition)

The resin composition of the present invention contains a cyclized resin or a precursor thereof, a radical polymerization initiator, and a radical polymerizable compound, wherein the radical polymerizable compound includes a compound A having a urea bond and not having an axis of symmetry, and the compound A satisfies at least one of condition 1 and condition 2 below.

Condition 1: Compound A has two or more radical polymerizable groups.

Condition 2: Compound A has at least one selected from the group consisting of a hydroxy group, an alkyleneoxy group, an amide group and a cyano group.

The resin composition of the present invention is preferably used for forming a photoresist film subjected to exposure and development, and is preferably used for forming a film subjected to exposure and development using a developing solution containing an organic solvent.

The resin composition of the present invention can be used for forming, for example, an insulating film of a semiconductor device, an interlayer insulating film for a redistribution layer, a stress buffer film, and the like, and is preferably used for forming an interlayer insulating film for a redistribution layer.

In addition, the resin composition of the present invention may be used for forming a photosensitive film for negative development.

In the present invention, negative development refers to a phenomenon in which an unexposed portion is removed by development in exposure and development, and a positive type development refers to a phenomenon in which an exposed portion is removed by development.

As the method of exposure, the developer, and the method of development, for example, the exposure method described in the exposure step in the description of the method for producing a cured product described later, the developer described in the development step, and the developing method are used.

ADVANTAGE OF THE INVENTION According to the resin composition of this invention, the hardened|cured material excellent in chemical resistance is obtained.

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

Regarding the composition containing the cyclized resin or its precursor, in prior literature, the use of a radically polymerizable compound having a urea bond has been studied.

However, when a radically polymerizable compound having a urea bond is used in a resin composition containing a cyclized resin or a precursor thereof, the radically polymerizable compounds tend to aggregate with each other, and thus the chemical resistance may decrease.

In particular, a polymerizable compound having two or more radical polymerizable groups and having a urea bond, or a polymerizable compound having a polar group such as a hydroxyl group, an alkyleneoxy group, an amide group, and a cyano group, and having a urea bond, tends to aggregate, and when polymerized after forming a composition film, variation in the density of the polymer in the film may occur, resulting in a decrease in chemical resistance.

Therefore, as a result of intensive studies by the present inventors, it was found that chemical resistance is improved by using Compound A, which is a compound having no axis of symmetry as a polymerizable compound having two or more radical polymerizable groups and having a urea bond, or a polymerizable compound having a polar group such as a hydroxyl group, an alkyleneoxy group, an amide group, and a cyano group, and having a urea bond.

This is presumed to be because the aggregation of the polymerizable compound is suppressed because Compound A does not have an axis of symmetry, and therefore Compound A exists in the film in a relatively homogeneous state when polymerized.

In addition, polymers of compounds having two or more radically polymerizable groups, polymers of compounds having polar groups such as hydroxyl groups, alkyleneoxy groups, amide groups, and cyano groups are difficult to elute in organic solvents, etc., and such polymers are relatively uniform. It is estimated that by being present in the film, the chemical resistance of the obtained cured film is greatly improved.

In addition, since aggregation is suppressed as mentioned above because compound A does not have an axis of symmetry, solubility in the developing solution in the unexposed part of the film|membrane is also improved, and it is thought that developability is excellent.

In addition, since aggregation of compound A is suppressed as described above, inhibition by the polymer of the polymeric compound in which ring closure of the precursor of the cyclized resin is aggregated is suppressed, for example, and the elongation at break of the resulting cured film is also estimated to be excellent.

Here, Patent Documents 1 and 2 do not describe using the compound A.

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

<specific resin>

The resin composition of the present invention contains at least one resin (specific resin) selected from the group consisting of cyclized resins and precursors thereof.

The cyclized resin is preferably a resin containing an imide ring structure or an oxazole ring structure in the main chain structure.

In the present invention, the main chain refers to a relatively longest bonded chain in a resin molecule.

Examples of the cyclization resin include polyimide, polybenzoxazole, and polyamideimide.

The precursor of a cyclized resin refers to a resin that causes a change in chemical structure by an external stimulus to become a cyclized resin, preferably a resin that causes a change in chemical structure by heat to become a cyclized resin, and more preferably a resin that becomes a cyclized resin by generating a ring closure reaction and forming a cyclic structure by heat.

As a precursor of cyclization resin, a polyimide precursor, a polybenzoxazole precursor, a polyamideimide precursor, etc. are mentioned.

That is, the resin composition of the present invention preferably contains at least one resin (specific resin) selected from the group consisting of polyimide, polyimide precursor, polybenzoxazole, polybenzoxazole precursor, polyamideimide, and polyamideimide precursor as the specific resin.

It is preferable that the resin composition of this invention contains polyimide or a polyimide precursor as a specific resin.

In addition, the specific resin preferably has a polymerizable group, and more preferably contains a radical polymerizable group.

When specific resin has a radical polymerizable group, it is preferable that the resin composition of this invention contains the radical crosslinking agent mentioned later. If necessary, a sensitizer described below may be further included. From such a resin composition of the present invention, a negative photoresist film is formed, for example.

When specific resin has a polymeric group, it is also preferable that resin has a molecular chain containing a polymeric group and a urea bond.

It is preferable that the said molecular chain couple|bond with the main chain of resin as a side chain, for example.

When a specific resin contains a repeating unit represented by formula (2) described later, the molecular chain is preferably included in at least one of R ¹¹¹ , R ¹¹⁵ , R ¹¹³ and R ¹¹⁴ in the repeating unit represented by formula (2), for example.

When a specific resin contains a repeating unit represented by formula (4) described below, the molecular chain is preferably included in at least one of R ¹³¹ and R ¹³² in the repeating unit represented by formula (4), for example.

When a specific resin contains a repeating unit represented by formula (3) described later, the molecular chain is preferably included in at least one of R ¹²¹ , R ¹²² , R ¹²³ and R ¹²⁴ in the repeating unit represented by formula (3), for example.

When a specific resin contains a repeating unit represented by formula (X) described below, the molecular chain is preferably included in at least one of R ¹³³ and R ¹³⁴ in the repeating unit represented by formula (X), for example.

When a specific resin contains a repeating unit represented by formula (PAI-2) described later, the molecular chain is preferably included in at least one of R ¹¹¹ , R ¹¹⁷ and R ¹¹³ in the repeating unit represented by formula (PAI-2), for example.

When a specific resin contains a repeating unit represented by formula (PAI-3) described later, the molecular chain is preferably included in at least one of R ¹¹¹ and R ¹¹⁷ in the repeating unit represented by formula (PAI-3), for example.

From the viewpoint of chemical resistance, the acid value of the specific resin is preferably 0 mmol/g to 1.2 mmol/g, more preferably 0 mmol/g to 0.8 mmol/g, still more preferably 0 mmol/g to 0.6 mmol/g.

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

[Polyimide precursor]

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

[Formula 2]

In formula (2), A ¹ and A ² each independently represent an oxygen atom or -NH-, R ¹¹¹ represents a divalent organic group, R ¹¹⁵ represents a tetravalent organic group, and R ¹¹³ and R ¹¹⁴ each independently 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 3 to 20 carbon atoms, an aromatic group of 3 to 20 carbon atoms, or a group consisting of a combination thereof is preferable, and a group containing an aromatic group of 6 to 20 carbon atoms is more preferable. The linear or branched aliphatic group may have a hydrocarbon group in the chain substituted with a group containing a hetero atom, and the cyclic aliphatic group and aromatic group may have a reduced hydrocarbon group substituted with a group containing a hetero atom. As a preferred embodiment of the present invention, groups represented by -Ar- and -Ar-L-Ar- are exemplified, and groups represented by -Ar-L-Ar- are particularly preferred. However, Ar is each independently an aromatic group, and L is a single bond, an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be substituted with a fluorine atom, -O-, -CO-, -S-, -SO ₂ - or -NHCO-, or a group consisting of a combination of two or more of the above. These preferred ranges are as described above.

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

Specifically, it is preferably a diamine containing a straight-chain or branched aliphatic group having 2 to 20 carbon atoms, a cyclic aliphatic group having 3 to 20 carbon atoms, an aromatic group having 3 to 20 carbon atoms, or a group composed of a combination thereof, and more preferably a diamine containing an aromatic group having 6 to 20 carbon atoms. The linear or branched aliphatic group may have a hydrocarbon group in the chain substituted with a group containing a hetero atom, and the cyclic aliphatic group and aromatic group may have a reduced hydrocarbon group substituted with a group containing a hetero atom. Examples of the group containing an aromatic group include the following.

[Formula 3]

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

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

As diamine, it is 1, 2- diamino ethane, 1, 2- diamino propane, 1, 3- diamino propane, 1, 4- diamino butane, or 1, 6- diamino hexane specifically,; 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'-da dimethylcyclohexylmethane or isophoronediamine; m- or p-phenylenediamine, diaminotoluene, 4,4'- or 3,3'-diaminodiphenyl, 4,4'-diaminodiphenyl ether, 3,3-diaminodiphenyl ether, 4,4'- or 3,3'-diaminodiphenylmethane, 4,4'- or 3,3'-diaminodiphenylsulfone, 4,4'- or 3,3' -Diaminodiphenylsulfide, 4,4'- or 3,3'-diaminobenzophenone, 3,3'-dimethyl-4,4'-diaminobiphenyl, 2,2'-dimethyl-4,4'-diaminobiphenyl, 3,3'-dimethoxy-4,4'-diaminobiphenyl, 2,2-bis(4-aminophenyl)propane, 2,2-bis(4-aminophenyl) ) Hexafluoropropane, 2,2-bis (3-hydroxy-4-aminophenyl) propane, 2,2-bis (3-hydroxy-4-aminophenyl) hexafluoropropane, 2,2-bis (3-amino-4-hydroxyphenyl) propane, 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane, bis (3-amino-4-hydroxyphenyl) sulfone, bis (4-amino -3-hydroxyphenyl) sulfone, 4,4'-diaminoparaterphenyl, 4,4'-bis (4-aminophenoxy) biphenyl, bis [4- (4-aminophenoxy) phenyl] sulfone, bis [4- (3-aminophenoxy) phenyl] sulfone, bis [4- (2-aminophenoxy) phenyl] sulfone, 1,4-bis (4-aminophenoxy) benzene, 9,10-bis (4- Aminophenyl) anthracene, 3,3'-dimethyl-4,4'-diaminodiphenylsulfone, 1,3-bis(4-aminophenoxy)benzene, 1,3-bis(3-aminophenoxy)benzene, 1,3-bis(4-aminophenyl)benzene, 3,3'-diethyl-4,4'-diaminodiphenylmethane, 3,3'-dimethyl-4,4'-diamino Diphenylmethane, 4,4'-diaminooctafluorobiphenyl, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, 9,9-bis(4-aminophenyl)-10-hydroanthracene, 3,3',4,4'-tetraaminobiphenyl, 3,3',4,4'- Tetraaminodiphenyl ether, 1,4-diaminoanthraquinone, 1,5-diaminoanthraquinone, 3,3-dihydroxy-4,4'-diaminobiphenyl, 9,9'-bis(4-aminophenyl)fluorene, 4,4'-dimethyl-3,3'-diaminodiphenylsulfone, 3,3',5,5'-tetramethyl-4,4'-diaminodiphenylmethyl Thein, 2,4- or 2,5-diaminocumene, 2,5-dimethyl-p-phenylenediamine, acetoguanamine, 2,3,5,6-tetramethyl-p-phenylenediamine, 2,4,6-trimethyl-m-phenylenediamine, bis(3-aminopropyl)tetramethyldisiloxane, bis(p-aminophenyl)octamethylpentasiloxane, 2 ,7-diaminofluorene, 2,5-diaminopyridine, 1,2-bis(4-aminophenyl)ethane, diaminobenzanilide, 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-2,2' - At least one type of diamine selected from bis(trifluoromethyl)biphenyl, 2,2',5,5',6,6'-hexafluorotolidine, and 4,4'-diaminoquaterphenyl.

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

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

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

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

formula (51)

[Formula 4]

In formula (51), R ⁵⁰ to R ⁵⁷ are each independently a hydrogen atom, a fluorine atom, or a monovalent organic group, at least one of R ⁵⁰ to R ⁵⁷ is a fluorine atom, a methyl group, or a trifluoromethyl group, and * each independently represents a bonding site to a nitrogen atom in formula (2).

As the monovalent organic group of R ⁵⁰ to R ⁵⁷ , 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 are exemplified.

[Formula 5]

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

Examples of the diamine 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 and the like. You may use these by 1 type or in combination of 2 or more types.

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

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

[Formula 6]

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

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

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

[Formula 7]

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

Specific examples of tetracarboxylic acid dianhydride include pyromellitic acid dianhydride (PMDA), 3,3',4,4'-biphenyltetracarboxylic acid dianhydride, 3,3',4,4'-diphenylsulfide tetracarboxylic acid dianhydride, 3,3',4,4'-diphenylsulfotetracarboxylic acid dianhydride, 3,3',4,4'-benzophenonete Tracarboxylic dianhydride, 3,3',4,4'-diphenylmethanetetracarboxylic dianhydride, 2,2',3,3'-diphenylmethanetetracarboxylic dianhydride, 2,3,3',4'-biphenyltetracarboxylic dianhydride, 2,3,3',4'-benzophenonetetracarboxylic dianhydride, 4,4'-oxyda Ifthalic 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-dica Boxyphenyl) 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 hydrides, 1,2,3,4-benzenetetracarboxylic acid dianhydrides, and C1-C6 alkyl and C1-C6 alkoxy derivatives thereof.

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

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

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

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

[Formula 8]

In Formula (III), R ²⁰⁰ represents a hydrogen atom, a methyl group, an ethyl group or a methylol group, and a hydrogen atom or a methyl group is preferable.

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

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

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

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

When the polyalkyleneoxy group includes a plurality of types of alkyleneoxy groups with different alkylene groups, the arrangement of the alkyleneoxy groups in the polyalkyleneoxy group may be a random arrangement, a block arrangement, or an arrangement having a pattern such as alternation.

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, still more preferably 2 to 5, still more preferably 2 to 4, particularly preferably 2 or 3, and most preferably 2.

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 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 repeating numbers such as ethyleneoxy groups in these groups are as described above.

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

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

Specific examples of the acid-decomposable group include tert-butoxycarbonyl group, isopropoxycarbonyl group, tetrahydropyranyl group, tetrahydrofuranyl group, ethoxyethyl group, methoxyethyl group, ethoxymethyl group, trimethylsilyl group, tert-butoxycarbonylmethyl group, and trimethylsilylether group. From the viewpoint of exposure sensitivity, an ethoxyethyl group or a tetrahydrofuranyl group is preferable.

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

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

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

Formula (2-A)

[Formula 9]

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

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

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

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

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

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

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

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

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

[Polyimide]

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

In the present 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 aqueous solution of tetramethylammonium, and from the viewpoint of pattern formation, it is preferably a polyimide that dissolves 0.5 g or more, and more preferably a polyimide that 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, the polyimide also preferably has a fluorine atom.

For example, the fluorine atom is preferably contained in R ¹³² in the repeating unit represented by formula (4) described later or in R ¹³¹ in the repeating unit represented by formula (4) described later, and ^{is more preferably contained as an alkyl fluoride group in R 132 in the repeating unit represented by formula (4) described below or in R 131 in} the repeating unit represented by formula (4) described later.

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

-silicon atom-

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

For example, a silicon atom is preferably included in R ¹³¹ in the repeating unit represented by formula (4) described later, and more preferably included as an organically modified (poly)siloxane structure described later in R ¹³¹ in the repeating unit represented by formula (4) described later.

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

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

-ethylenically unsaturated bonds-

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

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

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

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

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

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 a group represented by the following formula (IV).

[Formula 10]

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

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

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

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

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

[Formula 11]

In 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, X represents an oxygen atom or a sulfur atom, * represents a bonding site with another structure, and ● represents a bonding site with an oxygen atom to which R ²¹ in formula (IV) is bonded.

In the formulas (R1) to (R3), the preferred 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 same as the preferred embodiment of the alkylene group having 2 to 12 carbon atoms or the (poly)alkyleneoxy group having 2 to 30 carbon atoms in R ²¹ described above.

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, obtained by reacting a polyimide having a hydroxy group such as a phenolic hydroxy group with a compound having an isocyanato group and an ethylenically unsaturated bond (eg, 2-isocyanatoethyl methacrylate, etc.).

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

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

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

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

-Polymerizable groups other than groups having ethylenically unsaturated bonds-

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

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

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

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

-Polar Transducer-

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

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

-Acid value-

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

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

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

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

From the viewpoint of chemical resistance, the acid value of the polyimide is preferably 0 mmol/g to 1.2 mmol/g, more preferably 0 mmol/g to 0.8 mmol/g, and still more preferably 0 mmol/g to 0.6 mmol/g.

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

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

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

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

-Phenolic hydroxyl group-

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

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

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

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

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

[Formula 12]

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

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

Formula (4-1)

[Formula 13]

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

Formula (4-2)

[Formula 14]

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

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

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

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

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

As diamines containing two or more of ethylene glycol chains and propylene glycol chains combined in one molecule, 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, HUNTSMAN Co., Ltd.), 1-(2-(2-(2-aminopropoxy)ethoxy)propoxy)propan-2-amine, 1-(1-(1-(2-aminopropoxy)propan-2-yl)oxy)propan-2-amine, etc., but is not limited thereto.

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

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

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

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

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

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

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

-Imidization rate (closing rate)-

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

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

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

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

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

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

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

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

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

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

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

[Polybenzoxazole precursor]

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

[Formula 15]

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

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

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

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

As the dicarboxylic acid containing an aliphatic group, a dicarboxylic acid containing a straight-chain or branched (preferably straight-chain) aliphatic group is preferable, and a dicarboxylic acid composed of a straight-chain or branched (preferably straight-chain) aliphatic group and two -COOH is more preferable. 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, and particularly preferably 5 to 10. It is preferable that a linear aliphatic group is an alkylene group.

As the dicarboxylic acid containing a straight-chain aliphatic group, 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, Hexacose Phosphorus diacid, heptacosein diacid, octacosane diacid, nonacosein diacid, triacontane diacid, hentriacontane diacid, dotriacontane diacid, diglycolic acid, dicarboxylic acid represented by the following formula, and the like.

[Formula 16]

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

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

[Formula 17]

In the formula, A represents a divalent group selected from the group consisting of -CH ₂ -, -O-, -S-, -SO ₂ -, -CO-, -NHCO-, -C(CF ₃ ) ₂ -, and -C(CH ₃ ) ₂ -, 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 는, 또, 비스아미노페놀 유도체 유래의 기인 것이 바람직하고, 비스아미노페놀 유도체 유래의 기로서는, 예를 들면, 3,3'-다이아미노-4,4'-다이하이드록시바이페닐, 4,4'-다이아미노-3,3'-다이하이드록시바이페닐, 3,3'-다이아미노-4,4'-다이하이드록시다이페닐설폰, 4,4'-다이아미노-3,3'-다이하이드록시다이페닐설폰, 비스-(3-아미노-4-하이드록시페닐)메테인, 2,2-비스(3-아미노-4-하이드록시페닐)프로페인, 2,2-비스-(3-아미노-4-하이드록시페닐)헥사플루오로프로페인, 2,2-비스-(4-아미노-3-하이드록시페닐)헥사플루오로프로페인, 비스-(4-아미노-3-하이드록시페닐)메테인, 2,2-비스-(4-아미노-3-하이드록시페닐)프로페인, 4,4'-다이아미노-3,3'-다이하이드록시벤조페논, 3,3'-다이아미노-4,4'-다이하이드록시벤조페논, 4,4'-다이아미노-3,3'-다이하이드록시다이페닐에터, 3,3'-다이아미노-4,4'-다이하이드록시다이페닐에터, 1,4-다이아미노-2,5-다이하이드록시벤젠, 1,3-다이아미노-2,4-다이하이드록시벤젠, 1,3-다이아미노-4,6-다이하이드록시벤젠 등을 들 수 있다. These bisaminophenols may be used alone or in combination.

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

[Formula 18]

In the formula, X ₁ represents -O-, -S-, -C(CF ₃ ) ₂ -, -CH ₂ -, -SO ₂ -, or -NHCO-, and * and # each represent a binding site with another structure. 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. R ¹²² 가, 상기 식에 의하여 나타나는 구조인 경우, 합계 4개의 * 및 # 중, 어느 2개가 식 (3) 중의 R ¹²² 가 결합되는 질소 원자와의 결합 부위이며, 또한, 다른 2개가 식 (3) 중의 R ¹²² 가 결합되는 산소 원자와의 결합 부위인 것이 바람직하고, 2개의 *가 식 (3) 중의 R ¹²² 가 결합되는 산소 원자와의 결합 부위이며, 또한, 2개의 #이 식 (3) 중의 R ¹²² 가 결합되는 질소 원자와의 결합 부위이거나, 또는, 2개의 *가 식 (3) 중의 R ¹²² 가 결합되는 질소 원자와의 결합 부위이고, 또한, 2개의 #이 식 (3) 중의 R ¹²² 가 결합되는 산소 원자와의 결합 부위인 것이 보다 바람직하며, 2개의 *가 식 (3) 중의 R ¹²² 가 결합되는 산소 원자와의 결합 부위이고, 또한, 2개의 #이 식 (3) 중의 R ¹²² 가 결합되는 질소 원자와의 결합 부위인 것이 더 바람직하다.

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

[Formula 19]

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

[Formula 20]

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

In the formula (As), having a substituent also at the ortho position of the phenolic hydroxy group, that is, R ₃ , is considered to bring the distance between the carbonyl carbon of the amide bond and the hydroxy group closer, and is particularly preferable in that the effect of achieving a high cyclization rate is further enhanced when cured at low temperatures.

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 alkylene and substituted alkylene for R ₁ include linear or branched alkyl groups having 1 to 8 carbon atoms. Among them, -CH ₂ -, -CH(CH ₃ )-, and -C(CH ₃ ) ₂ - are more preferable from the viewpoint of obtaining a well-balanced polybenzoxazole precursor having sufficient solubility in solvents while maintaining the effect of high i-line transparency and high cyclization rate when cured at low temperature. .

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 JP-A-2013-256506 can be referred to, and these contents are incorporated herein by reference.

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

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

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

[Formula 21]

In formula (SL), Z has a structure a and a structure b, R ^1s is a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, R ^2s is a hydrocarbon group having 1 to 10 carbon atoms, at least one of R ^3s , 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, each of which may be the same or different. The polymerization of structure a and structure b may be block polymerization or random polymerization. The mol% of the Z portion is 5 to 95 mol% for the a structure, 95 to 5 mol% for the b structure, and 100 mol% for a+b.

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

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

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

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

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

[Polybenzoxazole]

The polybenzoxazole is not particularly limited as long as it is a polymer compound having a benzoxazole ring, but is preferably a compound represented by the following formula (X), and more preferably a compound represented by the following formula (X) and having a polymerizable group. As said polymerizable group, a radical polymerizable group is preferable.

[Formula 22]

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

When having a polymerizable group, the polymerizable group may be located at at least one of R ¹³³ and R ¹³⁴ , and may be located at the terminal of polybenzoxazole as shown in the following formula (X-1) or formula (X-2).

Formula (X-1)

[Formula 23]

In formula (X-1), at least one of R ¹³⁵ and R ¹³⁶ is a polymerizable group, and when not a polymerizable group, it is an organic group, and other groups have the same meaning as in formula (X).

Formula (X-2)

[Formula 24]

In formula (X-2), R ¹³⁷ is a polymerizable group, others are substituents, and other groups have the same meaning as in formula (X).

The polymerizable group has the same meaning as the polymerizable group described for the polymerizable group possessed by the polyimide precursor.

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

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

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

[Formula 25]

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

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

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

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

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

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

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

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

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

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

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

[Polyamide-imide precursor]

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

[Formula 26]

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

[Formula 27]

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

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

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

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

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

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

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

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

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

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

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

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

Further, specific examples of dicarboxylic acid compounds include malonic acid, dimethylmalonic acid, ethylmalonic acid, isopropylmalonic acid, di-n-butylmalonic acid, succinic acid, tetrafluorosuccinic acid, methylsuccinic acid, 2,2-dimethylsuccinic acid, 2,3-dimethylsuccinic acid, dimethylmethylsuccinic acid, glutaric acid, hexafluoroglutaric acid, 2-methylglutaric acid, and 3-methylglutaric acid. Taric 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-no 4ine diacid, dodecane diacid, tridecane diacid, tetradecane diacid, pentadecane diacid, hexadecane diacid, heptadecane diacid, octadecaine diacid, nonadecaine diacid, eicosane diacid, henaicosane diacid, docosane diacid, trichosane diacid, tetracosane diacid, pentacosane diacid, hexacosane diacid , heptacoseine diacid, octacoceine diacid, nonacoseine diacid, triacontane diacid, hentriacontane diacid, dotriacontane diacid, diglycolic acid, phthalic acid, isophthalic acid, terephthalic acid, 4,4'-biphenylcarboxylic acid, 4,4'-biphenylcarboxylic acid, 4,4'-dicarboxydiphenyl ether, benzophenone- 4,4'-dicarboxylic acid etc. are mentioned.

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

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

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

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

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

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

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

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

[Polyamideimide]

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

In the present specification, alkali-soluble polyamideimide refers to polyamideimide that dissolves 0.1 g or more at 23 ° C. with respect to 100 g of 2.38 mass% tetramethylammonium aqueous solution. Although the upper limit of the amount of dissolution is not particularly limited, it is preferably 100 g or less.

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

-Fluorine atom-

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

The fluorine atom is, for example, preferably contained in R ¹¹⁷ or R 111 in the repeating unit represented by formula (PAI-3) described later, and more preferably contained as an alkyl fluoride group in R ¹¹⁷ or ^{R 111 in} the repeating unit represented by formula (PAI-3) described later.

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

-ethylenically unsaturated bonds-

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

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

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

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

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

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

-Polymerizable groups other than ethylenically unsaturated bonds-

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

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

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

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

-Polar Transducer-

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

-Acid value-

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

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

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

From the viewpoint of chemical resistance, the acid value of polyamideimide is preferably 0 mmol/g to 1.2 mmol/g, more preferably 0 mmol/g to 0.8 mmol/g, still more preferably 0 mmol/g to 0.6 mmol/g.

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

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

-Phenolic hydroxyl group-

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

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

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

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

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

[Formula 28]

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

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

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

-Imidization rate (closing rate)-

The imidation rate (also referred to as “ring closure rate”) of polyamideimide is preferably 70% or more, more preferably 80% or more, and 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 imidization rate is measured by the same method as the ring-closing rate of polyimide mentioned above.

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

Polyamideimide can be synthesized using, for example, a method in which a polyamideimide precursor is obtained by a known method and completely imidized using a known imidation reaction method, or a method in which the imidation reaction is stopped in the middle to introduce a part of the imide structure, or a method in which a part of the imide structure is introduced by blending the completely imidized polymer and the polyamideimide precursor.

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

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

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

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

[Method for Producing Polyimide Precursors, etc.]

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

Examples of the condensing agent include dicyclohexylcarbodiimide, diisopropylcarbodiimide, 1-ethoxycarbonyl-2-ethoxy-1,2-dihydroquinoline, 1,1-carbonyldioxy-di-1,2,3-benzotriazole, N,N'-disuccinimidyl carbonate, trifluoroacetic anhydride, and the like.

Examples of the alkylating agent include N,N-dimethylformamide dimethyl acetal, N,N-dimethylformamide diethyl acetal, N,N-dialkylformamide dialkyl acetal, trimethyl orthoformate and triethyl orthoformate.

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

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

The organic solvent can be appropriately determined depending on the raw material, but examples thereof include pyridine, diethylene glycol dimethyl ether (diglyme), N-methylpyrrolidone, N-ethylpyrrolidone, ethyl propionate, dimethylacetamide, dimethylformamide, tetrahydrofuran, and γ-butyrolactone.

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

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

-end sealant-

In the production method of the polyimide precursor or the like, in order to further improve storage stability, it is preferable to seal the carboxylic acid anhydride, acid anhydride derivative or amino group remaining at the resin terminal of the polyimide precursor or the like. When sealing the carboxylic acid anhydride and acid anhydride derivative remaining at the resin terminal, examples of the terminal blocker include monoalcohol, phenol, thiol, thiophenol, monoamine, and the like, and it is more preferable to use monoalcohol, phenol, or monoamine from the viewpoint of reactivity and stability of the film. Preferred monoalcohol compounds include primary alcohols such as methanol, ethanol, propanol, butanol, hexanol, octanol, dodecinol, benzyl alcohol, 2-phenylethanol, 2-methoxyethanol, 2-chloromethanol and furfuryl alcohol; Tertiary alcohols, such as secondary alcohol, t-butyl alcohol, and adamantane alcohol, are mentioned. Preferred compounds of phenols include phenols such as phenol, methoxyphenol, methylphenol, naphthalen-1-ol, naphthalen-2-ol, and hydroxystyrene. Further, preferred monoamine compounds include aniline, 2-ethynylaniline, 3-ethynylaniline, 4-ethynylaniline, 5-amino-8-hydroxyquinoline, 1-hydroxy-7-aminonaphthalene, 1-hydroxy-6-aminonaphthalene, 1-hydroxy-5-aminonaphthalene, 1-hydroxy-4-aminonaphthalene, 2-hydroxy-7- Aminonaphthalene, 2-hydroxy-6-aminonaphthalene, 2-hydroxy-5-aminonaphthalene, 1-carboxy-7-aminonaphthalene, 1-carboxy-6-aminonaphthalene, 1-carboxy-5-aminonaphthalene, 2-carboxy-7-aminonaphthalene, 2-carboxy-6-aminonaphthalene, 2-carboxy-5-aminonaphthalene , 2-aminobenzoic acid, 3-aminobenzoic acid, 4-aminobenzoic acid, 4-aminosalicylic acid, 5-aminosalicylic acid, 6-aminosalicylic acid, 2-aminobenzenesulfonic acid, 3-aminobenzenesulfonic acid, 4-aminobenzenesulfonic acid, 3-amino-4,6-dihydroxypyrimidine, 2-aminophenol, 3-aminophenol, 4-aminophenol, 2-aminothiophenol, 3-aminothiophenol, 4-aminothiophenol, etc. are mentioned. Two or more types of these may be used, and a plurality of different terminal groups may be introduced by reacting a plurality of terminal blocking agents.

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

-solid precipitation-

Manufacturing methods, such as a polyimide precursor, WHEREIN: The process of depositing solid may be included. Specifically, the absorption by-product of the dehydration condensation agent coexisting in the reaction solution is separated by filtration as necessary, and then the resulting polymer component is introduced into a poor solvent such as water, a lower aliphatic alcohol, or a mixture thereof, and the polymer component is precipitated, precipitated as a solid, and dried to obtain a polyimide precursor or the like. In order to improve the degree of purification, operations such as re-dissolving the polyimide precursor, re-precipitation, and drying may be repeated. Further, a step of removing ionic impurities using an ion exchange resin may be included.

〔content〕

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

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

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

Specifically, the resin composition of the present invention may contain a total of 2 or more types of specific resin and other resins described below, or may contain 2 or more types of specific resin, but it is preferable to include 2 or more types of specific resin.

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

<Other resins>

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

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

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

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

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

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

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

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

<Compound A>

The resin composition of the present invention contains, as a radically polymerizable compound, compound A having a urea bond and not having an axis of symmetry, and the compound A satisfies at least one of condition 1 and condition 2 below.

Condition 1: Compound A has two or more radical polymerizable groups.

Condition 2: Compound A has at least one of a hydroxy group, an alkyleneoxy group, an amide group and a cyano group.

[Symmetry axis]

Compound A is a compound having a structure without an axis of symmetry.

That compound A does not have an axis of symmetry means that the compound has no axis for generating molecules identical to those of the original molecules by rotating the entire compound, and is a left-right asymmetric compound. In addition, in the case where the structural formula of Compound A is expressed on paper, the fact that Compound A does not have an axis of symmetry means that the structural formula of Compound A cannot be expressed in a form having an axis of symmetry.

When compound A does not have an axis of symmetry, it is thought that aggregation of compound A is suppressed in the composition film.

[Urea binding]

The urea bond included in compound A refers to a bond represented by -NR ^N -C(=O)-NR ^N -. Each R ^N independently represents a hydrogen atom or a hydrocarbon group, more preferably a hydrogen atom, an alkyl group or an aryl group, more preferably a hydrogen atom or an alkyl group, and particularly preferably a hydrogen atom.

Although compound A may contain two or more urea bonds, the aspect which contains only one urea bond is also one of the preferable aspects of this invention.

[radical polymerizable group]

Compound A has a radical polymerizable group.

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 maleimide group, a (meth)acrylamide group, a (meth)acryloyloxy group, and the like, with a (meth)acryloyloxy group being preferable.

When the above condition 1 is satisfied, compound A has two or more radical polymerizable groups. In this case, two or more radically polymerizable groups may each have the same structure or may have different structures. Moreover, the aspect in which all structures of the radical polymerizable group contained in compound A are the same is also one of the preferable aspects of this invention.

In condition 1, as for the number of radical polymerizable groups, 2-10 are preferable, 2-4 are more preferable, 2 or 3 are more preferable, and 2 is especially preferable.

When the above condition 2 is satisfied, compound A includes a radical polymerizable group and at least one selected from the group consisting of a hydroxyl group, an alkyleneoxy group, an amide group, and a cyano group. In condition 2, the number of radical polymerizable groups contained in compound A may be 1 or more, preferably 1 to 10, more preferably 1 to 4, still more preferably 1 to 3, and particularly preferably 1 or 2.

From the viewpoint of chemical resistance, when compound A has two or more radical polymerizable groups, in compound A, at least one of the two or more radical polymerizable groups and at least one other of the two or more radical polymerizable groups are linked by a linking group containing a urea bond (hereinafter, also referred to as “linking group L”). An embodiment including a structure is also one of the preferred embodiments of the present invention.

The linking group L may contain a urea bond, but it is preferably a structure in which at least two selected from the group consisting of a urea bond and a hydrocarbon group, -O-, -C(=O)-, -S-, -S(=O) ₂ -, and -NR ^N - are bonded. R ^N is as described above.

As the hydrocarbon group, a saturated aliphatic hydrocarbon group, an aromatic hydrocarbon group, or a group represented by a combination thereof is preferable.

As the saturated aliphatic hydrocarbon group, a saturated aliphatic hydrocarbon group having 1 to 30 carbon atoms is preferable, a saturated aliphatic hydrocarbon group having 1 to 20 carbon atoms is more preferable, and a saturated aliphatic hydrocarbon group having 1 to 10 carbon atoms 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, and a group obtained by removing two or more hydrogen atoms from the benzene ring structure is still more preferable.

Among these, both ends of the urea bond are preferably bonded directly to a carbon atom, and both ends of the urea bond are more preferably bonded directly to a hydrocarbon group, and of both ends of the urea bond, one is directly bonded to an aromatic hydrocarbon group, and the other is a saturated aliphatic hydrocarbon group, an aromatic hydrocarbon group, or a group formed by a combination thereof. It is more preferable that the other directly bond with a saturated aliphatic hydrocarbon group. Preferred carbon atoms of the saturated aliphatic hydrocarbon group or the aromatic hydrocarbon group are as described above.

Hereinafter, specific examples of the linking group L are described, but the present invention is not limited thereto. In the following specific examples, * and # each represent a binding site with a radical polymerizable group.

[Formula 29]

[Formula 30]

[Hydroxy group, alkyleneoxy group, amide group or cyano group]

When the above condition 2 is satisfied, compound A has at least one selected from the group consisting of a hydroxyl group, an alkyleneoxy group, an amide group, and a cyano group.

From the viewpoint of chemical resistance of the resulting cured film, the hydroxy group may be either an alcoholic hydroxy group or a phenolic hydroxy group, but is preferably an alcoholic hydroxy group.

From the viewpoint of chemical resistance of the cured film obtained, the alkyleneoxy group is preferably an alkyleneoxy group having 2 to 20 carbon atoms, more preferably an alkyleneoxy group having 2 to 10 carbon atoms, more preferably an alkyleneoxy group having 2 to 4 carbon atoms, more preferably an ethylene group or a propylene group, and particularly preferably an ethylene group.

An alkyleneoxy group may be contained in compound A as a polyalkyleneoxy group. It is preferable that it is 2-10, and, as for the repeating number of the alkyleneoxy group in this case, it is more preferable that it is 2-6.

An amide group refers to a bond represented by -C(=O)-NR ^N- . R ^N is as described above. When compound A has an amide group, compound A can contain, for example, a group represented by RC(=O)-NR ^N -* or a group represented by *-C(=O)-NR ^N -R. R represents a hydrogen atom or a monovalent substituent, preferably a hydrogen atom or a hydrocarbon group, more preferably a hydrogen atom, an alkyl group or an aromatic hydrocarbon group. Compound A may have two or more structures selected from the group consisting of a hydroxy group, an alkyleneoxy group (however, a polyalkyleneoxy group in the case of constituting a polyalkyleneoxy group), an amide group, and a cyano group, but an embodiment having only one structure in a molecule is one of the preferred embodiments of the present invention.

The hydroxy group, alkyleneoxy group, amide group, and cyano group may be present at any position in Compound A, but from the viewpoint of chemical resistance, when the above-mentioned condition 2 is satisfied, at least one selected from the group consisting of the hydroxy group, alkyleneoxy group, amide group, and cyano group and at least one radical polymerizable group contained in Compound A are linked by a linking group (hereinafter also referred to as "linking group L2-1") containing a urea bond. This is also one of the preferred aspects of the present invention.

In particular, when compound A contains only one radical polymerizable group, the radical polymerizable group contained in compound A and at least one selected from the group consisting of a hydroxyl group, an alkyleneoxy group, an amide group, and a cyano group are preferably linked by a linking group (hereinafter also referred to as "linking group L2-2") containing a urea bond.

When compound A contains an alkyleneoxy group (however, when constituting a polyalkyleneoxy group, a polyalkyleneoxy group) and also has the linking group L2-1 or the linking group L2-2, the structure bonded to the side opposite to the linking group L2-1 or linking group L2-2 of the alkyleneoxy group (however, when constituting a polyalkyleneoxy group, the polyalkyleneoxy group) is not particularly limited, but is represented by a hydrocarbon group, a radical polymerizable group, or a combination thereof. Giga is preferred. The preferable aspect of the hydrocarbon group is the same as the preferable aspect of the hydrocarbon group in the linking group L described above. In addition, the preferred aspect of the radical polymerizable group is the same as the preferred aspect of the radical polymerizable group in the compound A described above.

When compound A contains an amide group and also has the linking group L2-1 or the linking group L2-2, the structure bonded to the side opposite to the linking group L2-1 or linking group L2-2 of the amide group is not particularly limited, but a hydrocarbon group, a radical polymerizable group, or a group represented by a combination thereof is preferable. The preferable aspect of the hydrocarbon group is the same as the preferable aspect of the hydrocarbon group in the linking group L described above. In addition, the preferred aspect of the radical polymerizable group is the same as the preferred aspect of the radical polymerizable group in the compound A described above. Further, in the above aspect, the carbon atom side of the amide group may bond to the linking group L2-1 or the linking group L2-2, and the nitrogen atom side of the amide group may bond to the linking group L2-1 or the linking group L2-2.

Specific examples of the linking group L2-1 or L2-2 include the same groups as the linking group L described above. However, * represents a bonding site with a radical polymerizable group, and when the structure shown as a specific example does not contain an alkyleneoxy group, # represents a bonding site with a structure containing at least one selected from the group consisting of a hydroxyl group, an alkyleneoxy group, an amide group and a cyano group, and an alkyleneoxy group in the structure shown as a specific example. to indicate the area.

[aromatic group]

It is preferable that compound A contains an aromatic group from viewpoints, such as compatibility with a specific resin.

It is preferable that the said aromatic group directly couple|bond with the urea bond contained in compound A. When compound A contains two or more urea bonds, it is preferable that one of the urea bonds and an aromatic group bond directly.

The aromatic group may be an aromatic hydrocarbon group, an aromatic heterocyclic group, or a structure in which they form a condensed ring, but it is preferably an aromatic hydrocarbon group.

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, and a group obtained by removing two or more hydrogen atoms from the benzene ring structure is still more preferable.

As the aromatic heterocyclic group, a 5- or 6-membered aromatic heterocyclic group is preferable. Examples of the aromatic heterocyclic ring in the aromatic heterocyclic group include pyrrole, imidazole, triazole, tetrazole, pyrazole, furan, thiophene, oxazole, isoxazole, thiazole, pyridine, pyrazine, pyrimidine, pyridazine, and triazine. These rings may be further condensed with other rings, such as indole and benzimidazole.

Moreover, as a heteroatom contained in the said aromatic heterocyclic group, a nitrogen atom, an oxygen atom, or a sulfur atom is preferable.

The aromatic group, for example, the above-mentioned linking group L or, at least one selected from the group consisting of a hydroxyl group, an alkyleneoxy group, an amide group and a cyano group, and at least one radical polymerizable group included in the compound A. It is preferably included in a linking group that connects.

[Number of atoms between urea bond and radical polymerizable group (link chain length)]

The number of atoms (link chain length) between the urea bond and the radical polymerizable group in the compound A is not particularly limited, but is preferably 30 or less, more preferably 2 to 20, and still more preferably 2 to 10.

When compound A contains 2 or more urea bonds, when it contains 2 or more radical polymerizable groups, or when it contains 2 or more urea bonds and also contains 2 or more radical polymerizable groups, among the number of atoms (link chain length) between a urea bond and a radical polymerizable group, the minimum one should just fall within the said range.

In the present specification, "the number of atoms between the urea bond and the polymerizable group (link chain length)" refers to the shortest (minimum number of atoms) of these connection objects among the atomic chains on the path connecting between two atoms or groups of atoms to be connected. For example, in the structure represented by the following formula, the number of atoms (linked chain length) between the urea bond and the radical polymerizable group (methacryloyloxy group) is two.

[Formula 31]

[Formula (1-1) or Formula (1-2)]

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

[Formula 32]

In formula (1-1), R ^P1 and R ^P2 each independently represent a group containing at least one radical polymerizable group;

In Formula (1-2), R ^P1 represents a group containing at least one radical polymerizable group, and L ³ represents a divalent linking group.

In formula (1-1), the number of radical polymerizable groups in R ^P1 and R ^P2 is preferably 1 to 10, more preferably 1 to 4, more preferably 1 or 2, respectively.

The preferable aspect of the radical polymerizable group in R ^P1 and R ^P2 is the same as the preferable aspect of the radical polymerizable group in the above-mentioned compound A.

It is also preferable that R ^P1 and R ^P2 are each independently a group represented by the following formula (RP-1).

[Formula 33]

In formula (RP-1), L ^RP1 represents a single bond or an m+1 valent linking group, X ^RP1 represents a radical polymerizable group, m represents an integer greater than or equal to 1, and * represents a binding site with a urea bond in formula (1-1).

In the formula (RP-1), L ^RP1 is preferably a hydrocarbon group, -O-, -C(=O)-, -S-, -S(=O) ₂ -, -NR ^N -, or a group in which two or more of these are bonded, and is a hydrocarbon group or a hydrocarbon group, and at least one group selected from the group consisting of -O-, -C(=O)-, -S-, -S(=O) ₂ -, and -NR ^N - is bonded Giga is more preferred. R ^N is as described above.

In addition, in L ^RP1 , it is preferable that the structure adjacent to * which is a bonding site with a urea bond is a hydrocarbon group.

As the hydrocarbon group in L ^RP1 , a saturated aliphatic hydrocarbon group, an aromatic hydrocarbon group, or a group obtained by a combination thereof is preferable, and a saturated aliphatic hydrocarbon group having 1 to 30 carbon atoms, an aromatic hydrocarbon group having 6 to 30 carbon atoms, or a group obtained by a combination thereof is more preferable, a saturated aliphatic hydrocarbon group having 1 to 10 carbon atoms, a group obtained by removing two or more hydrogen atoms from the benzene ring, or A group represented by a bond is more preferred.

Among these, when L ^RP1 is a divalent linking group (m = 1), L ^RP1 is preferably an alkylene group, an arylene group, an alkyleneoxy group, an alkyleneoxycarbonyl group, an alkylene carbamate group, or a group combining two or more thereof.

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

It is preferable that the said arylene group is an aromatic hydrocarbon group.

Moreover, it is preferable that it is a C6-C20 aromatic hydrocarbon group, and, as for the said arylene group, it is more preferable that it is a phenylene group.

As for carbon number of the alkylene group contained in the said alkyleneoxy group, alkyleneoxycarbonyl group, or an alkylene carbamate group, 2-20 are respectively preferable, and 2-10 are more preferable.

In formula (RP-1), the preferable aspect of X ^RP1 is the same as the preferable aspect of the radical polymerizable group in compound A described above.

In formula (RP-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.

In formula (1-2), the preferable aspect of R ^P1 is the same as the preferable aspect of R ^P1 in formula (1-1).

In formula (1-2), the preferable aspect of L ³ is the same as the preferable aspect when L ^RP1 in formula (RP-1) is a divalent linking group (m=1).

〔Molecular Weight〕

The molecular weight of Compound A is preferably 100 to 2,000, preferably 150 to 1500, and more preferably 200 to 900.

Specific examples of Compound A include, but are not limited to, the following compounds. In the following specific examples, subscripts in parentheses indicate the number of repetitions.

[Formula 34]

[Formula 35]

It is preferable that content of compound A with respect to the total solids of the resin composition of this invention is 1-40 mass %. The lower limit is more preferably 2% by mass or more, more preferably 3% by mass or more, and particularly preferably 5% by mass or more. It is more preferable that it is 30 mass % or less, and, as for an upper limit, it is still more preferable that it is 20 mass % or less.

Compound A 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 polymerizable compounds>

It is preferable that the resin composition of this invention further contains a polymeric compound different from the compound A mentioned above (it is also hereafter referred to as "another polymeric compound").

In particular, it is preferable to further include a compound different from the compound A (a radical crosslinking agent described later) as the radically polymerizable compound.

The other polymerizable compound is a compound having a polymerizable group and does not correspond to the compound A described above.

Specifically, the other polymerizable compound includes a compound having a radical polymerizable group but no urea bond, a compound having a radical polymerizable group and a urea bond but having an axis of symmetry, and a compound having one radical polymerizable group and a urea bond but not having any of a hydroxyl group, an alkyleneoxy group, an amide group, and a cyano group.

As another polymeric compound, a radical crosslinking agent or another crosslinking agent is mentioned, and it is preferable that a radical crosslinking agent is included.

[Radical Crosslinking Agent]

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

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

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

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

As the compound having two or more ethylenically unsaturated bonds, a compound having 2 to 15 ethylenically unsaturated bonds is preferable, a compound having 2 to 10 ethylenically unsaturated bonds is more preferable, and a compound having 2 to 6 is still more preferable.

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

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

Specific examples of the radical crosslinking agent include unsaturated carboxylic acids (e.g., acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.), esters thereof, and amides, preferably esters of unsaturated carboxylic acids with polyhydric alcohol compounds, and amides of unsaturated carboxylic acids with polyhydric amine compounds. In addition, an addition reaction product of an unsaturated carboxylic acid ester or amide having a nucleophilic substituent such as a hydroxy group, an amino group, or a sulfanyl group with monofunctional or polyfunctional isocyanates or epoxies, or a dehydration condensation reaction product of a monofunctional or polyfunctional carboxylic acid is also suitably used. Also suitable are addition reactants of unsaturated carboxylic acid esters or amides having an electrophilic substituent such as isocyanate group or epoxy group with monofunctional or polyfunctional alcohols, amines, or thiols, and substitution reactions of unsaturated carboxylic acid esters or amides having a leaving substituent such as halogeno or tosyloxy group 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 glycoldi(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, hexanedioldi(meth)acrylate, trimethylolpro Paint rye (acryloyloxypropyl) ether, tri (acryloyloxyethyl) isocyanurate, ethylene oxide or propylene oxide added to polyfunctional alcohols such as glycerin or trimethylolethane, and then (meth)acrylated compound, Japanese Patent Publication No. 48-041708, Japanese Patent Publication No. 50-006034, Japanese Patent Publication No. 51-037193 Polyfunctional acrylates and methacrylates, such as urethane (meth)acrylates as described in JP, polyester acrylates described in Japanese Patent Publication No. 48-064183, Japanese Patent Publication No. 49-043191, and Japanese Patent Publication No. 52-030490, epoxy acrylates that are reaction products of epoxy resins and (meth)acrylic acid, and mixtures thereof. 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 is possible to use a compound having a fluorene ring and having two or more groups having an ethylenically unsaturated bond, as described in Japanese Unexamined Patent Publication No. 2010-160418, Japanese Unexamined Patent Publication No. 2010-129825, Japanese Patent Publication No. 4364216, etc., and cardo resin.

In addition, as other examples, the specific unsaturated compounds described in Japanese Patent Publication No. 46-043946, Japanese Patent Publication No. 01-040337, and Japanese Patent Publication No. Hei 01-040336, and the vinylphosphonic acid type compound described in Japanese Unexamined Patent Publication No. Hei 02-025493, etc. are mentioned. 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.

Further, compounds described in Japanese Unexamined Patent Publication No. 10-062986 as formulas (1) and (2) together with specific examples thereof, obtained by adding ethylene oxide or propylene oxide to a polyfunctional alcohol and then (meth)acrylated compounds 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 product, KAYARAD D-330 (Nippon Kayaku Co., Ltd. product)), dipentaerythritol tetraacrylate (as a commercial product, KAYARAD D-320 (Nippon Kayaku Co., Ltd. product), A-TMMT (Shin Nakamura Chemical Industry Co., Ltd. product)), dipentaerythritol penta(meth)acrylate (Si As a commercial product, KAYARAD D-310 (manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol hexa(meth)acrylate (commercially available, KAYARAD DPHA (manufactured by Nippon Kayaku Co., Ltd.) and A-DPH (manufactured by Shin-Nakamura Chemical Industry Co., Ltd.)), and structures in which (meth)acryloyl groups thereof are bonded via an ethylene glycol residue or a propylene glycol residue are preferable. These oligomeric types can also be used.

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

As the radical crosslinking agent, urethane acrylates as described in Japanese Patent Publication No. 48-041708, Japanese Patent Application Publication No. 51-037193, Japanese Patent Publication No. 02-032293, and Japanese Patent Publication No. Hei 02-016765, Japanese Patent Publication No. 58-049860, Japanese Patent Publication No. 56-01 The urethane compounds having an ethylene oxide system skeleton described in No. 7654, Japanese Publication No. 62-039417, and Japanese Publication No. 62-039418 are also suitable. Further, as the radical crosslinking agent, compounds having an amino structure or a sulfide structure in the molecule described in Japanese Unexamined Patent Publication Nos. 63-277653, 63-260909, and 01-105238 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 a radical crosslinking agent obtained by reacting an unreacted hydroxy group of the aliphatic polyhydroxy compound with a non-aromatic carboxylic acid anhydride to have an acid group is more preferable. Particularly preferably, in a radical crosslinking agent obtained by reacting an unreacted hydroxyl group of an aliphatic polyhydroxy compound with a non-aromatic carboxylic acid anhydride to have an acid group, the aliphatic polyhydroxy compound is a compound of pentaerythritol or dipentaerythritol. As a commercial item, M-510, M-520 etc. are mentioned, for example as a Toagosei Co., Ltd. product polybasic acid modified acrylic oligomer.

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

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

Specific compounds include triethylene glycol diacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, tetraethylene glycol diacrylate, PEG (polyethylene glycol) 200 diacrylate, PEG200 dimethacrylate, PEG600 diacrylate, PEG600 dimethacrylate, polytetraethylene glycol diacrylate, and polytetraethylene glycol diacrylate. Methacrylate, neopentyl glycol diacrylate, neopentyl glycol dimethacrylate, 3-methyl-1,5-pentanediol diacrylate, 1,6-hexanediol diacrylate, 1,6-hexanediol dimethacrylate, dimethylol-tricyclodecane diacrylate, dimethylol-tricyclodecane dimethacrylate, Bisphenol A EO (ethylene oxide) adduct diacrylate, bisphenol A EO adduct dimethacrylate, bisphenol A PO (propylene oxide) adduct diacrylate, bisphenol A PO adduct dimethacrylate, 2-hydroxy-3-acryloyloxypropyl methacrylate, isocyanuric acid EO modified diacrylate, isocyanuric acid modified dimethacrylate, and others having a urethane bond A bifunctional acrylate or a bifunctional methacrylate having a urethane bond can be used. These can mix and use 2 or more types as needed.

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

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

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

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

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

[Other crosslinking agents]

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

In the present invention, the other crosslinking agent refers to a crosslinking agent other than the above-mentioned radical crosslinking agent, and is a photoacid generator or a compound having a plurality of groups in a molecule that promotes a reaction for forming a covalent bond with other compounds in the composition or reaction products thereof by photosensitization such as a photobase generator, and preferably a compound having a plurality of groups in a molecule that promotes a reaction for forming a covalent bond with other compounds in the composition or reaction products thereof by the action of an acid or base.

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

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

Examples of other crosslinking agents include compounds having a structure in which an amino group-containing compound such as melamine, glycoluril, urea, alkylene urea, or benzoguanamine is reacted with formaldehyde or formaldehyde and an alcohol to replace hydrogen atoms of the amino group with acyloxymethyl groups, methylol groups, or alkoxymethyl groups. 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 referred to as a melamine-based crosslinking agent, a crosslinking agent using glycoluril, urea, or an alkylene urea is referred to as a urea-based crosslinking agent, a crosslinking agent using alkylene urea is referred to as an alkylene urea-based crosslinking agent, and a crosslinking agent using benzoguanamine is referred to as a benzoguanamine-based crosslinking agent.

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

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

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

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

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

[Formula 36]

R ₁₀₀ represents an alkyl group or an acyl group.

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

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

[Formula 37]

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

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

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

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

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

The alkyl group may be linear or branched.

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

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

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

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

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

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

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

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

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

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

[Formula 38]

[Formula 39]

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

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

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

Specific examples of the urea-based crosslinking agent include monohydroxymethylation glycoluril, dihydroxymethylation glycoluril, trihydroxymethylation glycoluril, tetrahydroxymethylation glycoluril, monomethoxymethylation glycoluril, dimethoxymethylation glycoluril, trimethoxymethylation glycoluril, tetramethoxymethylation glycoluril, monoethoxymethylation glycoluril, and diethoxymethylation. Methylated glycoluril, triethoxymethylated glycoluril, tetraethoxymethylated glycoluril, monopropoxymethylated glycoluril, dipropoxymethylated glycoluril, tripropoxymethylated glycoluril, tetrapropoxymethylated glycoluril, monobutoxymethylated glycoluril, dibutoxymethylated glycoluril, tributoxymethylated glycoluril, or tetrabuu glycoluril type crosslinking agents such as toxymethylated glycoluril;

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

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

Propylene urea-based crosslinking agents such as monohydroxymethylated propylene urea, dihydroxymethylated propylene urea, monomethoxymethylated propylene urea, dimethoxymethylated propylene urea, monoethoxymethylated propylene urea, diethoxymethylated propylene urea, monopropoxymethylated propylene urea, 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-imidazolidinone, etc. are mentioned.

Specific examples of the benzoguanamine crosslinking agent include monohydroxymethylated benzoguanamine, dihydroxymethylated benzoguanamine, trihydroxymethylated benzoguanamine, tetrahydroxymethylated benzoguanamine, monomethoxymethylated benzoguanamine, dimethoxymethylated benzoguanamine, trimethoxymethylated benzoguanamine, tetramethoxymethylated benzoguanamine, and monoethoxy. Methylated benzoguanamine, diethoxymethylated benzoguanamine, triethoxymethylated benzoguanamine, tetraethoxymethylated benzoguanamine, monopropoxymethylated benzoguanamine, dipropoxymethylated benzoguanamine, tripropoxymethylated benzoguanamine, tetrapropoxymethylated benzoguanamine, monobutoxymethylated benzoguanamine, dibutoxymethylated benzo Guanamine, tributoxymethylation benzoguanamine, tetrabutoxymethylation benzoguanamine, etc. are mentioned.

In addition, as the 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) is also suitably used.

Specific examples of such compounds include benzenedimethanol, bis(hydroxymethyl)cresol, bis(hydroxymethyl)dimethoxybenzene, bis(hydroxymethyl)diphenyl ether, bis(hydroxymethyl)benzophenone, hydroxymethylphenyl hydroxymethylbenzoate, bis(hydroxymethyl)biphenyl, dimethylbis(hydroxymethyl)biphenyl, bis(methoxymethyl)benzene, bis(methoxymethyl)cresol, Bis(methoxymethyl)dimethoxybenzene, bis(methoxymethyl)diphenylether, 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-(trifluoromethyl)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, manufactured by Honshu Kagaku Kogyo), Nikalak (registered trademark; hereinafter the same) MX-290, Nikalak MX-280, Nikalak MX-270, Nikalak MX-279, Nikalak MW-100LM, Nikalak MX- 750LM (above, Sanwa Chemical Co., Ltd.) etc. are mentioned.

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

-Epoxy compound (compound having an epoxy group)-

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

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

As an example of an epoxy compound, it is bisphenol-A epoxy resin; bisphenol F-type epoxy resin; alkylene glycol type epoxy resins or polyhydric alcohol hydrocarbon type epoxy resins such as propylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, ethylene glycol diglycidyl ether, butylene glycol diglycidyl ether, hexamethylene glycol diglycidyl ether, and trimethylolpropane triglycidyl ether; polyalkylene glycol type epoxy resins such as polypropylene glycol diglycidyl ether; Epoxy group-containing silicones, such as polymethyl (glycidyloxypropyl) siloxane, etc. are mentioned, but are not limited to these. Specifically, Epiclon (registered trademark) 850-S, Epiclon (registered trademark) HP-4032, Epiclon (registered trademark) HP-7200, Epiclon (registered trademark) HP-820, Epiclon (registered trademark) HP-4700, Epiclon (registered trademark) HP-4770, Epiclon (registered trademark) EXA-830LVP, Epiclon (registered trademark) EXA-8183, Epiclon (registered trademark) EXA-8169, Epiclon (registered trademark) N-660, Epiclon (registered trademark) N-665-EXP-S, Epiclon (registered trademark) N-740 (above product names, manufactured by DIC Co., Ltd.), Rika Resin (registered trademark) BEO-20E, Rika Resin (registered trademark) BEO-60E, Rika Resin (registered trademark) HBE-100, Rika Resin (registered trademark) DME-100, Rika Resin (registered trademark) L-200 (trade name, manufactured by New Japan Rica Co., Ltd.), EP-4003S, EP-4000S, EP-4088S, EP-3950S (above product names, manufactured by ADEKA Co., Ltd.), Celoxide (registered trademark) 2021P, Celoxide (registered trademark) 2 081, Celloxide (registered trademark) 2000, EHPE3150, Epolyde (registered trademark) GT401, Epolide (registered trademark) PB4700, Epolide (registered trademark) PB3600 (above trade names, manufactured by Daicel Co., Ltd.), NC-3000, NC-3000-L, NC-3000-H, NC-3000-FH-75M, NC-31 BREN -S, BREN-10S (above brand name, Nippon Kayaku Co., Ltd. product), etc. are mentioned. Moreover, the following compounds are also used suitably.

[Formula 40]

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

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

-Oxetane compound (compound having an oxetanyl group)-

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

-Benzoxazine compound (compound having a benzoxazolyl group)-

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

Preferred examples of the benzoxazine compound include P-d-type benzoxazine, F-a-type benzoxazine (above, trade name, manufactured by Shikoku Kasei Kogyo Co., Ltd.), benzoxazine adducts of polyhydroxystyrene resins, and phenol novolak-type 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, more preferably 0.5 to 15% by mass, and particularly preferably 1.0 to 10% by mass, based on the total solid content of the resin composition of the present invention. 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.

[Polymerization initiator]

The resin composition of the present invention contains a radical polymerization initiator. The radical polymerization initiator is preferably a radical polymerization initiator capable of initiating polymerization by light and/or heat. In particular, it is preferable to include an optical radical polymerization initiator.

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

The photoradical polymerization initiator preferably contains at least one compound having a molar extinction coefficient of at least about 50 L·mol ^-1 ·cm ^-1 within a wavelength range of about 240 to 800 nm (preferably 330 to 500 nm). 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, halogenated hydrocarbon derivatives (e.g., compounds having a triazine skeleton, compounds having an oxadiazole skeleton, compounds having a trihalomethyl group, etc.), acylphosphine compounds such as acylphosphine oxide, oxime compounds such as hexaarylbiimidazole and oxime derivatives, organic peroxides, thio compounds, ketone compounds, aromatic onium salts, ketoxime ethers, α-aminoketone compounds such as aminoacetophenone, α-hydroxy ketone compounds such as hydroxyacetophenone, azo compounds, azide compounds, metallocene compounds, organoboron compounds, iron arene complexes, and the like. About these details, Paragraph 0165 of Unexamined-Japanese-Patent No. 2016-027357 - 0182 and Paragraph 0138 of International Publication No. 2015/199219 - description of 0151 can be considered into consideration, and this content is integrated in this specification. Moreover, Paragraphs 0065 to 0111 of Unexamined-Japanese-Patent No. 2014-130173, compounds described in Japanese Patent Publication No. 6301489, MATERIAL STAGE 37-60p, vol. 19, no. 3, the peroxide-based photopolymerization initiator described in 2019, the photopolymerization initiator described in International Publication No. 2018/221177, the photopolymerization initiator described in International Publication No. 2018/110179, the photopolymerization initiator described in Japanese Unexamined Patent Publication No. 2019-043864, the photopolymerization initiator described in Japanese Unexamined Patent Publication No. 2019-044030, The peroxide type initiator of Unexamined-Japanese-Patent No. 2019-167313 is mentioned, These content is also integrated in this specification.

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

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

Examples of the α-hydroxyketone initiator include Omnirad 184, Omnirad 1173, Omnirad 2959, Omnirad 127 (manufactured by IGM Resins B.V.), IRGACURE 184 (IRGACURE is a registered trademark), DAROCUR 1173, IRGACURE 500, IRGACURE-2959, and IRGACURE 127 (trade names: All made by BASF) can be used.

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

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

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

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

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

As specific examples of the oxime compound, the compound described in Japanese Unexamined Patent Publication No. 2001-233842, the compound described in Japanese Unexamined Patent Publication No. 2000-080068, the compound described in Japanese Unexamined Patent Publication No. 2006-342166, the compound described in J. C. S. Perkin II (1979, pp. 1653-1660), J. C. S. Perkin II (1979) . The compound described in No. 6, the compound described in International Publication No. 2015/152153, the compound described in International Publication No. 2017/051680, the compound described in Japanese Unexamined Patent Publication No. 2017-198865, the compound described in Paragraph Nos. 0025 to 0038 of International Publication No. 2017/164127, the compound described in International Publication No. 2013/167515 A compound etc. are mentioned, The content is integrated in this specification.

Preferable examples of the oxime compound include compounds having the following structures, 3-(benzoyloxy(imino))butan-2-one, 3-(acetoxy(imino))butan-2-one, 3-(propionyloxy(imino))butan-2-one, 2-(acetoxy(imino))pentan-3-one, 2-(acetoxy(imino))-1-phenylpropane- 1-one, 2-(benzoyloxy(imino))-1-phenylpropan-1-one, 3-((4-toluenesulfonyloxy)imino)butan-2-one, and 2-(ethoxycarbonyloxy(imino))-1-phenylpropan-1-one. In the resin composition of this invention, it is especially preferable to use an oxime compound (oxime type radical photopolymerization initiator) as an optical radical polymerization initiator. An oxime-based photoradical polymerization initiator has a linking group of >C=N-O-C(=O)- in its molecule.

[Formula 41]

As commercially available products, IRGACURE OXE 01, IRGACURE OXE 02, IRGACURE OXE 03, IRGACURE OXE 04 (above, manufactured by BASF), and Adeka Optomer N-1919 (manufactured by ADEKA Co., Ltd., photoradical polymerization initiator 2 described in Japanese Unexamined Patent Publication No. 2012-014052) are also suitably used. In addition, TR-PBG-304, TR-PBG-305 (manufactured by Changzhou Trolly New Electronic Materials Co., Ltd.), Adeka Arcs NCI-730, NCI-831 and Adeka Arcs NCI-930 (manufactured by ADEKA Co., Ltd.) can also be used. Also, DFI-091 (manufactured by Daito Chemicals Co., Ltd.) and SpeedCure PDO (manufactured by SARTOMER ARKEMA) can be used. Moreover, the oxime compound of the following structure can also be used.

[Formula 42]

As the radical photopolymerization initiator, an oxime compound having a fluorene ring can also be used. As a specific example of the oxime compound which has a fluorene ring, the compound of Unexamined-Japanese-Patent No. 2014-137466 and the compound of Unexamined-Japanese-Patent No. 6636081 are mentioned, The content of this is integrated in this specification.

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

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

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

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

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

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

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

[Formula 43]

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

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

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

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

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

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

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

Photoradical polymerization initiators, from the viewpoint of exposure sensitivity, trihalomethyltriazine compounds, benzyldimethylketal compounds, α-hydroxyketone compounds, α-aminoketone compounds, acylphosphine compounds, phosphine oxide compounds, metallocene compounds, oxime compounds, triarylimidazole dimers, onium salt compounds, benzothiazole compounds, benzophenone compounds, acetophenone compounds and their derivatives, cyclopentadiene-benzene-iron complexes And a compound selected from the group consisting of salts thereof, halomethyloxadiazole compounds, and 3-aryl-substituted coumarin compounds is preferred.

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

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

[Formula 44]

In formula (I), R^I00silver, an alkyl group of 1 to 20 carbon atoms, an alkyl group of 2 to 20 carbon atoms interrupted by one or more oxygen atoms, an alkoxy group of 1 to 12 carbon atoms, a phenyl group, or an alkyl group of 1 to 20 carbon atoms, an alkoxy group of 1 to 12 carbon atoms, a halogen atom, a cyclopentyl group, a cyclohexyl group, an alkenyl group of 2 to 12 carbon atoms, a carbon atom of 2 to 1 interrupted by one or more oxygen atoms A phenyl group substituted with at least one of an alkyl group of 8 and an alkyl group of 1 to 4 carbon atoms, or a biphenyl group, and R^I01silver, a group represented by formula (II), or R^I00is the same group as R^I02~R^I04are each independently an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, or a halogen atom.

[Formula 45]

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

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

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

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

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

[sensitizer]

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

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

Examples of the sensitizer include Michler's ketone, 4,4'-bis(diethylamino)benzophenone, 2,5-bis(4'-diethylaminobenzal)cyclopentane, 2,6-bis(4'-diethylaminobenzal)cyclohexanone, 2,6-bis(4'-diethylaminobenzal)-4-methylcyclohexanone, 4,4'-bis(dimethylamino)chalcone, 4,4'-bis(diethylamino)chalcone, p-dimethylaminocinnamylideneindanone, p-dimethylaminobenzylideneindanone, 2-(p-dimethylaminophenylbiphenylene)-benzothiazole, 2-(p-dimethylaminophenylvinylene)benzothiazole, 2-(p-dimethylaminophenylvinylene)isonaphthothiazole, 1,3-bis(4'-di Methylaminobenzal) 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-diethyl Aminocoumarin, 3-ethoxycarbonyl-7-diethylaminocoumarin (7-(diethylamino)coumarin-3-carboxylic acid ethyl), 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.

Moreover, you may use another sensitizing dye.

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

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

[Chain transfer agent]

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

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

When the resin composition of the present invention has a chain transfer agent, the content of the chain transfer agent is preferably 0.01 to 20 parts by mass, more preferably 0.1 to 10 parts by mass, and still more preferably 0.5 to 5 parts by mass, based on 100 parts by mass of the total solids of the resin composition of the present invention. 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.

<Base generator>

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

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

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

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

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

[Formula 46]

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

In formulas (B1) and (B2), as for Rb ¹ , Rb ² and Rb ³ , it is preferable that at least one of these includes a cyclic structure, and it is more preferable that at least two of them 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 more 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, and still more preferably 3 to 12), an alkenyl group (preferably 2 to 24 carbon atoms, more preferably 2 to 18, more preferably 3 to 12), an aryl group (preferably 6 to 22 carbon atoms, more preferably 6 to 18, and more preferably 6 to 1 0 is more preferable) or an arylalkyl group (preferably 7 to 25 carbon atoms, more preferably 7 to 19, and even 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 (preferably 1 to 24 carbon atoms, more preferably 2 to 18 carbon atoms, and still more preferably 3 to 12 carbon atoms) which may have a substituent, more preferably a cycloalkyl group (preferably 3 to 24 carbon atoms, more preferably 3 to 18 carbon atoms, and even more preferably 3 to 12 carbon atoms) which may have a substituent, and more preferably a cyclohexyl group which may have a substituent. Hands-on is more preferable.

Rb ³ 으로서는, 알킬기(탄소수 1~24가 바람직하고, 2~18이 보다 바람직하며, 3~12가 더 바람직하다), 아릴기(탄소수 6~22가 바람직하고, 6~18이 보다 바람직하며, 6~10이 더 바람직하다), 알켄일기(탄소수 2~24가 바람직하고, 2~12가 보다 바람직하며, 2~6이 더 바람직하다), 아릴알킬기(탄소수 7~23이 바람직하고, 7~19가 보다 바람직하며, 7~12가 더 바람직하다), 아릴알켄일기(탄소수 8~24가 바람직하고, 8~20이 보다 바람직하며, 8~16이 더 바람직하다), 알콕실기(탄소수 1~24가 바람직하고, 2~18이 보다 바람직하며, 3~12가 더 바람직하다), 아릴옥시기(탄소수 6~22가 바람직하고, 6~18이 보다 바람직하며, 6~12가 더 바람직하다), 또는 아릴알킬옥시기(탄소수 7~23이 바람직하고, 7~19가 보다 바람직하며, 7~12가 더 바람직하다)를 들 수 있다. 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 of exhibiting 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 47]

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

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

Rb ³⁵ is an alkyl group (preferably having 1 to 24 carbon atoms, more preferably 1 to 12, and still more preferably 3 to 8), an alkenyl group (preferably having 2 to 12 carbon atoms, more preferably 2 to 10, and still more preferably 3 to 8), an aryl group (preferably having 6 to 22 carbon atoms, more preferably 6 to 18, and still more preferably 6 to 12), an arylalkyl group ( 7-23 carbon atoms are preferable, 7-19 are more preferable, and 7-12 are still 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 48]

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

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

[Formula 49]

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

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

[Formula 50]

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

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

[Formula 51]

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

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

식 (N1) 중, R ^N1 및 R ^N2 는 각각 독립적으로 1가의 유기기(탄소수 1~24가 바람직하고, 2~18이 보다 바람직하며, 3~12가 더 바람직하다)를 나타내며, 탄화 수소기(탄소수 1~24가 바람직하고, 1~12가 보다 바람직하며, 1~10이 더 바람직하다)인 것이 바람직하고, 구체적으로는, 지방족 탄화 수소기(탄소수 1~24가 바람직하고, 1~12가 보다 바람직하며, 1~10이 더 바람직하다) 또는 방향족 탄화 수소기(탄소수 6~22가 바람직하고, 6~18이 보다 바람직하며, 6~10이 더 바람직하다)를 들 수 있으며, 지방족 탄화 수소기가 바람직하다. As R ^N1 and R ^N2 , it is preferable to use an aliphatic hydrocarbon group because the basicity of the generated base is high. In addition, the aliphatic hydrocarbon group and the aromatic hydrocarbon group may have a substituent, and the aliphatic hydrocarbon group and the aromatic hydrocarbon group may have an oxygen atom in the aliphatic hydrocarbon chain or in the aromatic ring or in the substituent. In particular, an aspect in which an aliphatic hydrocarbon group has an oxygen atom in a hydrocarbon chain is exemplified.

Examples of the aliphatic hydrocarbon group constituting R ^N1 and R ^N2 include a straight-chain or branched chain alkyl group, a cyclic alkyl group, a group related to a combination of a chain alkyl group and a cyclic alkyl group, and an alkyl group having an oxygen atom in the chain. The linear or branched chain alkyl group preferably has 1 to 24 carbon atoms, more preferably 2 to 18, still more preferably 3 to 12. Intangible or branching phase alkyl groups in a straight or branch, for example, methyl groups, ethyl groups, props, pentiles, hexyl groups, hepyl groups, octilline, uniline, decyl groups, mudisil, dodecil, isoprophase, iso viewililes, secondary liburgers Ki, Isohexyl groups are mentioned.

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

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

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

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

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

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

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

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

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

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

Specifically, as the linking group L, a straight-chain or branched chain alkylene group, a cyclic alkylene group, a group related to a combination of a chain-chain alkylene group and a cyclic alkylene group, an alkylene group having an oxygen atom in the chain, a straight-chain or branched chain alkenylene group, a cyclic alkenylene group, an arylene group, or an arylene alkylene group is preferable.

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

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

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

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

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

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

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

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

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

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

[Formula 52]

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

As a specific preferable compound of an ionic base generator, Paragraph No. 0148 of International Publication No. 2018/038002 - the compound of 0163 are also mentioned, for example.

Although the following compounds are mentioned as a specific example of an ammonium salt, this invention is not limited to these.

[Formula 53]

Although the following compounds are mentioned as a specific example of an iminium salt, this invention is not limited to these.

[Formula 54]

When the resin composition of the present invention contains a base generator, the content of the base generator is preferably 0.1 to 50 parts by mass relative to 100 parts by mass of the resin in the resin composition of the present invention. The lower limit is more preferably 0.3 parts by mass or more, and more preferably 0.5 parts by mass or more. The upper limit is more preferably 30 parts by mass or less, more preferably 20 parts by mass or less, still more preferably 10 parts by mass or less, may be 5 parts by mass or less, or may be 4 parts by mass or less.

1 type or 2 or more types can be used for a base generator. When using 2 or more types, it is preferable that the total amount is the said range.

<Solvent>

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

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

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

Ethers, for example, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether, diethylene glycol butyl methyl ether, triethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve Acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol dimethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether, ethylene glycol monobutyl ether acetate tate, diethylene glycol ethyl methyl ether, propylene glycol monopropyl ether acetate, dipropylene glycol dimethyl ether and the like are mentioned as suitable ones.

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

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

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

As amides, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N-cyclohexyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide, N,N-dimethylisobutylamide, 3-methoxy-N,N-dimethylpropionamide, 3-butoxy-N,N-dimethylpropionamide, N-formyl Morpholine, N-acetylmorpholine, etc. are mentioned as suitable ones.

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

As alcohols, methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 1-pentanol, 1-hexanol, benzyl alcohol, ethylene glycol monomethyl ether, 1-methoxy-2-propanol, 2-ethoxyethanol, diethylene glycol monoethyl ether, diethylene glycol monohexyl ether, triethylene glycol monomethyl ether, propylene glycol col monoethyl ether, propylene glycol monomethyl ether, polyethylene glycol monomethyl ether, polypropylene glycol, tetraethylene glycol, ethylene glycol monobutyl ether, ethylene glycol monobenzyl ether, ethylene glycol monophenyl ether, methylphenylcarbinol, n-amyl alcohol, methylamyl alcohol, and diacetone alcohol.

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-heptanone, cyclohexanone, cyclopentanone, γ-butyrolactone, dimethyl sulfoxide, ethyl carbitol acetate, butyl carby One solvent selected from tol acetate, N-methyl-2-pyrrolidone, propylene glycol methyl ether, and propylene glycol methyl ether acetate, levoglucosenone, and dihydrolevoglucosenone, or a mixed solvent composed of two or more kinds is preferred. A combination of dimethyl sulfoxide and γ-butyrolactone or a combination of N-methyl-2-pyrrolidone and ethyl lactate is particularly preferred.

The content of the solvent is preferably an amount such that the total solids concentration of the resin composition of the present invention is 5 to 80% by mass, more preferably 5 to 75% by mass, and more preferably 10 to 70% by mass, and still more preferably 20 to 70% by mass, from the viewpoint of coatability. What is necessary is just to adjust solvent content according to the desired thickness of a coating film, and a coating method.

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

<Metal Adhesion Improver>

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

[Silane coupling agent]

As a silane coupling agent, the compound of Paragraph 0167 of International Publication No. 2015/199219, the compound of Paragraph 0062 of Unexamined-Japanese-Patent No. 2014-191002 - the compound of 0073, the compound of Paragraph 0063 of International Publication No. 2011/080992 - 0071, the compound of Unexamined-Japanese-Patent No. 2014-19125, for example Paragraphs 0060 to 0061 of Paragraph 2, the compounds described in Paragraphs 0045 to 0052 of Unexamined-Japanese-Patent No. 2014-041264, the compounds described in Paragraph 0055 of International Publication No. 2014/097594, and the compounds described in Paragraphs 0067 to 0078 of Unexamined-Japanese-Patent No. 2018-173573, the contents of which are described herein. is used for Moreover, it is also preferable to use 2 or more types of silane coupling agents different as Paragraph 0050 of Unexamined-Japanese-Patent No. 2011-128358 - 0058 describe. Moreover, it is also preferable to use the following compound as a silane coupling agent. In the formulas below, Me represents a methyl group and Et represents an ethyl group.

[Formula 55]

Examples of other silane coupling agents include vinyltrimethoxysilane, vinyltriethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, and 3-glycidoxypropyltriethoxysilane. , p-styryltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane, N-2 -(Aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N-(1,3-dimethyl-butylidene)propylamine, N-phenyl-3-aminopropyltrimethoxysilane, tris-(trimethoxysilylpropyl)isocyanurate, 3-ureidopropyltrialkoxysyl Lane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-isocyanatepropyltriethoxysilane, and 3-trimethoxysilylpropylsuccinic anhydride. These can be used individually by 1 type or in combination of 2 or more types.

[Aluminum-based adhesive aid]

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

Moreover, as other metal adhesion improving agents, the compound described in Paragraph 0046 of Unexamined-Japanese-Patent No. 2014-186186 - 0049, and the sulfide-type compound of Paragraph 0032 - 0043 of Unexamined-Japanese-Patent No. 2013-072935 can also be used, These content is integrated in this specification.

The content of the metal adhesion improving agent is preferably 0.1 to 30 parts by mass, more preferably 0.1 to 10 parts by mass, and still more preferably 0.5 to 5 parts by mass, based on 100 parts by mass of the specific resin. By using the above lower limit or more, the adhesion between the pattern and the metal layer becomes good, and by using the above upper limit or less, the heat resistance and mechanical properties of the pattern become good. The metal adhesion improver may be one type or two or more types. When using 2 or more types, it is preferable that the sum total is the said range.

<Migration inhibitor>

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

The migration inhibitor is not particularly limited, but heterocyclic rings (pyrrole ring, furan ring, thiophene ring, imidazole ring, oxazole ring, thiazole ring, pyrazole ring, isoxazole ring, isothiazole ring, tetrazole ring, pyridine ring, pyridazine ring, pyrimidine ring, pyrazine ring, piperidine ring, piperazine ring, morpholine ring, 2H-pyran ring and 6H-pyran ring, triazine ring), compounds having thioureas and sulfanyl groups, hindered phenol-based compounds, salicylic acid derivative-based compounds, and hydrazide derivative-based compounds. In particular, triazole-based compounds such as 1,2,4-triazole, benzotriazole, 3-amino-1,2,4-triazole, and 3,5-diamino-1,2,4-triazole, and tetrazole-based compounds such as 1H-tetrazole, 5-phenyltetrazole, and 5-amino-1H-tetrazole can be preferably used.

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

As other migration inhibitors, the rust inhibitor described in Paragraph 0094 of Unexamined-Japanese-Patent No. 2013-015701, the compound described in Paragraphs 0073 to 0076 of Unexamined-Japanese-Patent No. 2009-283711, the compound described in Paragraph 0052 of Unexamined-Japanese-Patent No. 2011-059656, Paragraph of Unexamined-Japanese-Patent No. 2012-194520 The compound of 0114, 0116, and 0118, the compound of Paragraph 0166 of International Publication No. 2015/199219, etc. can be used, These content is integrated in this specification.

Specific examples of the migration inhibitor include the following compounds.

[Formula 56]

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

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

<Polymerization inhibitor>

It is preferable that the resin composition of this invention contains a polymerization inhibitor. Examples of the polymerization inhibitor include phenol-based compounds, quinone-based compounds, amino-based compounds, N-oxyl free radical compound-based compounds, nitro-based compounds, nitroso-based compounds, heteroaromatic compounds, and metal compounds.

Specific compounds of the polymerization inhibitor include p-hydroquinone, o-hydroquinone, o-methoxyphenol, p-methoxyphenol, di-tert-butyl-p-cresol, pyrogallol, p-tert-butylcatechol, 1,4-benzoquinone, diphenyl-p-benzoquinone, 4,4'-thiobis(3-methyl-6-tert-butylphenol), 2,2'-methylenebis(4-methyl- 6-tert-butylphenol), N-nitrosophenylhydroxyamine cerium salt, N-nitroso-N-phenylhydroxyamine aluminum salt, 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-nitroso-N-(1-naphthyl)hydroxyamine ammonium salt, bis(4-hydroxy-3,5-tert-butyl)phenylmethane, 1,3,5-tris(4-t-butyl-3-hydroxy-2 ,6-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 4-hydroxy-2,2,6,6-tetramethylpiperidine 1-oxyl free radical, 2,2,6,6-tetramethylpiperidine 1-oxyl free radical, phenothiazine, phenoxazine, 1,1-diphenyl-2-peak Lylhydrazyl, dibutyldithiocarbanate copper (II), nitrobenzene, N-nitroso-N-phenylhydroxylamine aluminum salt, N-nitroso-N-phenylhydroxylamine ammonium salt and the like are preferably used. Moreover, the polymerization inhibitor of Unexamined-Japanese-Patent No. 2015-127817, Paragraph 0060, and Paragraph 0031 of International Publication No. 2015/125469 - the compound of 0046 can also be used, The content is integrated in this specification.

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

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.

<Other additives>

In the resin composition of the present invention, various additives such as surfactants, higher fatty acid derivatives, thermal polymerization initiators, inorganic particles, ultraviolet absorbers, organic titanium compounds, antioxidants, aggregation inhibitors, phenolic compounds, other high molecular compounds, plasticizers, and other auxiliary agents (eg, antifoaming agents, flame retardants, etc.) By appropriately containing these components, properties such as membrane properties can be adjusted. For these components, for example, the description of paragraph No. 0183 of Japanese Unexamined Patent Publication No. 2012-003225 (paragraph No. 0237 of the corresponding US Patent Application Publication No. 2013/0034812), the description of paragraph Nos. , these contents are incorporated herein by reference. When blending these additives, the total compounding amount is preferably 3% by mass or less of the solid content of the resin composition of the present invention.

〔Surfactants〕

As surfactant, various surfactants, such as a fluorochemical surfactant, a silicone type surfactant, and a hydrocarbon type surfactant, can be used. The surfactant may be a nonionic surfactant, a cationic surfactant, or an anionic surfactant.

By incorporating a surfactant into the resin composition of the present invention, the liquid properties (particularly, fluidity) when prepared as a coating liquid are further improved, and the uniformity of the coating thickness and the liquid saving property can be further improved. That is, in the case of forming a film using a coating liquid to which a composition containing a surfactant is applied, the interfacial tension between the surface to be coated and the coating liquid is lowered, the wettability to the surface to be coated is improved, and the applicability to the surface to be coated is improved. For this reason, it is possible to more suitably form a film having a uniform thickness with little thickness unevenness.

As the fluorine-based surfactant, for example, Megafac F171, F172, F173, F176, F177, F141, F142, F143, F144, R30, F437, F475, F479, F482, F554, F780, RS-72-K (above, manufactured by DIC Corporation) ), Fluorad FC430, Copper FC431, Copper FC171, Novec FC4430, Copper FC4432 (above, manufactured by 3M Japan Co., Ltd.), Suffron S-382, Copper SC-101, Copper SC-103, Copper SC-104, Copper SC-105, Copper SC-1068, Copper SC-381, Copper SC-383, Copper S-393, Copper KH-40 (Above, Asahi Glass Co., Ltd. product), PF636, PF656, PF6320, PF6520, PF7002 (made by OMNOVA), etc. are mentioned. Paragraph 0015 of Unexamined-Japanese-Patent No. 2015-117327 - the compound of 0158 and Paragraph 0117 of Unexamined-Japanese-Patent No. 2011-132503 - the compound of 0132 can also be used for a fluorochemical surfactant, The content of these is integrated in this specification. A block polymer can also be used as a fluorochemical surfactant, and as a specific example, the compound of Unexamined-Japanese-Patent No. 2011-89090 is mentioned, for example, These content is integrated in this specification.

As the fluorine-based surfactant, a repeating unit derived from a (meth)acrylate compound having a fluorine atom and a repeating unit derived from a (meth)acrylate compound having 2 or more (preferably 5 or more) alkyleneoxy groups (preferably ethyleneoxy groups and propyleneoxy groups) can also be preferably used, and the following compounds are also exemplified as fluorine-based surfactants used in the present invention.

[Formula 57]

The weight average molecular weight of the above compound is preferably 3,000 to 50,000, and more preferably 5,000 to 30,000.

As the fluorochemical surfactant, a fluoropolymer having an ethylenically unsaturated group in the side chain may be used as the fluorochemical surfactant. As a specific example, Paragraph 0050 of Unexamined-Japanese-Patent No. 2010-164965 - 0090 and Paragraph 0289 - the compound of 0295 are mentioned, This content is integrated in this specification. Moreover, as a commercial item, DIC Corporation Megafac RS-101, RS-102, RS-718K etc. are mentioned, for example.

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

As the silicone surfactant, for example, Toray Silicone DC3PA, Toray Silicone SH7PA, Toray Silicone DC11PA, Toray Silicone SH21PA, Toray Silicone SH28PA, Toray Silicone SH29PA, Toray Silicone SH30PA, Toray Silicone SH8400 (above, manufactured by Toray Dow Corning Co., Ltd.), TSF-4440, TSF-4300, TSF-4445, TSF-4460, TSF -4452 (above, manufactured by Momentive Performance Materials Co., Ltd.), KP-341, KF6001, KF6002 (above, manufactured by Shin-Etsu Silicone Co., Ltd.), BYK307, BYK323, BYK330 (above, manufactured by Big Chemie Co., Ltd.), and the like.

As a hydrocarbon type surfactant, for example, Pionin A-76, Newcargen FS-3PG, Pionin B-709, Pionin B-811-N, Pionin D-1004, Pionin D-3104, Pionin D-3605, Pionin D-6112, Pionin D-2104-D, Pionin D-212, Pionin D-931, Pionin D-941, Pionin D-951, Pionin E-5310, Pionin P-1050-B, Pionin P-1028-P, Pionin P-4050-T (above, Takemoto Yushi Co., Ltd.), etc. are mentioned.

As the nonionic surfactant, glycerol, trimethylolpropane, trimethylolethane and their ethoxylates and propoxylates (eg, glycerol propoxylate, glycerol ethoxylate, etc.), polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, Sorbitan fatty acid ester etc. are illustrated. Commercially available products include Pluronic (registered trademark) L10, L31, L61, L62, 10R5, 17R2, 25R2 (manufactured by BASF), Tetronic 304, 701, 704, 901, 904, 150R1 (manufactured by BASF), Solsperse 20000 (manufactured by Nihon Lubrizol Co., Ltd.), NCW-101 .

As the cationic surfactant, specifically, organosiloxane polymer KP-341 (manufactured by Shin-Etsu Chemical Industry Co., Ltd.), (meth)acrylic acid-based (co)polymer Polyflow No. 75, no. 77, no. 90, no. 95 (made by Kyoeisha Chemical Co., Ltd.), W001 (made by Yusho Co., Ltd.), etc. are mentioned.

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

Surfactant may use only 1 type, and may combine 2 or more types.

The content of the surfactant is preferably 0.001 to 2.0% by mass, and more preferably 0.005 to 1.0% by mass, based on the total solid content of the composition.

[Higher Fatty Acid Derivatives]

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

Moreover, as a higher fatty acid derivative, the compound of Paragraph 0155 of International Publication No. 2015/199219 can also be used, and this content is integrated in this specification.

When the resin composition of the present invention has a higher fatty acid derivative, the content of the higher fatty acid derivative is preferably 0.1 to 10% by mass with respect to the total solid content of the resin composition of the present invention. 1 type of higher fatty acid derivative may be sufficient as it, and 2 or more types may be sufficient as it. When two or more types of higher fatty acid derivatives are used, it is preferable that the total is within the above range.

[Thermal polymerization initiator]

The resin composition of the present invention may contain a thermal polymerization initiator, and particularly may contain a thermal radical polymerization initiator. A thermal radical polymerization initiator is a compound that generates radicals by thermal energy to initiate or accelerate a polymerization reaction of a polymerizable compound. Since the polymerization reaction of resin and a polymeric compound can also advance by adding a thermal radical polymerization initiator, solvent resistance can be improved more. In addition, the photopolymerization initiator described above may also have a function of initiating polymerization by heat, and may be added as a thermal polymerization initiator.

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

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

[Inorganic Particles]

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

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

The average particle diameter of the fine particles is a primary particle diameter and is also a volume average particle diameter. The volume average particle size can be measured by a dynamic light scattering method using Nanotrac WAVE II EX-150 (manufactured by Nikkiso Co., Ltd.).

When the above measurement is difficult, it can also be measured by a centrifugal sedimentation light transmission method, an X-ray transmission method, or a laser diffraction/scattering method.

[Ultraviolet rays absorber]

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

Examples of the salicylate-based ultraviolet absorber include phenyl salicylate, p-octylphenyl salicylate, and p-t-butylphenyl salicylate. Hydroxy-4-methoxy benzophenone, 2,4-dihydroxy benzophenone, 2-hydroxy-4-octoxy benzophenone, etc. are mentioned. 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. Sol, 2-(2'-hydroxy-3'-isobutyl-5'-methylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-3'-isobutyl-5'-propylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-3',5'-di-tert-butylphenyl)benzotriazole, 2-(2'-hydroxy-5'-methylphenyl)benzotriazole , 2-[2'-hydroxy-5'-(1,1,3,3-tetramethyl)phenyl]benzotriazole, etc. are mentioned.

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. Examples of the triazine ultraviolet absorber include 2-[4-[(2-hydroxy-3-dodecyloxypropyl)oxy]-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2-[4-[(2-hydroxy-3-tridecyloxypropyl)oxy]-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3, mono(hydroxyphenyl)triazine compounds such as 5-triazine and 2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine; 2,4-bis(2-hydroxy-4-propyloxyphenyl)-6-(2,4-dimethylphenyl)-1,3,5-triazine, 2,4-bis(2-hydroxy-3-methyl-4-propyloxyphenyl)-6-(4-methylphenyl)-1,3,5-triazine, 2,4-bis(2-hydroxy-3-methyl-4-hexyloxyphenyl)-6-(2,4-dimethylphenyl) -bis(hydroxyphenyl)triazine compounds such as 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]-1,3,5-tri Tris (hydroxyphenyl) triazine compounds, such as azine, etc. are mentioned.

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, more preferably 0.01% by mass or more and 0.1% by mass or less, based on the total solid mass of the composition of the present invention.

[organic titanium compound]

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

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

Specific examples of organic titanium compounds are shown in I) to VII) below:

I) Titanium chelate compound: Especially, the titanium chelate compound which has 2 or more alkoxy groups is more preferable at the point from which the storage stability of a resin composition is favorable and a favorable curing pattern is obtained. Specific examples are titanium bis(triethanolamine)diisopropoxide, titanium di(n-butoxide)bis(2,4-pentanedionate), titanium diisopropoxide bis(2,4-pentanedionate), titanium diisopropoxide bis(tetramethylheptanedionate), titanium diisopropoxide bis(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 These include nium tetra(n-propoxide), titanium tetrastearyl oxide, titanium tetrakis[bis{2,2-(allyloxymethyl)butoxide}] and the like.

III) Titanocene compounds: For example, 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, etc. is

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

When blending an organic titanium compound, the compounding amount is preferably 0.05 to 10 parts by mass, more preferably 0.1 to 2 parts by mass, based on 100 parts by mass of the specific resin. When the compounding amount is 0.05 parts by mass or more, favorable heat resistance and chemical resistance are more effectively expressed in the resulting cured pattern, while when it is 10 parts by mass or less, the storage stability of the composition is more excellent.

[Antioxidant]

The composition of the present invention may contain an antioxidant. By containing an antioxidant as an additive, elongation characteristics of the film after curing and adhesion to a metal material can be improved. As an antioxidant, a phenol compound, a phosphite compound, a thioether compound, etc. are mentioned. As the phenolic compound, any phenolic compound known as a phenolic antioxidant can be used. As a preferable phenol compound, a hindered phenol compound is mentioned. A compound having a substituent at a site adjacent to the phenolic hydroxy group (ortho position) is preferred. As the substituent described above, a substituted or unsubstituted alkyl group having 1 to 22 carbon atoms is preferable. Further, the antioxidant is also preferably a compound having a phenol group and a phosphite ester group in the same molecule. Moreover, a phosphorus antioxidant can also be used suitably as an antioxidant. Phosphorus antioxidants include tris[2-[[2,4,8,10-tetrakis(1,1-dimethylethyl)dibenzo[d,f][1,3,2]dioxaphosphepin-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, ethyl bis(2,4-di-tert-butyl-6-methylphenyl) phosphite, and the like. Commercially available antioxidants include, for example, Adeka Stab AO-20, Adeka Stab AO-30, Adeka Stab AO-40, Adeka Stab AO-50, Adeka Stab AO-50F, Adeka Stab AO-60, Adeka Stab AO-60G, Adeka Stab AO-80, and Adeka Stab AO-330 (above, ADEKA Co., Ltd.) ) and the like. Moreover, the antioxidant can also use the compound of Paragraph No. 0023 of Unexamined-Japanese-Patent No. 6268967 - 0048, The content of this is integrated in this specification. Moreover, the composition of this invention may contain a latent antioxidant as needed. Examples of the latent antioxidant include a compound in which a site functioning as an antioxidant is protected with a protecting group, and the protective group is released by heating at 100 to 250° C. or at 80 to 200° C. in the presence of an acid/base catalyst to function as an antioxidant. As a latent antioxidant, the compound of international publication 2014/021023, international publication 2017/030005, and Unexamined-Japanese-Patent No. 2017-008219 is mentioned, The content of this is integrated in this specification. As a commercial item of a latent antioxidant, Adeka Akles GPA-5001 (made by ADEKA Corporation) etc. are mentioned.

Examples of preferable antioxidants include compounds represented by 2,2-thiobis(4-methyl-6-t-butylphenol), 2,6-di-t-butylphenol, and Formula (3).

[Formula 58]

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

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

Since it can act simultaneously on the resin and the metal material, k is more preferably an integer of 2 to 4. Examples of R7 include an alkyl group, a cycloalkyl group, an alkoxy group, an alkyl ether group, an alkylsilyl group, an alkoxysilyl group, an aryl group, an aryl ether group, a carboxyl group, a carbonyl group, an allyl group, a vinyl group, a heterocyclic group, -O-, -NH-, -NHNH-, combinations thereof, and the like, and may further have a substituent. Among them, those having an alkyl ether group or -NH- are preferable from the viewpoint of solubility in a developing solution or metal adhesion, and -NH- is more preferable from the viewpoint of interaction with resin and metal adhesion due to metal complexation.

Although the following are mentioned as an example of the compound represented by General formula (3), It is not limited to the following structure.

[Formula 59]

[Formula 60]

[Formula 61]

[Formula 62]

The addition amount of the antioxidant is preferably 0.1 to 10 parts by mass, more preferably 0.5 to 5 parts by mass, based on the resin. By setting the addition amount to 0.1 parts by mass or more, the effect of improving elongation properties and adhesion to metal materials is easily obtained even under a high temperature, high humidity environment, and by setting it to 10 parts by mass or less, for example, by interaction with a photosensitizer, the sensitivity of the resin composition is improved. Antioxidant may use only 1 type, and may use 2 or more types. When using 2 or more types, it is preferable that those total amounts become the said range.

[anti-agglomeration agent]

The resin composition of this embodiment may contain an aggregation inhibitor as needed. As an aggregation inhibitor, sodium polyacrylate etc. are mentioned.

In this invention, an aggregation inhibitor may be used individually by 1 type, and may be used in combination of 2 or more type.

The composition of the present invention may or may not contain an aggregation inhibitor, but when it is included, the content of the aggregation inhibitor is preferably 0.01% by mass or more and 10% by mass or less, more preferably 0.02% by mass or more and 5% by mass or less, based on the total solid mass of the composition of the present invention.

[phenolic compound]

The resin composition of this embodiment may contain a phenolic compound as needed. As the phenolic compound, Bis-Z, BisP-EZ, TekP-4HBPA, TrisP-HAP, TrisP-PA, BisOCHP-Z, BisP-MZ, BisP-PZ, BisP-IPZ, BisOCP-IPZ, BisP-CP, BisRS-2P, BisRS-3P, BisP-OCHP, methylenethris-FR-CR, BisRS-26X (above, Trade name, Honshu Chemical Co., Ltd. product), BIP-PC, BIR-PC, BIR-PTBP, BIR-BIPC-F (above, product name, Asahi Yukizai Kogyo Co., Ltd. product), etc. are mentioned.

In this invention, a phenol type compound may be used individually by 1 type, and may be used in combination of 2 or more type.

The composition of the present invention may or may not contain a phenolic compound, but when it is included, the content of the phenolic compound is preferably 0.01% by mass or more and 30% by mass or less, more preferably 0.02% by mass or more and 20% by mass or less, based on the total solid mass of the composition of the present invention.

[Other high molecular compounds]

Examples of other high molecular compounds include siloxane resins, (meth)acrylic polymers copolymerized with (meth)acrylic acid, novolak resins, resole resins, polyhydroxystyrene resins, copolymers thereof, and the like. The other high molecular compound may be a modified body into which a crosslinking group such as a methylol group, an alkoxymethyl group, or an epoxy group has been introduced.

In the present invention, the other high molecular compounds may be used singly or in combination of two or more.

The composition of the present invention may or may not contain other high molecular compounds, but when it is included, the content of the other high molecular compounds is preferably 0.01% by mass or more and 30% by mass or less, more preferably 0.02% by mass or more and 20% by mass or less, based on the total solid mass of the composition of the present invention.

<Characteristics of Resin Composition>

The viscosity of the resin composition of the present invention can be adjusted by the solid content concentration of the resin composition. From the viewpoint of the coating film thickness, 1,000 ^{mm 2} /s to 12,000 mm ² /s are preferable, 2,000 mm ² /s to 10,000 mm ² /s are more preferable, and 2,500 mm ² /s to 8,000 mm ² /s are still more preferable. It becomes easy to obtain a coating film with high uniformity in it being the said range. When it is 1,000 mm ² /s or more, it is easy to apply with a required film thickness as, for example, an insulating film for rewiring, and when it is 12,000 mm ² /s or less, a coating film excellent in coated surface is obtained.

<Restrictions on Materials Contained in Resin Composition>

The moisture content of the resin composition of the present invention is preferably less than 2.0% by mass, more preferably less than 1.5% by mass, and still more preferably less than 1.0% by mass. If it is less than 2.0%, the storage stability of the resin composition is improved.

As a method of maintaining the content of water, adjustment of humidity in storage conditions, reduction of the porosity of the container at the time of storage, etc. are mentioned.

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

In addition, as a method for reducing metal impurities unintentionally contained in the resin composition of the present invention, a raw material having a low metal content is selected as a raw material constituting the resin composition of the present invention, Filter filtration is performed on the raw material constituting the resin composition of the present invention, The inside of the apparatus is lined with polytetrafluoroethylene, etc., and contamination is suppressed as much as possible. Methods of distillation etc. are mentioned.

In the 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 even more preferably less than 200 ppm by mass, from the viewpoint of wiring corrosiveness. Especially, as for what exists in the state of a halogen ion, less than 5 mass ppm is preferable, less than 1 mass ppm is more preferable, and less than 0.5 mass ppm is still more preferable. As a halogen atom, a chlorine atom and a bromine atom are mentioned. It is preferable that the sum of chlorine atoms and bromine atoms, or chlorine ions and bromine ions, respectively is within the above range.

As a method of adjusting the content of halogen atoms, ion exchange treatment or the like is preferably used.

A conventionally well-known container can be used as a container for the resin composition of the present invention. In addition, as the container, for the purpose of suppressing the mixing of impurities into the raw materials or the resin composition of the present invention, it is also preferable to use a multi-layered bottle in which the inner wall of the container is composed of 6 types of 6-layer resins or a bottle in which 6 types of resins have a 7-layer structure. As such a container, the container of Unexamined-Japanese-Patent No. 2015-123351 is mentioned, for example.

<cured product of resin composition>

By curing the resin composition of the present invention, a cured product of this resin composition can be obtained.

The cured product of the present invention is a cured product formed by curing the resin composition of the present invention.

It is preferable that the resin composition is cured by heating, and the heating temperature is more preferably within the range of 120°C to 400°C, more preferably within the range of 140°C to 380°C, and particularly preferably within the range of 170°C to 350°C. The shape of the cured product of the resin composition is not particularly limited, and may be selected according to the application, such as a film shape, a rod shape, a spherical shape, or a pellet shape. In this invention, it is preferable that this hardened|cured material is film-like. In addition, by pattern processing of the resin composition, formation of a protective film on the wall surface, formation of via holes for conduction, adjustment of impedance, capacitance or internal stress, imparting a heat radiation function, etc. The shape of this cured product can also be selected according to the application. It is preferable that the film thickness of this hardened|cured material (film|membrane consisting of hardened|cured material) is 0.5 micrometer or more and 150 micrometer or less.

The shrinkage rate when the resin composition of the present invention is cured is preferably 50% or less, more preferably 45% or less, still more preferably 40% or less. Here, the shrinkage rate refers to the percentage of the volume change before and after curing of the resin composition, and can be calculated from the following formula.

Shrinkage rate [%] = 100 - (volume after curing ÷ volume before curing) × 100

<Characteristics of cured product of resin composition>

The imidation reaction rate of the cured product of the resin composition of the present invention is preferably 70% or more, more preferably 80% or more, and still more preferably 90% or more. When it is 70% or more, a cured product having excellent mechanical properties may be obtained.

The elongation at break of the cured product of the resin composition of the present invention is preferably 30% or more, more preferably 40% or more, and still more preferably 50% or more.

The glass transition temperature (Tg) of the cured product of the resin composition of the present invention is preferably 180°C or higher, more preferably 210°C or higher, and still more preferably 230°C or higher.

<Preparation of resin composition>

The resin composition of this invention can be prepared by mixing each said component. The mixing method is not particularly limited, and a conventionally known method can be used.

For the mixing, mixing by stirring blades, mixing by a ball mill, mixing by rotating the tank itself, or the like can be employed.

The temperature during mixing is preferably 10 to 30°C, more preferably 15 to 25°C.

Moreover, it is preferable to perform filtration using a filter for the purpose of removing foreign matters such as dust and fine particles in the resin composition of the present invention. As for the filter hole diameter, the aspect which is 5 micrometers or less is mentioned, for example, 1 micrometer or less is preferable, 0.5 micrometer or less is more preferable, and 0.1 micrometer or less is still more preferable. The material of the filter is preferably polytetrafluoroethylene, polyethylene or nylon. When the material of the filter is polyethylene, it is more preferably HDPE (high density polyethylene). As the filter, one previously washed with an organic solvent may be used. In the filter filtration process, you may connect and use multiple types of filters in series or parallel. In the case of using a plurality of types of filters, filters having different pore diameters or materials may be used in combination. As a connection aspect, the aspect which connected the HDPE filter with a pore diameter of 1 micrometer as a 1st stage|stage, and the HDPE filter with a pore diameter of 0.2 micrometer as a 2nd stage|stage was connected in series, for example. Moreover, you may filter various materials multiple times. When filtering multiple times, circulation filtration may be sufficient. Moreover, you may perform filtration by pressurizing. When filtration is performed by pressurization, the pressurized pressure can be, for example, 0.01 MPa or more and 1.0 MPa or less, preferably 0.03 MPa or more and 0.9 MPa or less, more preferably 0.05 MPa or more and 0.7 MPa or less, and more preferably 0.05 MPa or more and 0.5 MPa or less.

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

After filtration using a filter, the resin composition filled in the bottle may be further subjected to a step of degassing under reduced pressure.

(Method of producing cured product)

The method for producing a cured product of the present invention preferably includes a film forming step of forming a film by applying the resin composition onto a substrate.

Further, the method for producing a cured product of the present invention more preferably includes an exposure step of selectively exposing the film formed by the film formation step and the film formation step, and a developing step of forming a pattern by developing the film exposed by the exposure step using a developing solution.

The method for producing a cured product of the present invention includes at least one of the film forming step, the exposure step, the developing step, and a heating step of heating the pattern obtained by the developing step and a post-development exposure step of exposing the pattern obtained by the developing step.

Moreover, it is also preferable that the manufacturing method of this invention includes the said film formation process and the process of heating the said film|membrane.

Hereinafter, the detail of each process is demonstrated.

<Film formation process>

The resin composition of the present invention can be used in a film formation step of forming a film by applying it on a substrate.

The method for producing a cured product of the present invention preferably includes a film forming step of forming a film by applying the resin composition onto a substrate.

〔write〕

The type of substrate can be appropriately determined depending on the application, but a semiconductor production substrate such as silicon, silicon nitride, polysilicon, silicon oxide, amorphous silicon, quartz, glass, optical film, ceramic material, a vapor deposition film, a magnetic film, a reflective film, a metal substrate such as Ni, Cu, Cr, and Fe (for example, a substrate formed of metal or a substrate formed by plating or vapor deposition), paper, SOG (Spin On Glass), TFT (thin film transistor) array substrate, and mold A substrate, an electrode plate of a plasma display panel (PDP), and the like are exemplified, and are not particularly limited. In the present invention, semiconductor fabrication substrates are particularly preferred, and silicon substrates, Cu substrates, and mold substrates are more preferred.

In addition, layers such as an adhesion layer or an oxide layer by hexamethyldisilazane (HMDS) or the like may be provided on the surface of these substrates.

In addition, the shape of the substrate is not particularly limited, and may be circular or rectangular.

As the size of the substrate, if it is circular, the diameter is, for example, 100 to 450 mm, preferably 200 to 450 mm. If it is a rectangular shape, the length of a short side is 100-1000 mm, for example, Preferably it is 200-700 mm.

Moreover, as a base material, for example, a plate shape, preferably a panel shape base material (substrate) is used.

In the case of forming a film by applying a resin composition to the surface of a resin layer (for example, a layer made of a cured material) or the surface of a metal layer, the resin layer or metal layer serves as the base material.

As a means for applying the resin composition of the present invention onto a substrate, application is preferable.

Specific examples of the applied means include dip coating, air knife coating, curtain coating, wire bar coating, gravure coating, extrusion coating, spray coating, spin coating, slit coating, ink jetting and the like. From the viewpoint of film thickness uniformity, spin coating, slit coating, spray coating, or inkjet is more preferred. From the viewpoint of film thickness uniformity and productivity, spin coating and slit coating are preferred. A film having a desired thickness can be obtained by adjusting the solid content concentration of the resin composition and application conditions according to the method. In addition, the coating method can be appropriately selected depending on the shape of the substrate. For a circular substrate such as a wafer, a spin coating method, a spray coating method, an inkjet method, etc. are preferable, and a slit coating method, a spray coating method, an inkjet method, etc. are preferable for a rectangular substrate. In the case of the spin coating method, it can be applied for about 10 seconds to 3 minutes at a rotational speed of 500 to 3,500 rpm, for example.

Moreover, a method of transferring onto a base material a coating film applied and formed on a temporary support body in advance by the above application method can also be applied.

Regarding the transfer method, the production methods described in paragraphs 0023 and 0036 to 0051 of JP2006-023696 and paragraphs 0096 to 0108 of JP2006-047592 can be suitably used in the present invention.

Moreover, you may perform the process of removing an excess film|membrane in the edge part of a base material. Examples of such a process include edge bead rinse (EBR), back rinse, and the like.

Alternatively, a pre-wet process may be employed in which various solvents are applied to the substrate before the resin composition is applied to the substrate to improve wettability of the substrate, and then the resin composition is applied.

<Drying process>

The film may be subjected to a step of drying the formed film (layer) in order to remove the solvent after the film formation step (layer formation step) (drying step).

That is, the method for producing a cured product of the present invention may include a drying step of drying the film formed in the film formation step.

Moreover, it is preferable that the said drying process is performed after a film formation process and before an exposure process.

The drying temperature of the film in the drying step is preferably 50 to 150°C, more preferably 70°C to 130°C, still more preferably 90°C to 110°C. Moreover, you may dry by reduced pressure. As drying time, 30 seconds - 20 minutes are illustrated, 1 minute - 10 minutes are preferable, and 2 minutes - 7 minutes are more preferable.

<Exposure process>

The film may be subjected to an exposure step of selectively exposing the film.

That is, the manufacturing method of the hardened|cured material of this invention may also include the exposure process of selectively exposing the film|membrane formed by the film formation process.

Exposing selectively means exposing a part of the film. Further, by selective exposure, an exposed region (exposed portion) and an unexposed region (non-exposed portion) are formed in the film.

The exposure amount is not particularly determined as long as the resin composition of the present invention can be cured, but is preferably 50 to 10,000 mJ/cm ² and more preferably 200 to 8,000 mJ/cm ² in terms of exposure energy at a wavelength of 365 nm, for example.

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, three of (1) semiconductor laser (wavelength 830nm, 532nm, 488nm, 405nm, 375nm, 355nm etc.), (2) metal halide lamp, (3) high-pressure mercury lamp, g-line (wavelength 436nm), h-line (wavelength 405nm), i-line (wavelength 365nm), broadband (g, h, i-line) wavelength), (4) excimer laser, KrF excimer laser (wavelength 248 nm), ArF excimer laser (wavelength 193 nm), F ₂ excimer laser (wavelength 157 nm), (5) extreme ultraviolet; EUV (wavelength: 13.6 nm), (6) electron beam, (7) YAG laser second harmonic 532 nm, third harmonic 355 nm, and the like. Regarding the resin composition of the present invention, exposure by a high-pressure mercury lamp is particularly preferred, and exposure by i-line is particularly preferred. In this way, a particularly high exposure sensitivity can be obtained.

In addition, the method of exposure is not particularly limited, and any method is sufficient as long as at least a part of the film made of the resin composition of the present invention is exposed, but exposure using a photomask, exposure by a laser direct imaging method, and the like are exemplified.

<Post-exposure heating process>

The film may be subjected to a step of heating after exposure (post-exposure heating step).

That is, the method for producing a cured product of the present invention may include a post-exposure heating step of heating the film exposed in the exposure step.

The post-exposure heating step can be performed after the exposure step and before the developing step.

It is preferable that it is 50 degreeC - 140 degreeC, and, as for the heating temperature in the heating process after exposure, it is more preferable that it is 60 degreeC - 120 degreeC.

30 seconds - 300 minutes are preferable, and, as for the heating time in a heating process after exposure, 1 minute - 10 minutes are more preferable.

The temperature increase rate in the post-exposure heating step is preferably 1 to 12°C/minute, more preferably 2 to 10°C/minute, and still more preferably 3 to 10°C/minute from the temperature at the start of heating to the maximum heating temperature.

Moreover, you may change the temperature increase rate suitably in the middle of heating.

The heating means in the post-exposure heating step is not particularly limited, and a known hot plate, oven, infrared heater, or the like can be used.

Moreover, it is also preferable to carry out in the atmosphere of low oxygen concentration by flowing an inert gas, such as nitrogen, helium, and argon, at the time of heating.

<Development process>

The film after exposure may be subjected to a developing step in which a pattern is formed by developing using a developing solution.

That is, the method for producing a cured product of the present invention may include a developing step of forming a pattern by developing the film exposed in the exposure step using a developing solution. By carrying out development, one of the exposed part and the non-exposed part of the film|membrane is removed, and a pattern is formed.

Here, a phenomenon in which an unexposed portion of a film is removed by a developing process is referred to as a negative-type phenomenon, and a phenomenon in which an exposed portion of a film is removed by a developing process is referred to as a positive-type phenomenon.

〔developer〕

As a developing solution used in the developing process, an aqueous alkali solution or a developing solution containing an organic solvent is exemplified.

When the developing solution is an aqueous alkali solution, examples of basic compounds that the aqueous alkali solution may contain include inorganic alkalis, primary amines, secondary amines, tertiary amines, and quaternary ammonium salts, TMAH (tetramethylammonium hydroxide), potassium hydroxide, sodium carbonate, sodium hydroxide, sodium silicate, sodium metasilicate, ammonia, ethylamine, n-propylamine, diethylamine, di-n-butylamine, triethylamine, Methyldiethylamine, Dimethylethanolamine, Triethanolamine, Tetraethylammonium Hydroxide, Tetrapropylammonium Hydroxide, Tetrabutylammonium Hydroxide, Tetrapentylammonium Hydroxide, Tetrahexylammonium Hydroxide, Tetraoctylammonium Hydroxide, Ethyl Trimethylammonium Hydroxide, Butyl Trimethylammonium Hydroxide, Methyltriamylammonium Hydroxide, Dibutyl Dipentylammonium Hydroxide, Dimethylbis(2-hydroxyethyl ) Ammonium hydroxide, trimethylphenylammonium hydroxide, trimethylbenzylammonium hydroxide, triethylbenzylammonium hydroxide, pyrrole, and piperidine are preferable, and TMAH is more 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.

When the developing solution contains 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, alkyl Alkyl oxyacetates (e.g., alkyloxyacetate, ethyl alkyloxyacetate, butyl alkyloxyacetate (e.g., methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, etc.), 3-alkyloxypropionic acid alkyl esters (e.g., 3-alkyloxymethyl methylpropionate, 3-alkyloxyethylpropionate, etc. (e.g., 3-methoxypropionic acid) methyl, 3-methoxyethylpropionate, 3-ethoxymethylpropionate, 3-ethoxyethylpropionate, etc.), 2-alkyloxypropionate alkyl esters (e.g., 2-alkyloxymethylpropionate, 2-alkyloxyethylpropionate, 2-alkyloxypropylpropionate, etc. (e.g., 2-methoxymethylpropionate, 2-methoxypropionate) ethyl acid, 2-methoxypropylpropionate, 2-ethoxymethylpropionate, 2-ethoxyethylpropionate)), 2-alkyloxy-2-methylmethylpropionate and 2-alkyloxy-2-methylethylpropionate (e.g., 2-methoxy-2-methylmethylpropionate, 2-ethoxy-2-methylethylpropionate, etc.), methyl pyruvate, Ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutanoate, ethyl 2-oxobutanoate, etc., and as ethers, for example, diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, Ethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether (PGME), propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, etc., and ketones, for example, methyl ethyl ketone, cyclohexanone, cyclopentane On, 2-heptanone, 3-heptanone, N-methyl-2-pyrrolidone, etc., and as cyclic hydrocarbons, for example, aromatic hydrocarbons such as toluene, xylene, anisole, etc., cyclic terpenes such as limonene, dimethylsulfoxide as sulfoxides, and methanol, ethanol, propanol, isopropanol, butanol, pentanol, octanol, diethylene glycol as alcohols , propylene glycol, methyl isobutyl carbinol, triethylene glycol, etc., and, as amides, N-methylpyrrolidone, N-ethylpyrrolidone, dimethylformamide, etc. are mentioned suitably.

When the developing solution contains an organic solvent, the organic solvent can be used alone or in combination of two or more. In the present invention, a developer containing at least one selected from the group consisting of cyclopentanone, γ-butyrolactone, dimethylsulfoxide, N-methyl-2-pyrrolidone, and cyclohexanone is particularly preferred, a developer containing at least one selected from the group consisting of cyclopentanone, γ-butyrolactone and dimethylsulfoxide is more preferred, and a developer containing cyclopentanone is most preferred.

When the developing solution contains an organic solvent, the content of the organic solvent relative to the total mass of the developing solution is preferably 50% by mass or more, more preferably 70% by mass or more, still more preferably 80% by mass or more, and particularly preferably 90% by mass or more. Moreover, 100 mass % may be sufficient as the said content.

The developing solution may further contain other components.

As another component, a well-known surfactant, a well-known antifoaming agent, etc. are mentioned, for example.

[Supply Method of Developer]

The method of supplying the developer is not particularly limited as long as a desired pattern can be formed, and there is a method of immersing a film-formed substrate in a developer, a puddle phenomenon of supplying a developer to a film formed on 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 permeability 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 penetration of the developer into the image portion, a method of supplying the developer through a spray nozzle is more preferable.

Alternatively, after continuously supplying the developing solution with a straight nozzle, the substrate is spun to remove the developing solution from the substrate, and after spin drying, a step of continuously supplying the developing solution with the straight nozzle again and then spinning the substrate to remove the developing solution from the substrate may be employed, or this process may be repeated a plurality of times.

In addition, 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, and a combination thereof.

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

In the developing step, after the treatment using the developing solution, the pattern may be further washed (rinsed) with a rinsing solution. Moreover, you may employ|adopt the method of supplying a rinsing liquid while the developing solution which touches on a pattern is not completely dry.

[rinse liquid]

When the developing solution is an aqueous alkali solution, water can be used as a rinse solution, for example. When the developing solution is a developing solution containing an organic solvent, as the rinse solution, for example, a solvent different from the solvent contained in the developing solution (eg, water, an organic solvent different from the organic solvent contained in the developing solution) can be used.

Examples of the organic solvent in the case where 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, and δ-valerolac. Tone, alkyloxyacetate (e.g., methyl alkyloxyacetate, ethyl alkyloxyacetate, butyl alkyloxyacetate (e.g., methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, etc.), alkyl 3-alkyloxypropionic acid (e.g., methyl 3-alkyloxypropionate, ethyl 3-alkyloxypropionate, etc. (e.g., 3-methoxypropionate) methyl pionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, etc.), 2-alkyloxypropionate alkylesters (e.g.: 2-alkyloxymethylpropionate, 2-alkyloxyethylpropionate, 2-alkyloxypropyl propionate, etc. (e.g., 2-methoxymethylpropionate, 2-methoxy Ethyl propionate, 2-methoxypropylpropionate, 2-ethoxymethylpropionate, 2-ethoxyethylpropionate)), 2-alkyloxy-2-methylmethylpropionate and 2-alkyloxy-2-methylethylpropionate (e.g., 2-methoxy-2-methylmethylpropionate, 2-ethoxy-2-methylethylpropionate, etc.), pyruvic acid Methyl, 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 tate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether (PGME), propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, and the like, and ketones, for example, methyl ethyl ketone, cyclohexanone, cycles lopentanone, 2-heptanone, 3-heptanone, N-methyl-2-pyrrolidone, etc., and aromatic hydrocarbons such as toluene, xylene, anisole, etc. as cyclic hydrocarbons, cyclic terpenes such as limonene, dimethylsulfoxide as sulfoxides, and methanol, ethanol, propanol, isopropanol, butanol, pentanol, octanol, diethylene glycol as alcohols Lycol, propylene glycol, methyl isobutyl carbinol, triethylene glycol, etc., and, as amides, N-methylpyrrolidone, N-ethylpyrrolidone, dimethylformamide, etc. are mentioned suitably.

When the rinse liquid contains an organic solvent, the organic solvent can be used alone or in combination of two or more. In the present invention, cyclopentanone, γ-butyrolactone, dimethylsulfoxide, N-methylpyrrolidone, cyclohexanone, PGMEA and PGME are particularly preferred, cyclopentanone, γ-butyrolactone, dimethylsulfoxide, PGMEA and PGME are more preferred, and cyclohexanone and PGMEA are still more preferred.

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

The rinse liquid may further contain other components.

As another component, a well-known surfactant, a well-known antifoaming agent, etc. are mentioned, for example.

[How to supply rinse liquid]

The method of supplying the rinsing liquid is not particularly limited as long as a desired pattern can be formed, and there are a method of immersing the substrate in the rinsing liquid, a method of supplying the rinsing liquid to the substrate by raising the liquid, a method of supplying the rinsing liquid to the substrate through a shower, and a method of continuously supplying the rinse liquid onto the substrate by means such as a straight nozzle.

From the viewpoints of permeability of the rinsing liquid, removability of non-image areas, and manufacturing efficiency, there is a method of supplying the rinsing liquid through a shower nozzle, a straight nozzle, a spray nozzle, or the like. A method of continuously supplying the rinsing liquid through a spray nozzle is preferable. The type of nozzle is not particularly limited, and examples thereof include straight nozzles, shower nozzles, and spray nozzles.

That is, the rinsing step is preferably a step of supplying a rinsing liquid to the film after exposure through a straight nozzle or continuously supplying the rinsing liquid to the film after exposure, and more preferably a process of supplying the rinsing liquid through a spray nozzle.

Further, as a method for supplying the rinsing liquid in the rinsing step, a process in which the rinsing liquid is continuously supplied to the substrate, a process in which the rinsing liquid is maintained on the substrate in a substantially stationary state, a process in which the rinsing liquid is vibrated on the substrate with ultrasonic waves, and a combination thereof can be employed.

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

<Heating process>

The pattern obtained by the developing step (pattern after rinsing in the case of performing the rinsing step) may be subjected to a heating step of heating the pattern obtained by the above development.

That is, the manufacturing method of the hardened|cured material of this invention may also include the heating process of heating the pattern obtained by the image development process.

Further, the method for producing a cured product of the present invention may include a heating step of heating a pattern obtained by another method or a film obtained by the film forming step without performing the developing step.

In the heating step, resins such as polyimide precursors are cyclized to become resins such as polyimide.

Further, crosslinking of unreacted crosslinkable groups in specific resins or crosslinking agents other than specific resins also proceeds.

The heating temperature (maximum heating temperature) in the heating step is preferably 50 to 450°C, more preferably 150 to 350°C, still more preferably 150 to 250°C, still more preferably 160 to 250°C, and particularly preferably 160 to 230°C.

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

The heating in the heating step is preferably performed at a temperature rising rate of 1 to 12°C/min from the temperature at the start of heating to the highest heating temperature. The temperature increase rate is more preferably 2 to 10°C/minute, more preferably 3 to 10°C/minute. By setting the temperature increase rate to 1 ° C./min or more, excessive volatilization of the acid or solvent can be prevented while securing productivity, and by setting the temperature increase rate to 12 ° C./min or less, residual stress of the cured product can be relaxed.

In addition, in the case of an oven capable of rapid heating, the heating is preferably carried out at a heating rate of 1 to 8 ° C./sec from the temperature at the time of heating start to the maximum heating temperature, more preferably 2 to 7 ° C./sec, and more preferably 3 to 6 ° C./sec.

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 the resin composition of the present invention on a substrate, it is the temperature of the film (layer) after this drying, for example, 30 to 200 ° C. lower than the boiling point of the solvent contained in the resin composition of the present invention. It is preferable to raise the temperature.

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

In particular, in the case of forming a multilayer laminate, the heating temperature is preferably 30 ° C. or higher, more preferably 80 ° C. or higher, still more preferably 100 ° C. or higher, and particularly preferably 120 ° C. or higher, from the viewpoint of adhesion between layers.

The upper limit of the heating temperature is preferably 350°C or lower, more preferably 250°C or lower, and still more preferably 240°C or lower.

Heating may be performed stepwise. For example, steps such as raising the temperature from 25°C to 120°C at 3°C/min, holding at 120°C for 60 minutes, raising the temperature from 120°C to 180°C at 2°C/min and holding at 180°C for 120 minutes may be performed. Moreover, it is also preferable to process while irradiating an ultraviolet-ray as described in US Patent Publication No. 9159547. It is possible to improve the properties of the film by such a pretreatment process. What is necessary is just to perform a pretreatment process in a short time of about 10 second - about 2 hours, and 15 second - 30 minutes are more preferable. The pretreatment may be carried out in two or more stages, for example, the first stage pretreatment step may be performed in the range of 100 to 150 ° C., and then the second stage pretreatment step 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 carried out in an atmosphere of low oxygen concentration by flowing an inert gas such as nitrogen, helium, or argon or under reduced pressure to prevent decomposition of the specific resin. The oxygen concentration is preferably 50 ppm (volume ratio) or less, and more preferably 20 ppm (volume ratio) or less.

Although it does not specifically limit as a heating means in a heating process, For example, a hot plate, an infrared furnace, an electrothermal oven, a hot air oven, an infrared oven, etc. are mentioned.

<Exposure process after development>

The pattern obtained by the developing step (pattern after rinsing in the case of performing the rinsing step) may be subjected to a post-development exposure step for exposing the pattern after the developing step instead of or in addition to the heating step.

That is, the method for producing a cured product of the present invention may also include a post-development exposure step of exposing the pattern obtained by the developing step. The method for producing a cured product of the present invention may include a heating step and a post-development exposure step, or may include only one of the heating step and the post-development exposure step.

In the post-development exposure step, for example, a reaction in which cyclization of a polyimide precursor or the like advances can be promoted by photosensitization of a photobase generator.

In the post-development exposure process, at least a part of the pattern obtained in the development process may be exposed, but it is preferable that all of the patterns are exposed.

The exposure amount in the post-development exposure step is preferably 50 to 20,000 mJ/cm ² , more preferably 100 to 15,000 mJ/cm ² in terms of exposure energy at a wavelength to which the photosensitive compound has sensitivity.

The post-development exposure process can be performed using, for example, the light source in the exposure process described above, and broadband light is preferably used.

<Metal layer formation process>

The pattern obtained by the developing step (preferably provided in at least one of the heating step and the post-development exposure step) may be applied to a metal layer forming step of forming a metal layer on the pattern.

That is, the method for producing a cured product of the present invention preferably includes a metal layer forming step of forming a metal layer on a pattern obtained by the developing step (preferably provided in at least one of the heating step and the post-development exposure step).

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

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, Unexamined-Japanese-Patent No. 2004-101850, U.S. Patent No. 7888181B2, and U.S. Patent No. 9177926B2 can be used. For example, photolithography, PVD (Physical Vapor Deposition), CVD (Chemical Vapor Deposition), lift-off, electroplating, electroless plating, etching, printing, methods combining these, and the like can be considered. More specifically, a patterning method in which sputtering, photolithography and etching are combined, and a patterning method in which photolithography and electrolytic plating are combined are exemplified. As a preferable aspect of plating, electrolytic plating using a copper sulfate or copper cyanide plating solution is exemplified.

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

<Use>

Examples of the manufacturing method of the cured product of the present invention or applicable fields of the cured product of the present invention include insulating films for 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 these applications, for example, Science & Technology Co., Ltd. "High-functionality of polyimide and application technology" April 2008, Masaaki Kakimoto/supervisor, CMC Technical Library "Fundamentals and Development of Polyimide Materials" November 2011, published by the Japan Polyimide and Aromatic Polymer Research Association/edition "Latest Polyimide Basics and Applications" NTS, August 2010 month, etc.

In addition, the production method of the cured product of the present invention or the cured product of the present invention can also be used for production of a plate surface such as an offset board surface or screen board surface, use for etching of molded parts, and production of a protective lacquer and dielectric layer in electronics, particularly microelectronics.

(Laminate and manufacturing method of the laminate)

The laminate of the present invention refers to a structure having a plurality of layers comprising a cured product of the present invention.

The laminate of the present invention is a laminate comprising two or more layers of cured material, and may be a laminate of three or more layers.

Among the two or more layers of the cured material included in the laminate, at least one is a layer made of the cured material of the present invention, and from the viewpoint of suppressing shrinkage of the cured material or deformation of the cured material due to the shrinkage, it is also preferable that all layers made of the cured material included in the laminate are layers made of the cured material of the present invention.

That is, the manufacturing method of the laminate of the present invention preferably includes the manufacturing method of the cured product of the present invention, and more preferably includes repeating the manufacturing method of the cured product of the present invention a plurality of times.

It is preferable that the layered product of the present invention includes two or more layers of layers made of a cured product and includes a metal layer between any one of the layers made of the cured product. It is preferable that the said metal layer is formed by the said metal layer formation process.

That is, it is preferable that the manufacturing method of the laminated body of this invention further includes the metal layer formation process of forming a metal layer on the layer which consists of hardened|cured material between the manufacturing method of hardened|cured material performed multiple times. A preferable aspect of the metal layer forming process is as described above.

Preferable examples of the above-mentioned laminate include a laminate comprising at least a layered structure in which three layers of a layer made of a first cured material, a metal layer, and a layer made of a second cured material are laminated in this order.

It is preferable that both the layer composed of the first cured material and the layer composed of the second cured material are layers made of the cured material of the present invention. The resin composition of the present invention used for forming the layer composed of the first cured material and the resin composition of the present invention used for forming the layer composed of the second cured material may be compositions having the same composition or different compositions. The metal layer in the laminate of the present invention is preferably used as metal wiring such as a redistribution layer.

<Laminating process>

It is preferable that the manufacturing method of the laminated body of this invention includes a lamination process.

The lamination process is a series of steps including performing one of (a) film formation process (layer formation process), (b) exposure process, (c) development process, (d) heating process and post-development exposure process in this order on the surface of the pattern (resin layer) or metal layer. However, an aspect in which at least one of the film formation process of (a) and the heating process and post-development exposure process of (d) may be repeated. Moreover, you may include (e) metal layer formation process after at least one of (d) a heating process and a post-development exposure process. It goes without saying that the above drying step or the like may be appropriately further included in the lamination step.

When the lamination process is further performed after the lamination process, a surface activation treatment process may be further performed after the exposure process, the heating process, or the metal layer forming process. As the surface activation treatment, plasma treatment is exemplified. Details of the surface activation treatment will be described later.

It is preferable to perform the said lamination process 2 to 20 times, and it is more preferable to perform it 2 to 9 times.

For example, a resin layer/metal layer/resin layer/metal layer/resin layer/metal layer is preferably composed of 2 or more layers and 20 or less layers, and a configuration in which 2 or more layers and 9 layers or less is more preferable.

Each of the above layers may be the same or different in composition, shape, film thickness, and the like.

In this invention, after providing a metal layer especially, the aspect which further forms the hardened|cured material (resin layer) of the said resin composition of this invention so that the said metal layer may be covered is preferable. Specifically, (a) a film forming step, (b) an exposure step, (c) a developing step, (d) at least one of a heating step and an exposure step after development, (e) a metal layer forming step, or (a) a film forming step, (d) at least one of a heating step and a post-development exposure step, and (e) a metal layer forming step. By alternately performing the lamination step of laminating the resin composition layer (resin layer) of the present invention and the metal layer forming step, the resin composition layer (resin layer) of the present invention and the metal layer can be laminated alternately.

(Surface activation treatment process)

The method for producing a laminate of the present invention preferably includes a surface activation treatment step of subjecting at least a part of the metal layer and the resin composition layer to a surface activation treatment.

The surface activation treatment step is usually performed after the metal layer formation step, but after the development step (preferably after at least one of the heating step and the post-development exposure step), the resin composition layer is subjected to a surface activation treatment step, and then the metal layer formation step may be performed.

The surface activation treatment may be performed on at least a portion of the metal layer, at least a portion of the exposed resin composition layer, or on at least a portion of both the metal layer and the exposed resin composition layer. The surface activation treatment is preferably performed on at least a part of the metal layer, and it is preferable to perform the surface activation treatment on a part or all of the region where the resin composition layer is formed on the surface of the metal layer. In this way, by performing surface activation treatment on the surface of the metal layer, adhesion to the resin composition layer (film) provided on the surface can be improved.

In addition, it is preferable to perform the surface activation treatment also on a part or all of the resin composition layer (resin layer) after exposure. In this way, by subjecting the surface of the resin composition layer to surface activation treatment, adhesion to the metal layer or resin layer provided on the surface of the surface activation treatment can be improved. In particular, when the resin composition layer is cured, such as in the case of negative development, it is difficult to receive damage by surface treatment and the adhesion is easy to improve.

Specifically, as the surface activation treatment, 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} , etching treatment by NF ₃ /O 2 , surface treatment by ultraviolet (UV) ozone method, surface treatment by immersion in an aqueous hydrochloric acid solution to remove an oxide film, and then between amino groups It is selected from immersion treatment for an organic surface treatment agent containing a compound having at least one type of all group, mechanical roughening treatment using a brush, plasma treatment is preferred, and 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 .

(Semiconductor device and its manufacturing method)

The present invention also discloses a semiconductor device comprising the cured product of the present invention or the laminate of the present invention.

Further, the present invention also discloses a method for manufacturing a semiconductor device including the method for manufacturing a cured product of the present invention or the method for manufacturing a laminate of the present invention. As a specific example of a semiconductor device using the resin composition of the present invention for forming an interlayer insulating film for a redistribution layer, the description of paragraphs 0213 to 0218 of Japanese Unexamined Patent Publication No. 2016-027357 and the description of FIG. 1 can be referred to, and these contents are 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 of Compound A>

[Synthesis of CS-1]

In a flask equipped with a stirrer and a condenser, 27.44 g (200 mmol) of 2-(4-aminophenyl)ethyl alcohol (manufactured by Tokyo Kasei Kogyo Co., Ltd.) and 0.03 g of p-methoxyphenol (manufactured by Tokyo Kasei Kogyo Co., Ltd.) were dissolved in 250 mL of tetrahydrofuran and cooled to 0°C. Next, 29.48 g (190 mmol) of Karenz MOI (manufactured by Showa Denko Co., Ltd.) was added dropwise over 1 hour, stirred at 0°C to 10°C for 1 hour, then heated to 25°C and stirred for 2 hours. Subsequently, this was crystallized in a solution of 800 mL of ethyl acetate/200 mL of hexane, and filtered. Subsequently, the filtrate was stirred with 500 mL of ethyl acetate for 1 hour and filtered. This was dried at 45 degreeC for 24 hours, and 45g of CS-1 was obtained. It was confirmed from ¹ H-NMR spectrum that it was CS-1. The structure of CS-1 is shown by the following formula (CS-1).

[Formula 63]

[Synthesis of CS-2 to CS-4]

In the same way, CS-2 to CS-4 were synthesized. The structures of CS-2 to CS-4 are shown in formulas (CS-2) to (CS-4) below.

[Formula 64]

[Synthesis of CS-5]

In a flask equipped with a stirrer and a condenser, 14.6 g (50 mmol) of CS-1 synthesized above, 0.005 g of p-methoxyphenol (manufactured by Tokyo Kasei Kogyo Co., Ltd.), and 4.75 g of pyridine (manufactured by Tokyo Kasei Kogyo Co., Ltd.) were dissolved in 80 mL of tetrahydrofuran (manufactured by Tokyo Kasei Kogyo Co., Ltd.) and cooled to 0 ° C. Subsequently, 5.75 g (55 mmol) of methacrylic acid chloride (manufactured by Tokyo Kasei Kogyo Co., Ltd.) was added dropwise over 1 hour, stirred at 0°C to 10°C for 1 hour, then heated to 25°C and stirred for 2 hours. Subsequently, this was dissolved in 800 mL of ethyl acetate and transferred to a separatory funnel. This was washed with 300 mL of water, 300 mL of diluted hydrochloric acid, 300 mL of saturated sodium bicarbonate, and saturated brine, dried over magnesium sulfate, filtered, the solvent was removed with an evaporator, and dried at 45 ° C. for 24 hours to obtain 15 g of CS-5. It was confirmed from the ¹ H-NMR spectrum that it was CS-5. The structure of CS-5 is shown by the following formula (CS-5).

[Formula 65]

[Synthesis of CS-6 to CS-15]

In the synthesis of CS-5, CS-6 to CS-15 were synthesized in the same manner except that methacrylic acid chloride was changed to another acid halide or isocyanate compound. The structures of CS-6 to CS-15 are shown in the following formulas (CS-6) to formula (CS-15).

[Formula 66]

[Synthesis of CS-16]

In a flask equipped with a stirrer and a condenser, 27.42 g (200 mmol) of 4-aminobenzoic acid (manufactured by Tokyo Kasei Kogyo Co., Ltd.) and 0.03 g of p-methoxyphenol (manufactured by Tokyo Kasei Kogyo Co., Ltd.) were dissolved in 250 mL of tetrahydrofuran, and cooled to 0 ° C. Next, 41.83 g (210 mmol) of Karenz MOI-EG (manufactured by Showa Denko Co., Ltd.) was added dropwise over 1 hour, stirred at 0°C to 10°C for 1 hour, then heated to 25°C and stirred for 2 hours. Subsequently, this was crystallized in 700 mL of ethyl acetate/300 mL of hexane, and filtered. This was transferred to a flask equipped with a stirrer and a condenser, and dissolved in 250 mL of tetrahydrofuran. Next, 30.6 g (160 mmol) of 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride (manufactured by Tokyo Kasei Kogyo Co., Ltd.), 19.5 g (150 mmol) 2-hydroxyethyl methacrylate (manufactured by Tokyo Kasei Kogyo Co., Ltd.), 0.6 g (5 mmol) of 4-dimethylaminopyridine (manufactured by Tokyo Kasei Kogyo Co., Ltd.) added. This was stirred at 25°C for 3 hours, dissolved in 600 mL of ethyl acetate, and transferred to a separatory funnel. This was washed with 300 mL of water, 300 mL of dilute hydrochloric acid, 500 mL of saturated sodium bicarbonate, and saturated saline, dried over magnesium sulfate and filtered, then the solvent was removed with an evaporator to obtain 40 g of CS-16. It was confirmed from ¹ H-NMR spectrum that it was CS-16. The structure of CS-16 is shown by the following formula (CS-16).

[Formula 67]

[Synthesis of CS-17 to CS-24]

CS-17 to CS-24 were synthesized in the same manner as in the synthesis of CS-16. The structures of CS-17 to CS-24 are shown in the following formulas (CS-17) to formula (CS-24). In the structure below, subscripts in parentheses indicate the number of repetitions.

[Formula 68]

[Synthesis of CS-25 to CS-27]

CS-25 to CS-27 were synthesized in the same manner as in CS-1, except that the reaction temperature was 50°C using trade name: Neostan U-600 (manufactured by Nitto Kasei) as a bismuth catalyst. The structures of CS-25 to CS-27 are shown in the following formulas (CS-25) to formula (CS-27).

[Formula 69]

[Synthesis of CS-28 to CS-31]

CS-28 was synthesized in the same manner as in CS-5 described above. CS-29 was synthesized by the same method as in CS-1 described above. In addition, CS-30 to CS-31 were synthesized in the same manner as in CS-16 described above. The structures of CS-28 to CS-31 are shown in the following formulas (CS-28) to formula (CS-31).

[Formula 70]

[Synthesis of CS-32 to CS-33]

CS-32 to CS-33 were synthesized in the same manner as in CS-1 described above. The structures of CS-32 to CS-33 are shown in the following formulas (CS-32) to formula (CS-33).

[Formula 71]

(Synthesis of cyclized resin or its precursor)

<Synthesis Example A-1: Synthesis of polybenzoxazole precursor A-1 from 2,2'-bis(3-amino-4-hydroxyphenyl)hexafluoropropane and 4,4'-oxydibenzoyl chloride>

28.0 g (76.4 mmol) of 2,2'-bis(3-amino-4-hydroxyphenyl)hexafluoropropane was stirred and dissolved in 200 g of N-methylpyrrolidone. Subsequently, 12.1 g (153 mmol) of pyridine was added, and a solution in which 20.7 g (70.1 mmol) of 4,4'-oxydibenzoyl chloride was dissolved in 75 g of N-methylpyrrolidone was added dropwise over 1 hour while maintaining the temperature at -10 to 0 ° C. After stirring for 30 minutes, 1.00 g (12.7 mmol) of acetyl chloride was added, and the mixture was further stirred for 60 minutes. Next, the polybenzoxazole precursor resin was precipitated in 6 liters of water, and the water-polybenzoxazole precursor resin mixture was stirred at a speed of 500 rpm for 15 minutes. The polybenzoxazole precursor resin was filtered off, stirred again in 6 liters of water for 30 minutes, and filtered again. Next, the obtained polybenzoxazole precursor resin was dried under reduced pressure at 45°C for 3 days to obtain polybenzoxazole precursor A-1. This polybenzoxazole precursor A-1 was weight average molecular weight (Mw) = 21500 and number average molecular weight (Mn) = 9500.

The structure of the polybenzoxazole precursor A-1 is estimated to be a structure represented by the following formula (A-1).

[Formula 72]

<Synthesis Example A-2: Synthesis of polyimide>

In a flask equipped with a condenser and stirrer, while removing moisture, 26.0 g (50 mmol) of 4,4'-(4,4'-isopropylidenediphenoxy)bis(phthalic anhydride) (manufactured by Tokyo Kasei Kogyo Co., Ltd.) and 0.02 g of 2,2,6,6-tetramethylpiperidine 1-oxyl free radical (manufactured by Tokyo Kasei Kogyo Co., Ltd.) were added to N-methyl It was dissolved in 120.0 g of pyrrolidone (NMP). Subsequently, 11.9 g (45 mmol) of diamine (AA-1) described below was added, and the mixture was stirred at 25°C for 3 hours and further stirred at 45°C for 3 hours. Then, 15.8 g (200 mmol) of pyridine, 12.8 g (125 mmol) of acetic anhydride, and 50 g of N-methylpyrrolidone (NMP) were added, and stirred at 80 ° C. for 3 hours. 50 g of N-methylpyrrolidone (NMP) was added and diluted.

This reaction liquid was precipitated in 1 liter of methanol and stirred for 15 minutes at a speed of 3000 rpm. The resin was 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 A-2. The molecular weight of A-2 was Mw=21,000 and Mn=9,100.

It is estimated that the structure of polyimide A-2 is a structure represented by following formula (A-2).

[Formula 73]

[Synthesis Example AA-1: Synthesis of diamine AA-1]

In a flask equipped with a condenser and stirrer, 26.0 g (0.2 mol) of 2-hydroxyethyl methacrylate (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) and 17.4 g (0.22 mol) of dehydrated pyridine (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) were dissolved in 78 g of ethyl acetate, and cooled to 5° C. or less. Next, 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 the solution was added dropwise into the flask over 1 hour using a dropping funnel. After completion of the dropwise addition, the mixture was stirred at 10°C or lower for 30 minutes, heated up to 25°C, and stirred for 3 hours. Subsequently, 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.), 3.0 g (50 mmol) of acetic acid (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), 2,2,6,6-tetramethylpiperidine 1-oxyl 0.03 g of free radical (manufactured by Tokyo Kasei Kogyo Co., Ltd.) was weighed, and 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 outside temperature was raised to 85°C, stirred for 2 hours, cooled to 25°C or lower, and filtered using Celite (registered trademark). The filtrate was concentrated with a rotary evaporator and dissolved in 800 mL of ethyl acetate. This was transferred to a separatory funnel, and washed twice with 300 mL of saturated sodium bicarbonate, followed by washing with 300 mL of water and 300 mL of saturated saline in that order. After liquid separation and washing, drying with 30 g of magnesium sulfate, concentration and vacuum drying were performed using an evaporator to obtain 11.0 g of diamine (AA-1).

[Formula 74]

<Synthesis Example A-3: Synthesis of Polyimide Precursor (A-3)>

[Synthesis of polyimide precursor (A-3: polyimide precursor having radical polymerizable group) from 4,4'-oxydiphthalic dianhydride, 4,4'-diaminodiphenyl ether and 2-hydroxyethyl methacrylate]

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, 20.4 g (258 mmol) of pyridine, and 100 g of diglyme were mixed, and The mixture was stirred at the temperature for 18 hours to prepare a diester of 4,4'-oxydiphthalic acid and 2-hydroxyethyl methacrylate. Subsequently, after chlorination of the obtained diester with SOCl ₂ , it was converted into a polyimide precursor with 4,4′-diaminodiphenyl ether in the same manner as in Synthesis Example A-5, and a polyimide precursor (A-3) was obtained in the same manner as in Synthesis Example A-5. The weight average molecular weight of this polyimide precursor was 19,600.

The structure of A-3 is estimated to be a structure represented by the following formula (A-3).

[Formula 75]

<Synthesis Example A-4: Synthesis of Polyimide Precursor (A-4)>

[Synthesis of polyimide precursor (A-4: polyimide precursor having a radical polymerizable group) from 4,4'-oxydiphthalic dianhydride, 4,4'-diamino-2,2'-dimethylbiphenyl (orthotolidine) and 2-hydroxyethyl methacrylate]

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, 20.4 g (258 mmol) of pyridine, and 100 g of diglyme were mixed, and The mixture was stirred at the temperature for 18 hours to prepare a diester of 4,4'-oxydiphthalic acid and 2-hydroxyethyl methacrylate. Subsequently, the resulting diester was chlorinated with SOCl ₂ , and then converted into a polyimide precursor with 4,4'-diamino-2,2'-dimethylbiphenyl in the same manner as in Synthesis Example A-5, and a polyimide precursor (A-4) was obtained in the same manner as in Synthesis Example A-5. The weight average molecular weight of this polyimide precursor was 23,500.

The structure of A-4 is estimated to be a structure represented by the following formula (A-4).

[Formula 76]

<Synthesis Example A-5: Synthesis of Polyimide Precursor (A-5)>

[A-5: Synthesis of polyimide precursor resin A-5 from oxydiphthalic dianhydride, 4,4'-biphthalic anhydride, 2-hydroxyethyl methacrylate and 4,4'-diaminodiphenyl ether]

9.49 g (32.25 mmol) of 4,4'-biphthalic anhydride and 10.0 g (32.25 mmol) of oxydiphthalic dianhydride were suspended in 140 mL of diglyme while removing moisture in a drying reactor equipped with a flat-bottomed joint equipped with a stirrer, condenser and internal thermometer. 16.8 g (129 mmol) of 2-hydroxyethyl methacrylate, 0.05 g of hydroquinone, 0.05 g of pure water, and 10.7 g (135 mmol) of pyridine were successively added, and the mixture was stirred at a temperature of 60°C for 18 hours. After the mixture was then cooled to -20°C, 16.1 g (135.5 mmol) of thionyl chloride was added dropwise over 90 minutes. A white precipitate of pyridinium hydrochloride was obtained. Then, after warming the mixture to room temperature and stirring for 2 hours, 9.7 g (123 mmol) of pyridine and 25 mL of N-methylpyrrolidone (NMP) were added to obtain a clear solution. Subsequently, a solution of 11.8 g (58.7 mmol) of 4,4'-diaminodiphenyl ether in 100 mL of NMP was added dropwise over 1 hour to the resulting transparent solution. 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 a polyimide precursor (A-5). The weight average molecular weight of the obtained polyimide precursor A-5 was 23,800, and the number average molecular weight was 10,400.

The structure of A-5 is estimated to be a structure represented by the following formula (A-5).

[Formula 77]

<Synthesis Example A-6>

[A-6: Synthesis of polyimide precursor (A-6: polyimide precursor having a radical polymerizable group) 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 due to the reaction, it was allowed to cool to room temperature and was further left still for 16 hours.

Next, under ice-cooling, a solution in which 206.3 g of dicyclohexylcarbodiimide (DCC) was dissolved in 180 ml of γ-butyrolactone was added to the reaction mixture over 40 minutes while stirring. Subsequently, a suspension obtained by suspending 93.0 g of 4,4'-diaminodiphenyl ether in 350 ml of γ-butyrolactone was added over 60 minutes while stirring. Furthermore, after stirring at room temperature for 2 hours, 30 ml of ethyl alcohol was added and stirred for 1 hour. After that, 400 ml of γ-butyrolactone was added. A precipitate generated in the reaction mixture was collected by filtration to obtain a reaction liquid.

The obtained reaction liquid was added to 3 liters of ethyl alcohol to produce a precipitate composed of a crude polymer. The resulting crude polymer was collected by filtration and dissolved in 1.5 liters of tetrahydrofuran to obtain a crude polymer solution. The obtained crude polymer solution was dropped into 28 liters of water to precipitate the polymer, and the obtained precipitate was collected by filtration and vacuum dried to obtain a powdery polymer A-6. It was 24,000 as a result of measuring the weight average molecular weight (Mw) of this polymer A-6.

<Synthesis Example A-7>

[Synthesis of polyimide precursor (A-7: polyimide precursor having a radical polymerizable group) from 3,3',4,4'-biphenyltetracarboxylic dianhydride, 4,4'-diaminodiphenyl ether, and 2-hydroxyethyl methacrylate]

Polymer A-7 was obtained by reacting in the same manner as in Synthesis Example A-6, except that 147.1 g of 3,3',4,4'-biphenyltetracarboxylic dianhydride was used instead of 155.1 g of 4,4'-oxydiphthalic dianhydride in Synthesis Example 6. It was 22,900 as a result of measuring the weight average molecular weight (Mw) of this polymer A-7.

<Synthesis Example A-8>

In a flask equipped with a stirrer and a condenser, 19.19 g (36.7 mmol) of 4,4'-(4,4'-isopropylidenediphenoxy) diphthalic anhydride (manufactured by Tokyo Kasei Kogyo Co., Ltd.), 0.01 g of 4-methoxyphenol (manufactured by Tokyo Kasei Kogyo Co., Ltd.), 21.98 g (75 mmol) of CS-1 (above synthetic product), 12.92 g (163 mmol) of pyridine and 40.0 g of diethylene glycol dimethyl ether (manufactured by Tokyo Kasei Kogyo Co., Ltd.) were mixed and stirred at a temperature of 60°C for 6 hours. Subsequently, after cooling the mixture to -20°C, 9.19 g (76.3 mmol) of thionyl chloride was added dropwise over 90 minutes, followed by stirring for 2 hours. Next, 25 mL of N-methylpyrrolidone (NMP) was added, and a solution of 6.11 g (30.5 mmol) of 4,4'-diaminodiphenyl ether in 100 mL of NMP was added dropwise over 2 hours. Then, 16.9 g (367 mmol) of ethanol was 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 2 days under reduced pressure to obtain a polyimide precursor (A-8). The weight average molecular weight of obtained polyimide precursor A-8 was 30,100, and the number average molecular weight was 13,800.

The structure of A-8 is presumed to be a structure represented by the following formula (A-8).

[Formula 78]

<Synthesis of Comparative Compound C-1>

In a flask equipped with a stirrer and a condenser, 10.24 g (110 mmol) of aniline (manufactured by Tokyo Kasei Kogyo Co., Ltd.) was dissolved in 100 g of tetrahydrofuran, and cooled to 10°C. Next, 11.9 g (100 mmol) of phenyl isocyanate (manufactured by Tokyo Kasei Kogyo Co., Ltd.) was added dropwise over 1 hour, and stirred at 25°C for 2 hours. This was crystallized in 500 mL of 1N hydrochloric acid aqueous solution, filtered, reslurried with water, and dried at 50°C for 24 hours to obtain 18 g of C-1. It was confirmed from the ¹ H-NMR spectrum that it was C-1. The structure of C-1 is shown by the following formula (C-1).

[Formula 79]

<Examples and Comparative Examples>

In each Example, each resin composition was obtained by mixing the components described in the table below, respectively. Moreover, in each comparative example, each component for comparison was obtained by mixing the components described in the table below, respectively.

Specifically, the content of each component described in the table was made into the amount (parts by mass) described in the column "additional amount" of each column of the table.

The obtained resin composition and comparative composition were subjected to pressure filtration using a filter made of polytetrafluoroethylene having a fine pore width of 0.5 μm.

In addition, in the table|surface, description of "-" shows that the composition does not contain the component concerned.

[Table 1]

[Table 2]

[Table 3]

The detail of each component described in the table|surface is as follows.

[Resin (cyclized resin or its precursor)]

A-1 to A-8: A-1 to A-8 synthesized above

[Polymerization initiator (all brand names)]

・OXE-01: IRGACURE OXE 01 (manufactured by BASF)

・OXE-02: IRGACURE OXE 02 (manufactured by BASF)

[Compound A]

CS-1 to CS-33: synthetic products above

C-1: the above synthetic product

[base generator]

D-1 to D-2: Compounds with the following structures

D-3: WPBG-027 (manufactured by Fujifilm Wako Junyaku Co., Ltd.)

[Formula 80]

[migration inhibitor]

E-1 to E-6: Compounds with the following structures

[Formula 81]

[Metal Adhesion Improver]

F-1 to F-3: Compounds with the following structures

[Formula 82]

[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)

ADPH: dipentaerythritol hexaacrylate (manufactured by Shin-Nakamura Chemical Industry Co., Ltd.)

[Polymerization inhibitor]

G-1: 1,4-benzoquinone

G-2: 4-methoxyphenol

G-3: 1,4-dihydroxybenzene

G-4: a compound having the following structure

[Formula 83]

[Other additives]

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

〔solvent〕

DMSO: dimethyl sulfoxide

GBL: γ-butyrolactone

NMP: N-methylpyrrolidone

In the table, description of "DMSO/GBL" indicates that a mixture of DMSO and GBL was used in a mixing ratio (mass ratio) of DMSO:GBL = 80:20.

<evaluation>

[Evaluation of breaking elongation]

In each Example and Comparative Example, a resin composition layer was formed by applying a resin composition or a comparative composition on a silicon wafer by a spin coating method, respectively. The silicon wafer to which the obtained resin composition layer was applied was dried on a hot plate at 100° C. for 5 minutes to obtain a resin composition layer having a uniform thickness of about 15 μm on the silicon wafer.

The entire surface of the obtained resin composition layer was subjected to i-line exposure at an exposure energy of 500 mJ/cm ² using a stepper (Nikon NSR 2005 i9C).

The resin composition layer (resin layer) after exposure was heated at a heating rate of 10° C./min in a nitrogen atmosphere to reach the temperature described in the “temperature” column of “curing conditions” in the table, and then heated for 3 hours. The cured resin layer (cured film) was immersed in a 4.9% by mass hydrofluoric acid aqueous solution, and the cured film was peeled from the silicon wafer. The peeled cured film was punched out using a punching machine to prepare a test piece having a test width of 3 mm and a sample length of 30 mm. The resulting test piece was measured using a tensile tester (Tensilon) at a cross head speed of 300 mm/min under an environment of 25°C and 65% RH (relative humidity) at break in accordance with JIS-K6251 in the longitudinal direction of the test piece. The evaluation was performed 5 times each, and the arithmetic average value was used as an index value for the elongation rate (elongation rate at break) when the test piece broke.

The index value was evaluated according to the following evaluation criteria, and the evaluation result was described in the "elongation at break" column of the table. It can be said that the film strength (breaking elongation) of the cured film obtained is excellent, so that the said index value is large.

(Evaluation standard)

A: The index value was 60% or more.

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

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

D: The index value was less than 50%.

[Evaluation of chemical resistance]

Each resin composition or comparative composition prepared in each Example and Comparative Example was applied on a silicon wafer by a spin coating method, respectively, to form a resin composition layer. The silicon wafer to which the obtained resin composition layer was applied was dried on a hot plate at 100°C for 5 minutes to form a resin composition layer having a uniform thickness of 15 µm on the silicon wafer. The resin composition layer on the silicone wafer is used, using a stepper (NIKON NSR 2005 I9C), using an exposure energy of 500 mj/cm ² , and an expensive, expensive resin composition layer (resin layer), under the temperature of 10 ° C./minutes under the nitrogen atmosphere, and 180 minutes at the temperature of the "temperature" column of the table "curing condition". Liver heated to obtain a curing layer (resin layer) of the resin composition layer.

The obtained resin layer was immersed in the following chemical solution under the following conditions, and the dissolution rate was calculated.

Chemical solution: 90:10 (mass ratio) mixture of dimethyl sulfoxide (DMSO) and 25% by mass tetramethylammonium hydroxide (TMAH) aqueous solution

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

Evaluation was performed according to the following evaluation criteria, and the evaluation results were described in the "chemical resistance" column of the table. It can be said that the lower the dissolution rate, the better the chemical resistance.

-Evaluation standard-

A: The dissolution rate was less than 200 nm/min.

B: The dissolution rate was 200 nm/min or more and less than 300 nm/min.

C: The dissolution rate was 300 nm/min or more and less than 400 nm/min.

D: The dissolution rate was 400 nm/min or more.

[Evaluation of developer solubility (developability)]

The developer solubility evaluation was performed as follows.

Each resin composition or comparative composition prepared in each Example and each Comparative Example was applied on a silicon wafer by a spin coating method, respectively, to form a resin composition layer.

The silicon wafer to which the obtained resin composition layer was applied was dried on a hot plate at 100° C. for 5 minutes to obtain a resin composition layer having a uniform thickness of 35 μm on the silicon wafer.

The resin composition layer on the silicon wafer was exposed with an i-line at an exposure energy of 500 mJ/cm ² using a stepper (Nikon NSR 2005 i9C). The exposure was performed using a binary mask having a 1:1 line and space pattern having a width of 50 μm, a width of 70 μm, or a width of 100 μm.

In the example described as "solvent (cyclopentanone)" in the "developing method (developer)" column of the table, shower development was performed using cyclopentanone at 30 ° C. as a developer for the resin composition layer after exposure, and rinsing with PGMEA (propylene glycol monomethyl ether acetate) was performed.

In the example described as "alkali (TMAH)" in the "developing method (developer)" column of the table, the resin composition layer after exposure was developed using a 2.38% by mass tetramethylammonium hydroxide aqueous solution at 30 ° C. as a developer, and rinsed with ion-exchanged water.

At the time of exposure, using a 1: 1 line and space (L / S) pattern with a width of 100 μm, the minimum required time for dissolution of the unexposed portion when the thickness of the resin composition layer was 35 μm was set as the minimum development time, and evaluated according to the following evaluation criteria. It can be said that the shorter the minimum developing time, the better the solubility in the developing solution. The evaluation result was described in the "developability" column of the table|surface.

-Evaluation standard-

A: The minimum developing time was within 30 seconds.

B: The said minimum developing time was more than 30 second and less than 60 second.

C: The minimum developing time was more than 60 seconds and within 120 seconds.

D: Not completely dissolved at 120 seconds.

From the above results, it can be seen that the cured film comprising the resin composition according to the present invention is excellent in chemical resistance.

The comparative compositions according to Comparative Examples 1 to 4 do not contain Compound A.

It turns out that the cured film which consists of such a composition for comparison is inferior to chemical resistance.

<Example 101>

The resin composition used in Example 1 was applied layer by layer to the surface of the copper foil layer of the resin substrate having a copper foil layer formed on the surface by a spin coating method, dried at 100 ° C. for 4 minutes, and a film thickness of 20 μm After forming a resin composition layer, it was exposed using a stepper (manufactured by Nikon Co., Ltd., NSR1505 i6). 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, and after reaching 230°C, the temperature was maintained at 230°C for 3 hours to form an interlayer insulating film for a redistribution layer. This interlayer insulating film for the redistribution layer was excellent in insulating properties.

In addition, as a result of manufacturing semiconductor devices using these interlayer insulating films for redistribution layers, it was confirmed that they operated without problems.

Claims (13)

A cyclization resin or a precursor thereof;
a radical polymerization initiator, and
Contains a radically polymerizable compound;
The radically polymerizable compound includes compound A having a urea bond and not having an axis of symmetry,
The compound A is a resin composition that satisfies at least one of condition 1 and condition 2 below;
Condition 1: Compound A has two or more radical polymerizable groups;
Condition 2: Compound A has at least one selected from the group consisting of a hydroxy group, an alkyleneoxy group, an amide group and a cyano group. The method of claim 1,
The said cyclization resin or its precursor is at least 1 resin selected from the group which consists of polyimide, a polyimide precursor, polybenzoxazole, a polybenzoxazole precursor, polyamideimide, and a polyamideimide precursor, The resin composition. According to claim 1 or claim 2,
The resin composition whose acid value of the said cyclization resin or its precursor is 0 mmol/g - 1.2 mmol/g. The method according to any one of claims 1 to 3,
The resin composition in which the said compound A contains an aromatic group. The method according to any one of claims 1 to 4,
A resin composition further comprising a compound different from the compound A as the radically polymerizable compound. The method according to any one of claims 1 to 5,
The resin composition in which the said compound A is a compound represented by following formula (1-1) or formula (1-2).
[Formula 1]

In formula (1-1), R ^P1 and R ^P2 each independently represent a group containing at least one radical polymerizable group;
In Formula (1-2), R ^P1 represents a group containing at least one radical polymerizable group, and L ³ represents a divalent linking group. The method according to any one of claims 1 to 5,
A resin composition used for forming an interlayer insulating film for a redistribution layer. A cured product formed by curing the resin composition according to any one of claims 1 to 7. A laminate comprising two or more layers of layers comprising a cured material according to claim 8 and including a metal layer between any one of the layers comprising the cured material. A method for producing a cured product comprising a film formation step of applying the resin composition according to any one of claims 1 to 7 on a substrate to form a film. The method of claim 10,
A method for producing a cured product comprising: an exposure step of selectively exposing the film to light and a developing step of forming a pattern by developing the film using a developing solution. According to claim 10 or claim 11,
A method for producing a cured product comprising a heating step of heating the film to 50 to 450 ° C. A semiconductor device comprising the cured product according to claim 8 or the laminate according to claim 9.