TWI882163B - Curable resin composition, cured product, laminate, method for manufacturing cured product, and semiconductor device - Google Patents

Abstract

The present invention provides a curable resin composition, a cured product obtained by curing the curable resin composition, a laminate comprising the cured product, a method for producing the cured product, and a semiconductor device comprising the cured product or the laminate. The curable resin composition comprises at least one resin selected from the group consisting of a polyimide precursor and a polybenzoxazole precursor, and a compound B having at least one structure selected from the group consisting of an oxalic acid monoester structure, an oxalic acid diester structure, an oxalic acid monoamide structure, an oxalic acid diamide structure, and an oxalate amide structure and a polymerizable group.

Description

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

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

唑由於耐熱性及絕緣性等優異，因此適用於各種用途。作為上述用途並無特別限定，但是若舉出實際安裝用半導體元件為例，則可以舉出作為絕緣膜或密封材料的材料或保護膜的利用。又，亦可以用作撓性基板的基底膜或覆蓋膜等。 Polyimide or polybenzo

Azoles are suitable for various applications due to their excellent heat resistance and insulation properties. The above applications are not particularly limited, but if semiconductor devices for actual mounting are taken as an example, they can be used as materials for insulating films or sealing materials or protective films. In addition, they can also be used as base films or cover films of flexible substrates.

唑以包含選自包括聚醯亞胺前驅物及聚苯并

唑前驅物之群組中的至少1種樹脂之硬化性樹脂組成物的形態使用。 For example, in the above-mentioned applications, polyimide or polybenzo

The azole may include a compound selected from the group consisting of a polyimide precursor and a polybenzoic acid.

At least one resin in the group of azole promotors is used in the form of a curable resin composition.

This curable resin composition is applied to a substrate, for example, by coating to form a resin film, and then exposed, developed, heated, etc. as needed to form a cured product on the substrate.

唑前驅物例如藉由加熱而環化，在硬化物中分別成為聚醯亞胺、聚苯并

唑。 The polyimide precursor, the polybenzoic acid

The azole precursor is cyclized by heating, for example, and becomes polyimide, polybenzoic acid,

Azole.

唑等所具有之高性能以外，從該種製造上的適應性優異之觀點考慮，越來越期待上述硬化性樹脂組成物在產業上的應用開發。 The curable resin composition can be applied by a known coating method, so it can be said that the manufacturing adaptability is excellent. For example, the curable resin composition has a high degree of freedom in designing the shape, size, and application position of the curable resin composition when applied.

In addition to the high performance of azoles, etc., from the perspective of excellent adaptability in manufacturing, the above-mentioned curable resin composition is increasingly expected to be developed for industrial application.

For example, Patent Document 1 describes a photosensitive resin composition comprising a polyimide precursor, at least one resin in the polyimide, and at least one (meth)acrylic urethane ester, wherein the (meth)acrylic urethane ester has a specific partial structure, 4 to 15 (meth)acrylate groups, and a urethane structure in one molecule.

[Patent Document 1] International Publication No. 2017/131037

唑前驅物之群組中的至少1種樹脂之硬化性樹脂組成物中，要求提高所獲得之硬化物的耐藥品性。 In the mixture comprising a pre-driver selected from the group consisting of polyimide and polybenzo

In a curable resin composition comprising at least one resin in a group of azole promotors, it is required to improve the chemical resistance of the obtained cured product.

The purpose of the present invention is to provide a hardening resin composition that can obtain a hardened product with excellent chemical resistance, a hardened product obtained by hardening the hardening resin composition, a laminate containing the hardened product, a method for manufacturing the hardened product, and a semiconductor element containing the hardened product or the laminate.

Representative examples of the present invention are shown below.

唑前驅物之群組中的至少1種樹脂以及具有選自包括草酸單酯結構、草酸二酯結構、草酸單醯胺結構、草酸二醯胺結構及草酸酯醯胺結構之群組中的至少1種結構和聚合性基之化合物B。 <1> A hardening resin composition comprising a polyimide precursor and a polybenzoic acid

At least one resin from the group of oxalic acid proto-initiators and a compound B having at least one structure selected from the group consisting of an oxalic acid monoester structure, an oxalic acid diester structure, an oxalic acid monoamide structure, an oxalic acid diamide structure and an oxalate amide structure and a polymerizable group.

<2> The curable resin composition as described in <1>, wherein the compound B is a compound represented by the following formula (1).

^X1 and ^X2 are independently -O- or -NZ-, Z is a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms, ^R2 is a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms, and ^R1 represents a monovalent organic group including a polymerizable group.

<3> The curable resin composition as described in <1> or <2>, wherein the polymerizable group is a free radical polymerizable group.

<4> The curable resin composition as described in any one of <1> to <3>, further comprising at least one of a photopolymerization initiator and a thermal polymerization initiator.

<5> The curable resin composition as described in any one of <1> to <3>, further comprising a photopolymerization initiator.

<6> A curable resin composition as described in any one of <1> to <5>, wherein the resin comprises a repeating unit represented by formula (2).

In formula (2), ^A1 and ^A2 each independently represent an oxygen atom or -NH-, ^R111 represents a divalent organic group, ^R115 represents a tetravalent organic group, and ^R113 and ^R114 each independently represent a hydrogen atom or a monovalent organic group.

<7> A curable resin composition as described in any one of <1> to <6>, which is used to form an interlayer insulating film for a redistribution layer.

<8> A hardened material obtained by hardening the hardening resin composition described in any one of <1> to <7>.

<9> A laminate comprising two or more layers formed of the hardened material described in <8>, and a metal layer between any of the layers formed of the hardened material.

<10> A method for producing a cured product, comprising a film forming step of applying the curable resin composition described in any one of <1> to <7> to a substrate to form a film.

<11> The method for producing a cured product as described in <10> comprises an exposure step of selectively exposing the film and a development step of developing the film using a developer to form a pattern.

<12> The method for producing a cured product as described in <10> or <11>, comprising a heating step of heating the film at 50-450°C.

<13> A semiconductor device comprising the hardened material described in <8> or the laminated body described in <9>.

According to the present invention, there are provided a curable resin composition capable of obtaining a cured product having excellent chemical resistance, a cured product obtained by curing the curable resin composition, a laminate containing the cured product, a method for manufacturing the cured product, and a semiconductor element containing the cured product or the laminate.

The main implementation forms of the present invention are described below. However, the present invention is not limited to the implementation forms explicitly described.

In this manual, the numerical range indicated by the "~" sign indicates that the numerical values before and after the "~" are included in the range as the lower limit and upper limit, respectively.

In this manual, the term "step" not only refers to independent steps, but also includes steps that cannot be clearly distinguished from other steps as long as the intended effect of the step can be achieved.

Regarding the marking of groups (atomic groups) in this specification, the marking of unsubstituted and unsubstituted includes both groups (atomic groups) without substituents and groups (atomic groups) with substituents. For example, "alkyl" includes not only alkyl groups without substituents (unsubstituted alkyl groups), but also alkyl groups with substituents (substituted alkyl groups).

In this specification, unless otherwise specified, "exposure" includes not only exposure using light, but also exposure using particle beams such as electron beams and ion beams. In addition, as light used for exposure, the bright line spectrum of mercury lamps, far ultraviolet rays represented by excimer lasers, extreme ultraviolet rays (EUV rays), X-rays, electron beams and other actinic rays or radiation can be cited.

In this specification, "(meth)acrylate" means both or either "acrylate" and "methacrylate", "(meth)acrylic acid" means both or either "acrylic acid" and "methacrylic acid", and "(meth)acryl" means both or either "acryl" and "methacryl".

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

In this specification, the total solid content refers to the total mass of all components of the composition except the solvent. In addition, in this specification, the solid content concentration is the mass percentage of the components other than the solvent relative to the total mass of the composition.

In this specification, unless otherwise specified, the weight average molecular weight (Mw) and the number average molecular weight (Mn) are values measured using the gel permeation chromatography (GPC) method and are defined as polystyrene-equivalent values. In this specification, the weight average molecular weight (Mw) and the number average molecular weight (Mn) can be obtained by, for example, using HLC-8220GPC (manufactured by TOSOH CORPORATION) and connecting guard columns HZ-L, TSKgel Super HZM-M, TSKgel Super HZ 4000, TSKgel Super HZ3000 and TSKgel Super HZ2000 (all manufactured by TOSOH CORPORATION) in series. Unless otherwise specified, the molecular weights are measured using THF (tetrahydrofuran) as an eluent. Among them, when THF is not suitable as an eluent due to low solubility, NMP (N-methyl-2-pyrrolidone) can also be used. In addition, unless otherwise specified, the detection in the GPC measurement is that using a UV (ultraviolet) wavelength 254nm detector.

In this specification, when the positional relationship of each layer constituting a laminate is described as "upper" or "lower", it is sufficient as long as other layers exist on the upper side or lower side of the layer serving as a reference among the plurality of layers concerned. In other words, a third layer or a third element may be further sandwiched between the layer serving as a reference and the other layers mentioned above, and the layer serving as a reference and the other layers mentioned above do not need to be in contact. Furthermore, unless otherwise specified, the direction in which the layers are gradually stacked with respect to the substrate is referred to as "upper", or, in the case of a resin composition layer, the direction from the substrate toward the resin composition layer is referred to as "upper", and the opposite direction is referred to as "lower". Furthermore, the setting of the up and down directions is for the convenience of explaining this manual. In actual situations, the "up" direction in this manual may also be different from the lead pointing straight up.

In this specification, unless otherwise specified, each component contained in the composition may include two or more compounds corresponding to the component. In addition, unless otherwise specified, the content of each component in the composition represents the total content of all compounds corresponding to the component.

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

In this manual, a combination of the best practices is referred to as a better practice.

(hardening resin composition)

唑前驅物之群組中的至少1種樹脂(以下，亦稱為“特定樹脂”。)以及具有選自包括草酸單酯結構、草酸二酯結構、草酸單醯胺結構、草酸二醯胺結構及草酸酯醯胺結構之群組中的至少1種結構和聚合性基之化合物B(以下，簡稱為“化合物B”)。 The curable resin composition of the present invention (hereinafter referred to as "resin composition") comprises a polyimide precursor and a polybenzoic acid.

At least one resin from the group of oxalic acid proto-initiators (hereinafter, also referred to as "specific resin") and a compound B having at least one structure selected from the group consisting of an oxalic acid monoester structure, an oxalic acid diester structure, an oxalic acid monoamide structure, an oxalic acid diamide structure and an oxalate amide structure and a polymerizable group (hereinafter, referred to as "compound B").

The curable resin composition of the present invention can be a negative curable resin composition or a positive curable resin composition, but the negative curable resin composition is preferred.

A negative curable resin composition is a composition in which the unexposed portion (non-exposed portion) is removed by a developer when a layer formed of the curable resin composition is exposed.

A positive-type curable resin composition is a composition in which, when a layer formed of the curable resin composition is exposed, the exposed portion (exposed part) is removed by a developer.

The curable resin composition of the present invention preferably further comprises at least one of a photopolymerization initiator and a thermal polymerization initiator, and more preferably further comprises a photopolymerization initiator.

By including a photopolymerization initiator, it can be used as a negative curing resin composition.

Furthermore, by including a thermal polymerization initiator, it can be used as a negative curing resin composition or a positive curing resin composition.

The hardened material obtained from the hardening resin composition of the present invention has excellent chemical resistance.

Although the mechanism by which the above effects can be achieved is still unclear, it is speculated as follows.

The hardening resin composition of the present invention contains compound B.

It is believed that at least one structure selected from the group consisting of oxalic acid monoester structure, oxalic acid diester structure, oxalic acid monoamide structure, oxalic acid diamide structure and oxalate amide structure contained in compound B has high polarity and aggregates in the obtained hardened material. Therefore, it is believed that the penetration of the chemical solution in the obtained hardened material is suppressed and the hardened material has excellent chemical resistance.

It is believed that since the cured product has excellent chemical resistance, when, for example, a laminate is prepared by applying another curable resin composition containing a solvent to the cured product obtained by curing the curable resin composition of the present invention and curing the cured product, even if the cured product comes into contact with a developer or other curable resin composition, dissolution of the cured product is suppressed.

It is believed that according to the present invention, a hardened material can be obtained, which has suppressed solubility in polar solvents such as dimethyl sulfoxide (DMSO) and N-methylpyrrolidone (NMP), alkaline aqueous solutions such as tetramethylammonium hydroxide (TMAH) aqueous solutions, or mixed solutions of the above polar solvents and the above alkaline aqueous solutions, and has excellent drug resistance.

唑前驅物、其他聚合性化合物)中所包含之聚合性基聚合而形成聚合物。 Furthermore, compound B has a polymerizable group, so in the cured product, the polymerizable groups in compound B are mutually or the polymerizable groups in compound B are polymerizable with other components (e.g., polyimide precursor, polybenzoic acid precursor, etc.).

The polymerizable groups contained in the azole precursor and other polymerizable compounds are polymerized to form a polymer.

It is speculated that the polymer containing at least one structure selected from the group consisting of oxalic acid monoester structure, oxalic acid diester structure, oxalic acid monoamide structure, oxalic acid diamide structure and oxalate amide structure has high flexibility, so the film strength (elongation at break) of the obtained cured product is also excellent.

In addition, it is estimated that during curing (for example, during curing based on the heating step described later), the mobility of the polymer is improved by the effect of compound B to promote the ring closing reaction, and it is speculated that this is also one of the reasons for the excellent film strength (elongation at break).

Furthermore, it is believed that compound B has excellent solubility in the developer before polymerization by including at least one structure selected from the group including oxalic acid monoester structure, oxalic acid diester structure, oxalic acid monoamide structure, oxalic acid diamide structure and oxalate amide structure. Therefore, it is speculated that when the curable resin composition of the present invention is used in patterning including exposure and development, the resolution is also excellent.

Among them, in Patent Documents 1 and 2, there is no description or suggestion of a curable resin composition containing a specific resin and compound B.

The following is a detailed description of the components contained in the curable resin composition of the present invention.

<Specific resin>

唑前驅物之群組中的至少1種樹脂(特定樹脂)。 The curable resin composition of the present invention comprises a polyimide precursor and a polybenzoic acid.

At least one resin (specific resin) in the group of azole promotors.

The curable resin composition of the present invention preferably contains a polyimide precursor as a specific resin.

Furthermore, it is preferred that the specific resin contains a repeating unit represented by the formula (2) described below.

Furthermore, it is preferred that the specific resin has a polymerizable group.

As the polymerizable group in the specific resin, there can be cited known polymerizable groups such as free radical polymerizable groups, epoxy groups, cyclohexane groups, hydroxymethyl groups, and alkoxymethyl groups.

As the above-mentioned free radical polymerizable group, a group having an ethylenic unsaturated bond is preferred.

As the group having an ethylenic unsaturated bond, there can be cited vinyl, allyl, vinylphenyl, etc., groups directly bonded to an aromatic ring and having a vinyl group that can be substituted, (meth)acrylamide, (meth)acryloxy, etc., with (meth)acryloxy being preferred.

Among these, the specific resin containing a free radical polymerizable group is preferred.

When the specific resin has a radical polymerizable group, the curable resin composition preferably includes the photo radical polymerization initiator described below as a photosensitizer, more preferably includes the photo radical polymerization initiator described below as a photosensitizer and includes the radical crosslinking agent described below, and further preferably includes the photo radical polymerization initiator described below as a photosensitizer, includes the radical crosslinking agent described below, and includes the sensitizer described below. For example, a negative photosensitive layer is formed by such a curable resin composition.

Furthermore, the specific resin may have a polar conversion group such as an acid-degradable group.

When the specific resin has an acid-degradable group, it is preferred that the curable resin composition contains the photoacid generator described below as a photosensitizer. The curable resin composition can be used to form, for example, a positive photosensitive layer or a negative photosensitive layer of a chemically amplified type.

[Polyimide precursor]

The type of the polyimide precursor used in the present invention is not particularly specified, but it is preferred to contain a repeating unit represented by the following formula (2).

In formula (2), ^A1 and ^A2 each independently represent an oxygen atom or -NH-, ^R111 represents a divalent organic group, ^R115 represents a tetravalent organic group, and ^R113 and ^R114 each independently represent a hydrogen atom or a monovalent organic group.

In formula (2), ^A1 and ^A2 each independently represent an oxygen atom or -NH-, and an oxygen atom is preferred.

R ¹¹¹ in formula (2) represents a divalent organic group. Examples of the divalent organic group include groups containing linear or branched aliphatic groups, cyclic aliphatic groups and aromatic groups, preferably linear or branched aliphatic groups having 2 to 20 carbon atoms, cyclic aliphatic groups having 3 to 20 carbon atoms, aromatic groups having 3 to 20 carbon atoms or a combination thereof, and more preferably a group containing an aromatic group having 6 to 20 carbon atoms. The linear or branched aliphatic groups may be substituted by a group containing a heteroatom in the alkyl group in the chain, and the cyclic aliphatic groups and aromatic groups may be substituted by a group containing a heteroatom in the alkyl group of a ring member. As a preferred embodiment of the present invention, groups represented by -Ar- and -Ar-L-Ar- can be exemplified, and a group represented by -Ar-L-Ar- is particularly preferred. Here, Ar is independently an aromatic group, and L is a group including a single bond, an aliphatic alkyl group having 1 to 10 carbon atoms which may be substituted by a fluorine atom, -O-, -CO-, -S-, -SO ₂ - or -NHCO-, or a combination of two or more of the above. The preferred ranges are as described above.

R ¹¹¹ is preferably derived from a diamine. Examples of the diamine used in the production of the polyimide precursor include linear or branched aliphatic, cyclic aliphatic or aromatic diamines. Only one diamine may be used, or two or more diamines may be used.

Specifically, diamines containing a straight or branched aliphatic group with 2 to 20 carbon atoms, a cyclic aliphatic group with 3 to 20 carbon atoms, an aromatic group with 3 to 20 carbon atoms, or a combination of these groups are preferred, and diamines containing an aromatic group with 6 to 20 carbon atoms are more preferred. The straight or branched aliphatic group may be substituted by a group containing heteroatoms via a alkyl group in the chain, and the cyclic aliphatic group and aromatic group may be substituted by a group containing heteroatoms via a alkyl group of a ring member. As examples of groups containing aromatic groups, the following can be cited.

In the formula, A represents a single bond or a divalent linking group, preferably a single bond or an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be substituted by a fluorine atom, -O-, -C(=O)-, -S-, -SO ₂ -, -NHCO-, or a combination thereof, more preferably a single bond, an alkylene group having 1 to 3 carbon atoms which may be substituted by a fluorine atom, -O-, -C(=O)-, -S-, or -SO ₂ -, further preferably -CH ₂ -, -O-, -S-, -SO ₂ -, -C(CF ₃ ) ₂ -, or -C(CH ₃ ) ₂ -.

In the formula, * indicates the bonding site with other structures.

Specifically, the diamine includes 1,2-diaminoethane, 1,2-diaminopropane, 1,3-diaminopropane, 1,4-diaminobutane and 1,6-diaminohexane; 1,2-diaminocyclopentane or 1,3-diaminocyclopentane, 1,2-diaminocyclohexane, 1,3-diaminocyclohexane or 1,4-diaminocyclohexane, 1,2-bis(aminomethyl)cyclohexane, 1,3-bis(aminomethyl)cyclohexane or 1,4-bis(aminomethyl)cyclohexane, bis-(4-aminocyclohexyl)methane, bis-(3-aminocyclohexyl)methane, 4,4'-diamino-3,3'- Dimethylcyclohexylmethane and isophoronediamine; meta-phenylenediamine or para-phenylenediamine, diaminotoluene, 4,4'-diaminobiphenyl or 3,3'-diaminobiphenyl, 4,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl ether, 4,4'-diaminodiphenylmethane and 3,3'-diaminodiphenylmethane, 4,4'-diaminodiphenyl sulfonate and 3,3-diaminodiphenyl sulfonate, 4,4'-diaminodiphenyl ether and 3,3'-diaminodiphenyl ether, 4,4'-diaminobenzophenone or 3,3'-diaminobenzophenone, 3,3'-dimethyl-4,4'-diaminobiphenyl, 2,2'-diamino 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)sulfonate, bis(4-amino-3-hydroxyphenyl)sulfonate, 4,4'-diaminoterphenyl, 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'-diaminodiphenyl Methane, 4,4'-diaminooctafluorobiphenyl, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, 9,9-bis(4-aminophenyl)-10-hydroanthracene, 3,3',4,4'-tetraaminobiphenyl, 3,3',4,4'-tetraaminodiphenyl ether, 1,4-diaminoanthraquinone, 1,5-diaminoanthraquinone, 3,3-dihydroxy-4,4'-diaminobiphenyl, 9,9'-bis(4-aminophenyl)fluorene, 4,4'-dimethyl-3,3'-diaminodiphenylsulfone, 3,3',5,5'-tetramethyl- 4,4'-diaminodiphenylmethane, 2,4-diaminocumene and 2,5-diaminocumene, 2,5-dimethyl-p-phenylenediamine, acetoguanamine, 2,3,5,6-tetramethyl-p-phenylenediamine, 2,4,6-trimethyl-m-phenylenediamine, bis(3-aminopropyl)tetramethyldisiloxane, bis(p-aminophenyl)octamethylpentasiloxane, 2,7-diaminofluorene, 2,5-diaminopyridine, 1,2-bis(4-aminophenyl)ethane, diaminobenzanilide, esters of diaminobenzoic acid, 1,5-diaminonaphthalene, diaminotrifluorotoluene, 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-trifluoromethyl At least one diamine selected from the group consisting of 4,4'-bis(4-amino-3-trifluoromethylphenoxy)biphenyl, 4,4'-bis(4-amino-2-trifluoromethylphenoxy)diphenylsulfonium, 4,4'-bis(3-amino-5-trifluoromethylphenoxy)diphenylsulfonium, 2,2-bis[4-(4-amino-3-trifluoromethylphenoxy)phenyl]hexafluoropropane, 3,3',5,5'-tetramethyl-4,4'-diaminobiphenyl, 4,4'-diamino-2,2'-bis(trifluoromethyl)biphenyl, 2,2',5,5',6,6'-hexafluorotoluidine and 4,4'-diaminoquaternaryl.

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

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

From the viewpoint of the flexibility of the obtained organic film, R ¹¹¹ is preferably represented by -Ar-L-Ar-. Ar is independently an aromatic group, and L is a group including an aliphatic alkyl group having 1 to 10 carbon atoms which may be substituted by a fluorine atom, -O-, -CO-, -S-, -SO ₂ - or -NHCO-, or a combination of two or more of the foregoing. Ar is preferably a phenylene group, and L is preferably an aliphatic alkyl group having 1 or 2 carbon atoms which may be substituted by a fluorine atom, -O-, -CO-, -S- or -SO ₂ -. The aliphatic alkyl group here is preferably an alkylene group.

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

In formula (51), R ⁵⁰ to R ⁵⁷ are 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 * independently represents a bonding site with the nitrogen atom in formula (2).

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

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 with the nitrogen atom in formula (2).

As diamines providing the structure of formula (51) or formula (61), 2,2'-dimethylbenzidine, 2,2'-bis(trifluoromethyl)-4,4'-diaminobiphenyl, 2,2'-bis(fluoro)-4,4'-diaminobiphenyl, 4,4'-diaminooctafluorobiphenyl, etc. can be cited. These can be used alone or in combination of two or more.

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

In formula (5) or formula (6), * independently represents the bonding site with other structures.

In formula (5), R ¹¹² is a single bond or a divalent linking group, preferably a single bond or an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be substituted by a fluorine atom, -O-, -CO-, -S-, -SO ₂ - and -NHCO-, and a combination thereof, more preferably a single bond, an alkylene group having 1 to 3 carbon atoms which may be substituted by a fluorine atom, -O-, -CO-, -S- and -SO ₂ -, and even 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 -.

Furthermore, R ¹¹¹ may be a structure including a polymerizable group.

For example, R ¹¹¹ may be a structure derived from a diamine compound having a polymerizable group.

The diamine compound having a polymerizable group is not particularly limited, but a compound containing an aromatic ring structure is preferred, and a compound having a structure containing an amine group and a polymerizable group and a structure directly connected to an aromatic ring structure is more preferred.

As the polymerizable group, a group containing an ethylenic unsaturated bond, a cyclic ether group, a hydroxymethyl group or an alkoxymethyl group is preferred, a vinyl group, a (meth)allyl group, a (meth)acrylamide group, a (meth)acryloyloxy group, a cis-butylenediimide group, a vinylphenyl group, an epoxy group, an oxobutylene group, a hydroxymethyl group or an alkoxymethyl group is more preferred, and a (meth)acryloxy group, a (meth)acrylamide group, an epoxy group, a hydroxymethyl group or an alkoxymethyl group is further preferred.

Specific examples of R ¹¹⁵ include a tetracarboxylic acid residue remaining after the anhydride group is removed from tetracarboxylic dianhydride, etc. As a structure corresponding to R ¹¹⁵ , the polyimide precursor may contain only one tetracarboxylic dianhydride residue or two or more.

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

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

Specific examples of tetracarboxylic dianhydrides include pyromellitic dianhydride (PMDA), 3,3',4,4'-biphenyltetracarboxylic dianhydride, 3,3',4,4'-diphenyl sulfide tetracarboxylic dianhydride, 3,3',4,4'-diphenylsulfone tetracarboxylic dianhydride, 3,3',4,4'-benzophenone tetracarboxylic dianhydride, 3,3',4,4'-diphenylmethane tetracarboxylic dianhydride, 2,2',3,3'-diphenylmethane tetracarboxylic dianhydride, 2,3,3',4'-biphenyltetracarboxylic dianhydride, 2,3,3',4'-benzophenone tetracarboxylic dianhydride, 4,4'-oxydiphthalic dianhydride, 2,3,6,7-naphthalene tetracarboxylic dianhydride, 1,4,5,7-naphthalene tetracarboxylic dianhydride, 2,2-bis(3,4-dicarboxyphenyl)propane Dianhydride, 2,2-bis(2,3-dicarboxyphenyl)propane dianhydride, 2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane dianhydride, 1,3-diphenylhexafluoropropane-3,3,4,4-tetracarboxylic dianhydride, 1,4,5,6-naphthalenetetracarboxylic dianhydride, 2,2',3,3'-diphenyltetracarboxylic dianhydride, 3,4,9,10-perylenetetracarboxylic dianhydride, 1,2,4,5-naphthalenetetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 1,8,9,10-phenanthrenetetracarboxylic dianhydride, 1,1-bis(2,3-dicarboxyphenyl)ethane dianhydride, 1,1-bis(3,4-dicarboxyphenyl)ethane dianhydride, 1,2,3,4-benzenetetracarboxylic dianhydride and their alkyl and alkoxy derivatives having 1 to 6 carbon atoms.

In addition, tetracarboxylic dianhydride (DAA-1) to (DAA-5) described in paragraph 0038 of International Publication No. 2017/038598 can also be cited as a preferred example.

In formula (2), at least one of R ¹¹¹ and R ¹¹⁵ may have an OH group. More specifically, R ¹¹¹ includes a residual group of a diaminophenol derivative.

唑基、嵌段異氰酸酯基、胺基。作為聚醯亞胺前驅物所具有之自由基聚合性基，具有乙烯性不飽和鍵之基團為較佳。 In formula (2), R ¹¹³ and R ¹¹⁴ each independently represent a hydrogen atom or a monovalent organic group. As the monovalent organic group, a linear or branched alkyl group, a cyclic alkyl group, an aromatic group or a polyalkylene group is preferred. Furthermore, at least one of R ¹¹³ and R ¹¹⁴ preferably contains a polymerizable group, and it is more preferred that both contain polymerizable groups. It is also preferred that at least one of R ¹¹³ and R ¹¹⁴ contains two or more polymerizable groups. As the polymerizable group, a group capable of undergoing a crosslinking reaction by the action of heat, free radicals, etc. is preferred to be a free radical polymerizable group. 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 oxobutylene group, a benzophenone group,

Azolyl, blocked isocyanate, amine. As the free radical polymerizable group of the polyimide precursor, a group having an ethylenic unsaturated bond is preferred.

As the group having an ethylenic unsaturated bond, there can be cited vinyl, allyl, isoallyl, 2-methylallyl, a group having an aromatic ring directly bonded to a vinyl group (e.g., vinylphenyl, etc.), (meth)acrylamide, (meth)acryloxy, a group represented by the following formula (III), etc., and the group represented by the following formula (III) is preferred.

In formula (III), R ²⁰⁰ represents a hydrogen atom, a methyl group, an ethyl group or a hydroxymethyl group, preferably a hydrogen atom or a methyl group.

In formula (III), * represents the bonding site with other structures.

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.

Preferred examples of R ²⁰¹ include alkylene groups such as ethylene, propylene, trimethylene, tetramethylene, pentamethylene, hexamethylene, octamethylene, dodecamethylene, 1,2-butanediyl, 1,3-butanediyl, -CH ₂ CH(OH)CH ₂ -, polyalkyleneoxy groups, more preferred alkylene groups such as ethylene and propylene, -CH ₂ CH(OH)CH ₂ -, cyclohexyl, polyalkyleneoxy groups, and even more preferred alkylene groups such as ethylene and propylene or polyalkyleneoxy groups.

In the present invention, a polyalkoxy group refers to an alkoxy group directly bonded to two or more groups. The alkylene groups in the multiple alkoxy groups contained in the polyalkoxy group may be the same or different.

When the polyalkoxyl group includes a plurality of alkoxyl groups with different alkylene groups, the arrangement of the alkoxyl groups in the polyalkoxyl group may be a random arrangement, a block arrangement, or an alternating arrangement.

The carbon number of the alkylene group (including the carbon number of the substituent when the alkylene group has a substituent) is preferably 2 or more, 2 to 10 is more preferred, 2 to 6 is more preferred, 2 to 5 is further preferred, 2 to 4 is further preferred, 2 or 3 is particularly preferred, and 2 is the best.

Furthermore, the above-mentioned alkylene group may have a substituent. Preferred substituents include alkyl groups, aryl groups, halogen atoms, etc.

Furthermore, the number of alkoxy groups contained in the polyalkoxy group (the number of repetitions of the polyalkoxy group) is preferably 2 to 20, more preferably 2 to 10, and even more preferably 2 to 6.

As polyalkoxy groups, from the perspective of solvent solubility and solvent resistance, polyethyleneoxy, polypropoxy, polytrimethyleneoxy, polytetramethyleneoxy or a group obtained by bonding multiple vinyloxy groups with multiple propoxy groups is preferred, polyethyleneoxy or polypropoxy is more preferred, and polyethyleneoxy is further preferred. In the above-mentioned group obtained by bonding multiple vinyloxy groups with multiple propoxy groups, the vinyloxy groups and propoxy groups can be arranged randomly, can be arranged in blocks, and can also be arranged in alternating patterns. The preferred aspects of the repeated number of vinyloxy 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 can form a conjugate with a tertiary amine compound having an ethylenically unsaturated bond. An example of such a tertiary amine compound having an ethylenically unsaturated bond is N,N-dimethylaminopropyl methacrylate.

In formula (2), at least one of ^R113 and ^R114 may be a polar conversion group such as an acid-decomposable group. The acid-decomposable group is not particularly limited as long as it is decomposed by an acid to generate an alkali-soluble group such as a phenolic hydroxyl group or a carboxyl group, but an acetal group, a ketal group, a silyl group, a silyl ether group, a tertiary alkyl ester group, etc. are preferred. From the viewpoint of exposure sensitivity, an acetal group or a ketal group is more preferred.

Specific examples of acid-decomposable groups include tert-butoxycarbonyl, isopropoxycarbonyl, tetrahydropyranyl, tetrahydrofuranyl, ethoxyethyl, methoxyethyl, ethoxymethyl, trimethylsilyl, tert-butoxycarbonylmethyl, trimethylsilyl ether, etc. From the perspective of exposure sensitivity, ethoxyethyl or tetrahydrofuranyl is preferred.

Furthermore, the polyimide precursor preferably has fluorine atoms in its structure. The fluorine atom content in the polyimide precursor is preferably 10% by mass or more, and preferably 20% by mass or less.

In addition, in order to improve the adhesion with the substrate, the polyimide precursor can be copolymerized with an aliphatic group having a siloxane structure. Specifically, as the diamine, there can be cited the use of bis(3-aminopropyl)tetramethyldisiloxane, bis(p-aminophenyl)octamethylpentasiloxane, etc.

The repeating unit represented by formula (2) is preferably a repeating unit represented by formula (2-A). That is, at least one of the polyimide precursors used in the present invention is preferably a precursor having a repeating unit represented by formula (2-A). By making the polyimide precursor contain a repeating unit represented by formula (2-A), the width of the exposure tolerance can be increased.

In formula (2-A), ^A1 and ^A2 represent oxygen atoms, ^R111 and ^R112 each independently represent a divalent organic group, ^R113 and ^R114 each independently represent a hydrogen atom or a monovalent organic group, at least one of ^R113 and ^R114 is a group containing a polymerizable group, and it is preferred that both are groups containing a polymerizable group.

A ¹ , A ² , R ¹¹¹ , R ¹¹³ and R ¹¹⁴ have the same meanings as A ¹ , A ² , R ¹¹¹ , R ¹¹³ and R ¹¹⁴ in formula (2), respectively, 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. Furthermore, it may contain structural isomers of the repeating unit represented by formula (2). Moreover, it is self-evident that the polyimide precursor may contain other types of repeating units in addition to the repeating units of the above formula (2).

As an embodiment of the polyimide precursor of the present invention, the content of the repeating unit represented by formula (2) is 50 mol% or more of all the repeating units. The above total content is more preferably 70 mol% or more, more preferably 90 mol% or more, and particularly preferably more than 90 mol%. The upper limit of the above total content is not particularly limited, and all the repeating units in the polyimide precursor except the terminal can also be the repeating units represented by formula (2).

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

The molecular weight dispersion of the polyimide precursor is preferably 1.5 or more, more preferably 1.8 or more, and even more preferably 2.0 or more. There is no particular upper limit on the molecular weight dispersion of the polyimide precursor, for example, preferably 7.0 or less, more preferably 6.5 or less, and even more preferably 6.0 or less.

In this specification, the molecular weight dispersion is the value calculated using the weight average molecular weight/number average molecular weight.

Furthermore, when the resin composition includes a plurality of polyimide precursors as specific resins, it is preferred that the weight average molecular weight, number average molecular weight and dispersion of at least one polyimide precursor are within the above ranges. Furthermore, it is also preferred that the weight average molecular weight, number average molecular weight and dispersion calculated using the plurality of polyimide precursors as one resin are within the above ranges.

唑前驅物〕 Polyphenylene

Azole prodrug

唑前驅物的其結構等，並無特別規定，但是較佳為包含下述式(3)所表示之重複單元。 Regarding the polyphenylene oxide used in the present invention

The structure of the azole promotors is not particularly limited, but preferably comprises repeating units represented by the following formula (3).

In formula (3), ^R121 represents a divalent organic group, ^R122 represents a tetravalent organic group, and ^R123 and ^R124 each independently represent a hydrogen atom or a monovalent organic group.

In formula (3), R ¹²³ and R ¹²⁴ have the same meanings as R ¹¹³ in formula (2), and the preferred ranges thereof are also the same. That is, it is preferred that at least one of them is a polymerizable 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 preferred. As the aliphatic group, a linear aliphatic group is preferred. R ¹²¹ is preferably a dicarboxylic acid residue. Only one dicarboxylic acid residue may be used, or two or more dicarboxylic acid residues may be used.

As the dicarboxylic acid residue, dicarboxylic acids containing aliphatic groups and dicarboxylic acid residues containing aromatic groups are preferred, and dicarboxylic acid residues containing aromatic groups are more preferred.

As the dicarboxylic acid containing an aliphatic group, a dicarboxylic acid containing a straight chain or branched chain (preferably a straight chain) aliphatic group is preferred, and a dicarboxylic acid containing a straight chain or branched chain (preferably a straight chain) aliphatic group and 2 -COOH groups is more preferred. The carbon number of the straight chain or branched chain (preferably a straight chain) aliphatic group is preferably 2 to 30, more preferably 2 to 25, more preferably 3 to 20, more preferably 4 to 15, and particularly preferably 5 to 10. The straight chain aliphatic group is preferably an alkylene group.

As the dicarboxylic acid containing a linear aliphatic group, there can be mentioned 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-tetrafluorohexanediol, 1,2-dimethyl ... Methyl pimelic acid, suberic acid, dodecanedioic acid, azelaic acid, sebacic acid, hexafluorosebacic acid, 1,9-azelaic acid, dodecanedioic acid, tridecanedioic acid, tetradecanedioic acid, pentadecanedioic acid, hexadecanedioic acid, heptadecanedioic acid, octadecanedioic acid, nonadecanedioic acid, eicosanedioic acid, eicosanedioic acid Monoacanedioic acid, behenedioic acid, tricosanedioic acid, tetracosanedioic acid, pentacosanedioic acid, hexacosanedioic acid, heptacosanedioic acid, octacanedioic acid, nonacosanedioic acid, triacontanedioic acid, triacontanedioic acid, triacontanedioic acid, diglycolic acid acid) and the dicarboxylic acid represented by the following formula, etc.

(In the formula, Z is a carbonyl group with 1 to 6 carbon atoms, and n is an integer from 1 to 6.)

As dicarboxylic acids containing aromatic groups, the following dicarboxylic acids having aromatic groups are preferred, and the following dicarboxylic acids containing only aromatic groups and 2 -COOH groups are more preferred.

[Chemical formula 13]

In the formula, A represents a divalent group selected from the group consisting of _-CH2- , -O-, -S-, _-SO2- , -CO-, -NHCO-, -C( _CF3 ) _2- , and -C( _CH3 ) _2- , and * represents a bonding site with other structures independently.

Specific examples of dicarboxylic acids containing an aromatic group include 4,4'-carbonyldibenzoic acid, 4,4'-dicarboxydiphenyl ether, and phthalic acid.

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

^R122 is preferably a group derived from a diaminophenol derivative. Examples of the group derived from a diaminophenol derivative include 3,3'-diamino-4,4'-dihydroxybiphenyl, 4,4'-diamino-3,3'-dihydroxybiphenyl, 3,3'-diamino-4,4'-dihydroxydiphenylsulfone, 4,4'-diamino-3,3'-dihydroxydiphenylsulfone, bis-(3-amino-4-hydroxyphenyl)methane, 2,2-bis-(3-amino-4-hydroxyphenyl)propane, 2,2-bis-(3-amino-4-hydroxyphenyl)propane, 2,2-bis-(4-amino-3-hydroxyphenyl)hexafluoropropane, bis-(4-amino-3-hydroxyphenyl)methane, 2,2-bis-(4-amino-3-hydroxyphenyl)propane, 4,4'-diamino-3,3'-dihydroxybenzophenone, 3,3'-diamino-4,4'-dihydroxybenzophenone, 4,4'-diamino-3,3'-dihydroxydiphenyl ether, 3,3'-diamino-4,4'-dihydroxydiphenyl ether, 1,4-diamino-2, 5-dihydroxybenzene, 1,3-diamino-2,4-dihydroxybenzene, 1,3-diamino-4,6-dihydroxybenzene, and the like. The diaminophenols can be used alone or in combination.

Among the diaminophenol derivatives, the following diaminophenol derivatives having an aromatic group are preferred.

In the formula, _X1 represents -O-, -S-, -C( _CF3 ) _2- , _-CH2- , _-SO2- , -NHCO-, * and # represent the bonding site with other structures respectively. R represents a hydrogen atom or a monovalent substituent, preferably a hydrogen atom or a alkyl group, more preferably a hydrogen atom or an alkyl group. In addition, ^R122 is also preferably a structure represented by the above formula. When R ¹²² is a structure represented by the above formula, any two of the four * and # in total are bonding sites to the nitrogen atom to which R ¹²² in formula (3) is bonded, and the other two are bonding sites to the oxygen atom to which R ¹²² in formula (3) is bonded. It is more preferred that two * are bonding sites to the oxygen atom to which R ¹²² in formula (3) is bonded, and two # are bonding sites to the nitrogen atom to which R ¹²² in formula (3) is bonded, or two * are bonding sites to the nitrogen atom to which R 122 in formula (3) is bonded, and two # are bonding sites to the oxygen atom to which R ¹²² in formula (3) is bonded. It is more preferred that two * are bonding sites to the oxygen atom to which R 122 in formula (3) is bonded, and two # are bonding sites to the oxygen atom to which R ¹²² in formula (3) is bonded. It is further preferred that the two #s are bonding sites to the oxygen atom to which ^{R 122} is bonded and the two #s are bonding sites to the nitrogen atom to which R ¹²² in formula (3) is bonded.

The diaminophenol derivative is preferably a compound represented by formula (A-s).

In formula (As), _R1 is an organic group selected from a hydrogen atom, an alkylene group, a substituted alkylene group, -O-, -S-, _-SO2- , -CO-, -NHCO-, a single bond or the group of the following formula (A-sc). _R2 is any one of a hydrogen atom, an alkyl group, an alkoxy group, an acyloxy group, and a cyclic alkyl group, and they may be the same or different. _R3 is any one of a hydrogen atom, a linear or branched alkyl group, an alkoxy group, an acyloxy group, and a cyclic alkyl group, and they may be the same or different.

(In formula (A-sc), * represents the aromatic ring bond with the aminophenol group of the diaminophenol derivative represented by the above formula (A-s).)

In the above formula (As), it is considered that having a substituent at the adjacent position of the phenolic hydroxyl group, that is, at _R3 , brings the carbonyl carbon of the amide bond and the hydroxyl group closer together, which is particularly preferred in terms of further improving the effect of achieving a high cyclization rate during curing at a low temperature.

In the above formula (As), when _R2 is an alkyl group and _R3 is an alkyl group, it is preferable because high transparency to I-rays and high cyclization rate can be maintained when curing at a low temperature.

唑前驅物之方面而言，-CH₂-、-CH(CH₃)-、-C(CH₃)₂-為更佳。 In the above formula (As), _R1 is preferably an alkylene group or a substituted alkylene group. Specific examples of the alkylene group and the substituted alkylene group of _R1 include a linear or branched alkyl group having 1 to 8 carbon atoms, wherein a polyphenylene oxide having a good balance of high transparency to I-rays and a high cyclization rate when hardened at a low temperature and sufficient solubility in a solvent can be obtained.

From the perspective of the azole protozollant, -CH ₂ -, -CH(CH ₃ )-, and -C(CH ₃ ) ₂ - are more preferred.

For the production method of the diaminophenol derivative represented by the above formula (A-s), for example, reference can be made to paragraphs 0085 to 0094 and Example 1 (paragraphs 0189 to 0190) of Japanese Patent Application No. 2013-256506, and such contents are incorporated into this specification.

As specific examples of the structure of the diaminophenol derivative represented by the above formula (A-s), the ones described in paragraphs 0070 to 0080 of Japanese Patent Publication No. 2013-256506 can be cited, and these contents are incorporated into this specification. Of course, it is not limited to these, which is self-evident.

唑前驅物還可以包含其他種類的重複單元。 In addition to the repeating units of the above formula (3), polybenzoic acid

The azole prodrugs may also contain other types of repeating units.

唑前驅物包含下述式(SL)所表示之二胺殘基作為其他種類的重複單元為較佳。 In terms of being able to suppress the warp associated with ring closure, polyphenylene sulfide

The azole precursor preferably contains a diamine residue represented by the following formula (SL) as another type of repeating unit.

[Chemical formula 17]

b：

a:

b:

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

唑前驅物在脫水閉環後的彈性模數，能夠兼顧能夠抑制翹曲之效果和提高溶劑溶解性之效果。 In formula (SL), as preferred Z, R ^5s and R ^6s in structure b are phenyl. In addition, the molecular weight of the structure represented by formula (SL) is preferably 400 to 4,000, and more preferably 500 to 3,000. By setting the molecular weight within the above range, the polyphenylene oxide can be more effectively reduced.

The elastic modulus of the azole prodrug after dehydration and ring closure can take into account both the effect of suppressing warp and the effect of improving solvent solubility.

When the diamine residue represented by formula (SL) is included as another type of repeating unit, it is also preferred to further include a tetracarboxylic acid residue remaining after removing the anhydride group from tetracarboxylic dianhydride as a repeating unit. Examples of such a tetracarboxylic acid residue include R ¹¹⁵ in formula (2).

唑前驅物的重量平均分子量(Mw)例如較佳為18,000~30,000，更佳為20,000~29,000，進一步較佳為22,000~28,000。又，數量平均分子量(Mn)較佳為7,200~14,000，更佳為8,000~12,000，進一 步較佳為9,200~11,200。 Polyphenylene

The weight average molecular weight (Mw) of the azole prodrug is preferably 18,000 to 30,000, more preferably 20,000 to 29,000, and further preferably 22,000 to 28,000, and the number average molecular weight (Mn) is preferably 7,200 to 14,000, more preferably 8,000 to 12,000, and further preferably 9,200 to 11,200.

唑前驅物的分子量的分散度為1.4以上為較佳，1.5以上為更佳，1.6以上為進一步較佳。聚苯并

唑前驅物的分子量的分散度的上限值並無特別規定，例如2.6以下為較佳，2.5以下為更佳，2.4以下為進一步較佳，2.3以下為進一步較佳，2.2以下為更進一步較佳。 The above polyphenylene

The molecular weight dispersion of the azole precursor is preferably 1.4 or more, more preferably 1.5 or more, and even more preferably 1.6 or more.

The upper limit of the molecular weight dispersion of the azole prodrug is not particularly limited, but is preferably 2.6 or less, more preferably 2.5 or less, further preferably 2.4 or less, further preferably 2.3 or less, and further preferably 2.2 or less.

唑前驅物作為特定樹脂之情況下，至少1種聚苯并

唑前驅物的重量平均分子量、數量平均分子量及分散度在上述範圍內為較佳。又，將上述複數種聚苯并

唑前驅物作為1個樹脂計算出之重量平均分子量、數量平均分子量及分散度分別在上述範圍內亦較佳。 Furthermore, the resin composition contains a plurality of polybenzoic acid

In the case of an azole precursor as a specific resin, at least one polyphenylene glycol

The weight average molecular weight, number average molecular weight and dispersion of the azole precursor are preferably within the above ranges.

The weight average molecular weight, number average molecular weight and dispersity of the azole prodrug calculated as one resin are preferably within the above ranges.

[Method for producing polyimide precursor, etc.]

The polyimide precursor can be obtained, for example, by the following methods: a method of reacting tetracarboxylic dianhydride and diamine at low temperature, a method of reacting tetracarboxylic dianhydride and diamine at low temperature to obtain polyamide and esterifying the obtained polyamide using a condensation agent or an alkylating agent, a method of obtaining a diester from tetracarboxylic dianhydride and alcohol and then reacting the obtained polyamide in the presence of a diamine and a condensation agent, a method of obtaining a diester from tetracarboxylic dianhydride and alcohol and then halogenating the remaining dicarboxylic acid using a halogenating agent and then reacting the obtained polyamide with diamine, etc. Among the above production methods, a method of obtaining a diester from tetracarboxylic dianhydride and alcohol and then halogenating the remaining dicarboxylic acid using a halogenating agent and then reacting the obtained polyamide with diamine is more preferred.

Examples of the above-mentioned condensation 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.

As the above-mentioned alkylating agent, N,N-dimethylformamide dimethyl acetal, N,N-dimethylformamide diethyl acetal, N,N-dialkylformamide dialkyl acetal, trimethyl orthoformate, triethyl orthoformate, etc. can be cited.

As the above-mentioned halogenating agents, there can be cited sulfuryl chloride, oxalyl chloride, phosphorus oxychloride, etc.

In the production method of polyimide precursors, it is preferred to use an organic solvent during the reaction. The organic solvent may be one or more.

As the organic solvent, it can be appropriately set according to the raw materials, but examples thereof include pyridine, diethylene glycol dimethyl ether (diglyme), N-methylpyrrolidone, N-ethylpyrrolidone, ethyl propionate, dimethylacetamide, dimethylformamide, tetrahydrofuran, γ-butyrolactone, etc.

In the production method of polyimide precursors, it is preferred to add an alkaline compound during the reaction. The alkaline compound may be one or more.

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

-Capping agent-

In the production method of polyimide precursors, in order to further improve storage stability, it is preferred to seal the carboxylic anhydride, anhydride derivative or amine group remaining at the end of the resin of the polyimide precursor. When sealing the carboxylic anhydride and anhydride derivative remaining at the end of the resin, monohydric alcohol, phenol, thiol, thiophenol, monoamine, etc. can be cited as the end-capping agent. From the viewpoint of reactivity and film stability, it is more preferred to use monohydric alcohol, phenol or monoamine. Preferred monohydric alcohol compounds include primary alcohols such as methanol, ethanol, propanol, butanol, hexanol, octanol, dodecanol, benzyl alcohol, 2-phenylethanol, 2-methoxyethanol, 2-chloromethanol, and furfuryl alcohol, secondary alcohols such as isopropanol, 2-butanol, cyclohexanol, cyclopentanol, and 1-methoxy-2-propanol, and tertiary alcohols such as tertiary butanol and adamantane. Preferred phenol compounds include phenol, methoxyphenol, methylphenol, naphthalene-1-ol, naphthalene-2-ol, hydroxystyrene, and the like. Moreover, 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, and the like. Naphthalene, 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. Two or more of these can be used, and by reacting multiple types of end-capping agents, multiple different terminal groups can be introduced.

Furthermore, when sealing the amine group at the end of the resin, a compound having a functional group that can react with the amine group can be used for sealing. Preferred sealants for amine groups are carboxylic anhydride, carboxylic acid chloride, carboxylic acid bromide, sulfonic acid chloride, sulfonic acid anhydride, sulfonic acid carboxylic anhydride, etc., and carboxylic acid anhydride and carboxylic acid chloride are more preferred. Preferred compounds of carboxylic anhydride include acetic anhydride, propionic anhydride, oxalic anhydride, succinic anhydride, maleic anhydride, phthalic anhydride, benzoic anhydride, 5-norbornene-2,3-dicarboxylic anhydride, etc. In addition, as preferred compounds of carboxylic acid chlorides, there can be cited acetyl chloride, acryloyl chloride, propionyl chloride, methacryloyl chloride, trimethylacetyl chloride, cyclohexane methyl chloride, 2-ethylhexanoyl chloride, cinnamyl chloride, 1-adamantane methyl chloride, heptafluorobutyl chloride, stearyl chloride, benzoyl chloride, etc.

-Solid precipitation-

When manufacturing a polyimide precursor, etc., a step of precipitating a solid may be included. Specifically, After filtering out the water-absorbing byproduct of the dehydration condensation agent coexisting in the reaction solution as needed, the obtained polymer component is added to a poor solvent such as water, aliphatic lower alcohol or a mixture thereof, and the polymer component is precipitated as a solid and dried, thereby obtaining a polyimide precursor, etc. In order to increase the degree of purification, operations such as re-dissolving, re-precipitating, and drying the polyimide precursor, etc. may be repeated. Furthermore, 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 relative to the total solid content of the resin composition, more preferably 30% by mass or more, further preferably 40% by mass or more, and further preferably 50% by mass or more. In addition, the content of the resin in the resin composition of the present invention is preferably 99.5% by mass or less relative to the total solid content of the resin composition, more preferably 99% by mass or less, further preferably 98% by mass or less, further preferably 97% by mass or less, and still further preferably 95% by mass or less.

The resin composition of the present invention may contain only one specific resin or may contain two or more specific resins. When containing two or more specific resins, the total amount is preferably within the above range.

Furthermore, it is also preferred that the resin composition of the present invention contains at least 2 types of resins.

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

When the resin composition of the present invention contains two or more specific resins, it is preferred that the resin composition contains two or more polyimide precursors having different structures (R ¹¹⁵ in the above formula (2)) derived from dianhydride, for example.

<Other resins>

The resin composition of the present invention may contain the above-mentioned specific resin and other resins different from the specific resin (hereinafter, also referred to as "other resins").

As other resins, phenol resins, polyamide, epoxy resins, resins containing polysiloxane and siloxane structures, (meth)acrylic resins, (meth)acrylic amide resins, urethane resins, butyral resins, styrene resins, polyether resins, polyester resins, etc. can be cited.

For example, by further adding (meth) acrylic resin, a resin composition with excellent coating properties can be obtained, and a pattern (cured product) with excellent solvent resistance can be obtained.

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

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

Furthermore, the content of other resins in the resin composition of the present invention is preferably 80% by mass or less relative to the total solid content of the resin composition, more preferably 75% by mass or less, further preferably 70% by mass or less, further preferably 60% by mass or less, and still further preferably 50% by mass or less.

In addition, as a preferred embodiment of the resin composition of the present invention, the content of other resins can also be set to a low content. In the above embodiment, the content of other resins relative to the total solid content of the resin composition is preferably 20% by mass or less, 15% by mass or less is more preferred, 10% by mass or less is further preferred, 5% by mass or less is further preferred, and 1% by mass or less is further preferred. The lower limit of the above content is not particularly limited, as long as it is 0% by mass or more.

The resin composition of the present invention may contain only one other resin or may contain two or more. When containing two or more resins, the total amount is preferably within the above range.

<Compound B>

The curable resin composition of the present invention comprises a compound B having at least one structure selected from the group consisting of an oxalic acid monoester structure, an oxalic acid diester structure, an oxalic acid monoamide structure, an oxalic acid diamide structure, and an oxalate amide structure (hereinafter also referred to as a "specific structure") and a polymerizable group.

In the present invention, the oxalic acid monoester structure refers to a structure represented by the following formula (S-1) in which one of the * is directly bonded to a univalent or divalent or higher alkyl group.

In the present invention, the oxalic acid diester structure refers to a structure represented by the following formula (S-1) and a structure in which two * are directly bonded to a univalent or divalent or higher valent alkyl group. The alkyl groups bonded to the above two * may be the same or different.

In the present invention, the oxalic acid monoamide structure refers to a structure represented by the following formula (S-2) and a structure in which the * bonded to the nitrogen atom is directly bonded to a univalent or divalent or higher alkyl group and the * bonded to the oxygen atom is directly bonded to a hydrogen atom.

In the present invention, the oxalic acid diamide structure refers to a structure in which two * in the following formula (S-3) are directly bonded to a univalent or divalent or higher valent alkyl group. The alkyl groups bonded to the above two * may be the same or different.

In the present invention, the oxalate amide structure refers to a structure in which two * in the following formula (S-2) are directly bonded to a univalent or divalent or higher valent alkyl group. The alkyl groups bonded to the above two * may be the same or different.

Among them, formula (S-1) is preferred from the perspective of compatibility of the components in the resin composition (e.g., solvent, resin, or components other than these).

In formula (S-1) to formula (S-3), R ^N each independently represents a hydrogen atom or a monovalent organic group, and * each independently represents a bonding site with other structures.

^RN preferably represents a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms, more preferably a hydrogen atom or a alkyl group having 1 to 20 carbon atoms, and even more preferably a hydrogen atom. When ^RN in the formula is plural, the ^RNs may be the same or different.

The above-mentioned alkyl group may be an aromatic alkyl group, an aliphatic alkyl group, or any of the groups represented by these bonds, but an aromatic alkyl group or an aliphatic alkyl group is preferred, and an alkyl group is more preferred.

Compound B may contain only one specific structure or may contain two or more specific structures. When compound B contains two or more specific structures, each specific structure may be the same or different.

The content of the specific structure in compound B is preferably 0.0001~0.1 mol/g, and more preferably 0.001~0.01 mol/g.

唑基等公知的聚合性基，自由基聚合性基、環氧基或烷氧基甲矽烷基為較佳，自由基聚合性基為更佳。 Examples of the polymerizable group contained in compound B include a radical polymerizable group, an epoxy group, an oxobutylene group, a hydroxymethyl group, an alkoxymethyl group, an alkoxysilyl group, a blocked isocyanate group,

A known polymerizable group such as an oxazolyl group, a radical polymerizable group, an epoxy group or an alkoxysilyl group is preferred, and a radical polymerizable group is more preferred.

As the above-mentioned free radical polymerizable group, a group having an ethylenic unsaturated bond is preferred.

As the group having an ethylenic unsaturated bond, there can be cited vinyl, allyl, butylene diimide, vinylphenyl, (meth)acrylamide, (meth)acryloxy, etc., with (meth)acryloxy being preferred.

Furthermore, the alkoxysilyl group may be any one of a monoalkoxysilyl group, a dialkoxysilyl group, and a trialkoxysilyl group, but a dialkoxysilyl group or a trialkoxysilyl group is preferred, and a trialkoxysilyl group is more preferred.

The carbon number of the alkoxy group in the above alkoxysilyl group is preferably 1 to 10, more preferably 1 to 4, further preferably 1 or 2, and particularly preferably 2.

Compound B may contain only one polymerizable group or may contain two or more. However, from the perspective of the drug resistance of the obtained compound, it is better to contain two or more, more preferably 2 to 10, and even more preferably 2 to 6. When compound B contains two or more polymerizable groups, the structures of the polymerizable groups may be the same or different.

The content of polymerizable groups in compound B is preferably 0.0001~0.1 mol/g, and more preferably 0.001~0.008 mol/g.

Among them, compound B is preferably a compound represented by the following formula (1).

^X1 and ^X2 are independently -O- or -NZ-, Z is a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms, ^R2 is a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms, and ^R1 represents a monovalent organic group including a polymerizable group.

In formula (1), ^X1 and ^X2 are independently -O- or -NZ-, preferably both are -O- or both are -NH-, and more preferably both are -O-.

Furthermore, when at least one of ^X1 and ^X2 is -O-, it is preferred in terms of compatibility with the components in the resin composition (for example, the solvent, the resin, or components other than these).

Furthermore, when at least one of ^X1 and ^X2 is -NZ-, the cohesiveness is strong and it is preferable in terms of chemical resistance.

In formula (1), Z is a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms, preferably a hydrogen atom or a alkyl group having 1 to 20 carbon atoms, and more preferably a hydrogen atom.

The above-mentioned alkyl group may be an aromatic alkyl group, an aliphatic alkyl group or any of the groups represented by these bonds, but an aromatic alkyl group or an aliphatic alkyl group is preferred, and an alkyl group is more preferred.

In formula (1), ^R1 represents a monovalent organic group containing a polymerizable group. Preferred embodiments of the polymerizable group are as described above as preferred embodiments of the polymerizable group contained in compound B.

In formula (1), ^R1 is preferably a group represented by the following formula (P-1).

In formula (P-1), ^L1 represents a single bond or a linking group having a valence of m+1, ^A2 represents a polymerizable group, m represents an integer greater than 1, and * represents a bonding site with ^X1 .

In formula (P-1), ^L1 is preferably a single bond or a alkyl group, an ether bond, a carbonyl group, a thioether bond, a sulfonyl group, -NR ^N -, or a group obtained by two or more of these bonds; more preferably, a single bond or a alkyl group, an ether bond, a carbonyl group, -NR ^N -, or a group obtained by two or more of these bonds; and even more preferably, a group represented by a alkyl group or a bond of a alkyl group and an ether bond.

The above-mentioned ^RN represents a hydrogen atom or a alkyl group, more preferably a hydrogen atom, an alkyl group or an aryl group, further preferably a hydrogen atom or an alkyl group, and particularly preferably a hydrogen atom.

As the alkyl group in the above ^L1 , a saturated aliphatic alkyl group having 1 to 30 carbon atoms, an aromatic alkyl group having 6 to 30 carbon atoms, or a group represented by these combinations is preferred, and a saturated aliphatic alkyl group having 1 to 10 carbon atoms, a group obtained by removing 2 or more hydrogen atoms from a benzene ring, or a group represented by these bonds is more preferred.

In formula (P-1), ^A2 represents the polymerizable group described as the polymerizable group contained in the above-mentioned compound B, and the preferred embodiment is also the same.

In formula (P-1), m is preferably an integer of 1 to 15, more preferably an integer of 1 to 10, further preferably an integer of 1 to 5, particularly preferably an integer of 1 to 3, and 1 is the best.

Among these, in the present invention, the embodiment in which m is 1 and ^L1 is a group represented by a alkyl group, a (poly) alkoxy group or a combination thereof is also preferred.

As the above-mentioned alkyl group, an alkylene group, a divalent aromatic alkyl group or a group represented by a combination thereof is preferred, and an alkylene group or a phenylene group is more preferred.

In this specification, (poly)alkoxyl groups represent alkoxyl groups or polyalkoxyl groups. In addition, in the present invention, polyalkoxyl groups refer to groups in which alkoxyl groups are directly bonded to two or more groups. The alkylene groups in the multiple alkoxyl groups contained in the polyalkoxyl groups may be the same or different. In the case where the polyalkoxyl groups contain multiple alkoxyl groups with different alkylene groups, the arrangement of the alkoxyl groups in the polyalkoxyl groups may be a random arrangement, an arrangement with blocks, or an arrangement with alternating patterns.

As the above-mentioned alkylene group, an alkylene group having 1 to 30 carbon atoms is preferred, an alkylene group having 1 to 20 carbon atoms is more preferred, and an alkylene group having 1 to 10 carbon atoms is further preferred.

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

As the alkylene group in the above-mentioned (poly)alkylene group, an alkylene group having 2 to 10 carbon atoms is preferred, an alkylene group having 2 to 4 carbon atoms is more preferred, an ethylene group or a propylene group is more preferred, and an ethylene group is further preferred.

Furthermore, the number of alkoxy groups contained in the polyalkoxy group (the number of repetitions of the polyalkoxy group) is preferably 2 to 20, more preferably 2 to 10, further preferably 2 to 5, and particularly preferably 2 to 4.

Among them, the group represented by the following formula is preferred as R ¹ , but is not limited thereto. In the following formula, * represents the bonding site with X ¹ in formula (1), R independently represents a hydrogen atom or a methyl group, Et represents an ethyl group, and n represents a repetition number, preferably 2 to 10.

In formula (1), ^R2 is preferably a hydrogen atom, a monovalent organic group not containing a polymerizable group, or a monovalent organic group containing a polymerizable group, and preferably a monovalent organic group containing a polymerizable group.

When R ² is a monovalent organic group containing a polymerizable group, preferred aspects of R ² are the same as the preferred aspects of R ¹ described above.

Furthermore, when ^R2 is a monovalent organic group containing a polymerizable group, ^R1 and ^R2 may be the same group or different groups. The aspect that ^R1 and ^R2 are the same group is also one of the preferred aspects of the present invention. Among them, when ^R2 is a group represented by formula (P-1), the description of the above "bonding site with ^X1 " is replaced by "bonding site with ^X2 ".

Furthermore, when R ² is a monovalent organic group not containing a polymerizable group, R ² is preferably a alkyl group having 1 to 20 carbon atoms, more preferably a alkyl group having 1 to 4 carbon atoms, and even more preferably an alkyl group having 1 to 4 carbon atoms.

The molecular weight of compound B (weight average molecular weight in the case of a molecular weight distribution) is preferably 100-2000, and more preferably 150-1000.

As specific examples of compound B, compounds with the following structures can be cited, but are not limited to them.

In the following chemical formula, Et represents ethyl, and n and m independently represent the number of repetitions, preferably integers of 2 to 10.

[Chemical formula 22]

The curable resin composition of the present invention preferably contains 0.01 to 20 mass % of compound B relative to 100 mass parts of the resin, more preferably 0.1 to 10 mass % and even more preferably 0.5 to 5 mass % .

The curable resin composition of the present invention may contain only one compound B or may contain two or more.

In the case of involving two or more types, it is better for the total amount to be within the above range.

<Solvent>

The resin composition of the present invention preferably contains a solvent.

Any known solvent can be used as the solvent. The solvent is preferably an organic solvent. Examples of organic solvents include compounds such as esters, ethers, ketones, cyclic hydrocarbons, sulfides, amides, ureas, and alcohols.

Examples of the esters include ethyl acetate, n-butyl acetate, isobutyl acetate, hexyl acetate, amyl formate, isoamyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, γ-butyrolactone, ε-caprolactone, δ-valerolactone, alkyl alkoxyacetates (e.g., methyl alkoxyacetate, ethyl alkoxyacetate, butyl alkoxyacetate (e.g., methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, etc.)), alkyl 3-alkoxypropionates (e.g., methyl 3-alkoxypropionate, ethyl 3-alkoxypropionate, etc. (e.g., methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate), Esters, etc.)), alkyl 2-alkoxypropionates (e.g., methyl 2-alkoxypropionate, ethyl 2-alkoxypropionate, propyl 2-alkoxypropionate, etc. (e.g., methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate)), methyl 2-alkoxy-2-methylpropionate and ethyl 2-alkoxy-2-methylpropionate (e.g., methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, etc.), methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetylacetate, ethyl acetylacetate, methyl 2-oxobutyrate, ethyl 2-oxobutyrate, ethyl hexanoate, ethyl heptanoate, dimethyl malonate, diethyl malonate, etc. are preferred.

As 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 solvent acetate, ethyl solvent acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol dimethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether, ethylene glycol monobutyl ether acetate, diethylene glycol ethyl methyl ether, propylene glycol monopropyl ether acetate, dipropylene glycol dimethyl ether, etc. can be cited as preferred ones.

As ketones, for example, methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, 3-methylcyclohexanone, levoglucosanone, dihydroglucosanone, etc. can be cited as preferred ones.

As cyclic hydrocarbons, aromatic hydrocarbons such as toluene, xylene, and anisole, and cyclic terpenes such as limonene are preferred.

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

As amides, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N-cyclohexyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide, N,N-dimethylisobutyramide, 3-methoxy-N,N-dimethylpropionamide, 3-butoxy-N,N-dimethylpropionamide, N-formylmorpholine, N-acetylmorpholine, etc. can be cited as preferred ones.

As ureas, N,N,N’,N’-tetramethylurea, 1,3-dimethyl-2-imidazolidinone, etc. can be cited as preferred ones.

As alcohols, there can be cited 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 monopropylene glycol monoethyl ether, propylene glycol monomethyl ether, polyethylene glycol monomethyl ether, polypropylene glycol, tetraethylene glycol, ethylene glycol monobutyl ether, ethylene glycol monoethylene glycol monobenzyl ether, ethylene glycol monoethylene glycol monophenyl ether, methyl phenyl alcohol, n-pentanol, methylpentanol and diacetone alcohol, etc.

Regarding solvents, from the perspective of improving the properties of the coated surface, it is better to mix two or more solvents.

In the present invention, it is preferred to use one solvent selected from 3-ethoxypropionic acid methyl ester, 3-ethoxypropionic acid ethyl ester, ethyl solvent acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, 3-methoxypropionic acid methyl ester, 2-heptanone, cyclohexanone, cyclopentanone, γ-butyrolactone, dimethyl sulfoxide, ethyl carbitol acetate, butyl carbitol acetate, N-methyl-2-pyrrolidone, propylene glycol methyl ether and propylene glycol methyl ether acetate, levoglucosanone, dihydroglucosanone or a mixed solvent consisting of two or more of them. It is particularly preferred to use dimethyl sulfoxide and γ-butyrolactone or to use N-methyl-2-pyrrolidone and ethyl lactate at the same time.

From the perspective of coating properties, the content of the solvent is preferably set to an amount where the total solid content concentration of the resin composition of the present invention is 5 to 80 mass %, more preferably 5 to 75 mass %, more preferably 10 to 70 mass %, and even more preferably 20 to 70 mass %. The solvent content can be adjusted according to the desired thickness of the coating and the coating method.

The resin composition of the present invention may contain only one solvent or may contain two or more solvents. When containing two or more solvents, it is preferred that the total amount is within the above range.

[Polymerization initiator]

The resin composition of the present invention preferably contains a polymerization initiator capable of initiating polymerization by light and/or heat. The resin composition of the present invention preferably contains at least one of a photopolymerization initiator and a thermal polymerization initiator, and particularly preferably contains a photopolymerization initiator.

The photopolymerization initiator is preferably a photoradical polymerization initiator. There is no particular limitation on the photoradical polymerization initiator, and it can be appropriately selected from known photoradical polymerization initiators. For example, a photoradical polymerization initiator that is sensitive to light in the ultraviolet region to the visible region is preferred. In addition, it can also be an activator that generates active radicals by reacting with a photoexcited sensitizer.

The photo-free radical polymerization initiator preferably contains at least one compound having a molar absorption coefficient of at least about 50 L/mol ^-1 /cm ^-1 in the wavelength range of about 240 to 800 nm (preferably 330 to 500 nm). The molar absorption coefficient of the compound can be measured using a known method. For example, it is preferably measured using an ultraviolet-visible spectrophotometer (Cary-5 spectrophotometer manufactured by Varian Medical Systems, Inc.) and using an ethyl acetate solvent at a concentration of 0.01 g/L.

骨架之化合物、具有

二唑骨架之化合物、具有三鹵甲基之化合物等)、醯基氧化膦等醯基膦化合物、六芳基雙咪唑、肟衍生物等肟化合物、有機過氧化物、硫化合物、酮化合物、芳香族鎓鹽、酮肟醚、胺基苯乙酮等α-胺基酮化合物、羥基苯乙酮等α-羥基酮化合物、偶氮系化合物、疊氮化合物、茂金屬化合物、有機硼化合物、鐵芳烴錯合物等。關於該等詳細內容，能夠參閱日本特開2016-027357號公報的0165~0182段、國際公開第2015/199219號的0138~0151段的記載，並將該內容編入本說明書中。又，可以舉出日本特開2014-130173號公報的 0065~0111段、日本專利第6301489號公報中所記載之化合物、MATERI AL STAGE 37~60p，vol.19，No.3，2019中所記載之過氧化物系光聚合起始劑、國際公開第2018/221177號中所記載的光聚合起始劑、國際公開第2018/110179號中所記載的光聚合起始劑、日本特開2019-043864號公報中所記載的光聚合起始劑、日本特開2019-044030號公報中所記載的光聚合起始劑、日本特開2019-167313號公報中所記載的過酸化物系起始劑，並將該等內容亦編入本說明書中。 As the photo-radical polymerization initiator, any known compound can be used. For example, halogenated hydrocarbon derivatives (e.g., having three

Skeleton compounds, having

Compounds having a triazole skeleton, compounds having a trihalomethyl group, etc.), acylphosphine compounds such as acylphosphine oxide, hexaarylbiimidazole, oxime compounds such as oxime derivatives, organic peroxides, sulfur compounds, ketone compounds, aromatic onium salts, ketoxime ethers, α-aminoketone compounds such as aminoacetophenone, α-hydroxyketone compounds such as hydroxyacetophenone, azo compounds, metallocene compounds, organic boron compounds, iron aromatic complexes, etc. For the details, reference can be made to paragraphs 0165 to 0182 of Japanese Patent Application Publication No. 2016-027357 and paragraphs 0138 to 0151 of International Publication No. 2015/199219, and the contents are incorporated into this specification. In addition, the compounds described in paragraphs 0065 to 0111 of Japanese Patent Application No. 2014-130173, Japanese Patent Application No. 6301489, and MATERI AL STAGE 37~60p, vol.19, No.3, 2019, the peroxide-based 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 Patent Publication No. 2019-043864, the photopolymerization initiator described in Japanese Patent Publication No. 2019-044030, and the peroxide-based initiator described in Japanese Patent Publication No. 2019-167313, and these contents are also incorporated into this specification.

As ketone compounds, for example, compounds described in paragraph 0087 of Japanese Patent Publication No. 2015-087611 can be exemplified, and the contents are incorporated into this specification. Among commercially available products, KAYACURE DETX-S (manufactured by Nippon Kayaku Co., Ltd.) can also be preferably used.

In one embodiment of the present invention, hydroxyacetophenone compounds, aminoacetophenone compounds and acylphosphine compounds can be preferably used as photoradical polymerization initiators. More specifically, for example, aminoacetophenone-based initiators described in Japanese Patent Publication No. 10-291969 and acylphosphine oxide-based initiators described in Japanese Patent No. 4225898 can be used, and the contents are incorporated into this specification.

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

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

As aminoacetophenone-based initiators, compounds described in Japanese Patent Publication No. 2009-191179, which have a maximum absorption wavelength that matches a wavelength light source such as 365nm or 405nm, can also be used, and the content is incorporated into this manual.

As the acylphosphine oxide-based initiator, 2,4,6-trimethylbenzyl-diphenyl-phosphine oxide and the like can be cited. In addition, Omnirad 819, Omnirad TPO (both manufactured by IGM Resins B.V.), IRGACURE-819 or IRGACURE-TPO (product names: all manufactured by BASF) can be used.

Examples of metallocene compounds include IRGACURE-784, IRGACURE-784EG (both manufactured by BASF), Keycure VIS 813 (manufactured by King Brother Chem), etc.

As a photo-radical polymerization initiator, oxime compounds can be more effectively used. By using oxime compounds, the exposure tolerance can be more effectively improved. Oxime compounds have a wider exposure tolerance (exposure margin) and also act as a photohardening accelerator, so they are particularly good.

Specific examples of oxime compounds include compounds described in Japanese Patent Application Publication No. 2001-233842, compounds described in Japanese Patent Application Publication No. 2000-080068, compounds described in Japanese Patent Application Publication No. 2006-342166, compounds described in J.C.S. Perkin II (1979, pp. 1653-1660), compounds described in J.C.S. Perkin II (1979, pp. 156-162), and compounds described in Journal of Photopolymer Science and Technology. Technology (1995, pp. 202-232), compounds described in Japanese Patent Publication No. 2000-066385, compounds described in Japanese Patent Publication No. 2004-534797, compounds described in Japanese Patent Publication No. 2017-019766, compounds described in Japanese Patent Publication No. 6065596, compounds described in International Publication No. 2 The compounds described in 015/152153, the compounds described in International Publication No. 2017/051680, the compounds described in Japanese Patent Publication No. 2017-198865, the compounds described in paragraphs 0025 to 0038 of International Publication No. 2017/164127, the compounds described in International Publication No. 2013/167515, etc., and the contents are incorporated into this specification.

Preferred oxime compounds include, for example, compounds having the following structures: 3-benzoyloxyiminobutane-2-one, 3-acetyloxyiminobutane-2-one, 3-propionyloxyiminobutane-2-one, 2-acetyloxyiminopentane-3-one, 2-acetyloxyimino-1-phenylpropane-1-one, 2-benzoyloxyimino-1-phenylpropane-1-one, 3-(4-toluenesulfonyloxy)iminobutane-2-one, and 2-ethoxycarbonyloxyimino-1-phenylpropane-1-one. In the resin composition of the present invention, it is particularly preferred to use an oxime compound (oxime-based photoradical polymerization initiator) as the photoradical polymerization initiator. Oxime-based photo-free radical polymerization initiators have a linking group >C=N-O-C(=O)- in the molecule.

Among the commercially available products, IRGACURE OXE 01, IRGACURE OXE 02, IRGACURE OXE 03, IRGACURE OXE 04 (all manufactured by BASF), ADEKA OPTOMER N-1919 (manufactured by ADEKA CORPORATION, photoradical polymerization initiator 2 described in Japanese Patent Publication No. 2012-014052) can also be preferably used. In addition, TR-PBG-304, TR-PBG-305 (manufactured by Changzhou Tronly New Electronic Materials CO., LTD.), ADEKA ARKLS NCI-730, NCI-831 and ADEKA ARKLS NCI-930 (manufactured by ADEKA CORPORATION) can also be used. In addition, DFI-091 (manufactured by DAITO CHEMIX Co., Ltd.) and SpeedCure PDO (manufactured by SARTOMER ARKEMA) can be used. In addition, oxime compounds having the following structures can also be used.

As a photoradical polymerization initiator, an oxime compound having a fluorene ring can also be used. As specific examples of oxime compounds having a fluorene ring, compounds described in Japanese Patent Publication No. 2014-137466 and compounds described in Japanese Patent No. 06636081 can be cited, and the contents are incorporated into this specification.

As a photoradical polymerization initiator, an oxime compound having a skeleton in which at least one benzene ring in a carbazole ring is replaced by a naphthalene ring can also be used. As a specific example of such an oxime compound, the compound described in International Publication No. 2013/083505 can be cited, and the content is incorporated into this specification.

In addition, oxime compounds having fluorine atoms can also be used. Specific examples of such oxime compounds include compounds described in Japanese Patent Publication No. 2010-262028, compounds 24, 36 to 40 described in paragraph 0345 of Japanese Patent Publication No. 2014-500852, and compound (C-3) described in paragraph 0101 of Japanese Patent Publication No. 2013-164471, and the contents are incorporated into this specification.

As a photopolymerization initiator, an oxime compound having a nitro group can be used. It is also preferable that the oxime compound having a nitro group is set as a dimer. As specific examples of oxime compounds having a nitro group, the compounds described in paragraphs 0031 to 0047 of Japanese Patent Publication No. 2013-114249, paragraphs 0008 to 0012 and paragraphs 0070 to 0079 of Japanese Patent Publication No. 2014-137466, and the compounds described in paragraphs 0007 to 0025 of Japanese Patent Publication No. 4223071 can be cited, and the contents are incorporated into this specification. In addition, as an oxime compound having a nitro group, ADEKA ARKLS NCI-831 (manufactured by ADEKA CORPORATION) can also be cited.

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

As a photo-radical polymerization initiator, an oxime compound obtained by bonding a substituent having a hydroxyl group to a carbazole skeleton can also be used. As such a photo-polymerization initiator, compounds described in International Publication No. 2019/088055 can be cited, and the contents are incorporated into this specification.

As a photopolymerization initiator, an oxime compound having an aromatic ring group Ar ^OX1 with an electron-withdrawing group introduced into the aromatic ring (hereinafter, also referred to as an oxime compound OX) can also be used. As the electron-withdrawing group possessed by the above-mentioned aromatic ring group Ar ^OX1 , there can be cited 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. Acyl groups and nitro groups are preferred. Acyl groups are more preferred, and benzoyl groups are further preferred because of the reason that a film with excellent light resistance can be easily formed. The benzoyl group may have a substituent. As the substituent, a halogen atom, a cyano group, a nitro group, a hydroxyl group, an alkyl group, an alkoxy group, an aryl group, an aryloxy group, a heterocyclic group, a heterocyclic oxygen group, an alkenyl group, an alkylthio group, an arylthio group, an acyl group or an amino group is preferred; an alkyl group, an alkoxy group, an aryl group, an aryloxy group, a heterocyclic oxygen group, an alkylthio group, an arylthio group or an amino group is more preferred; an alkoxy group, an alkylthio group or an amino group is further preferred.

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

In the formula, ^RX1 represents an alkyl group, an alkenyl group, an alkoxy group, an aryl group, an aryloxy group, a heterocyclic group, a heterocyclic oxy group, an alkylthio group, an arylthio group, an alkylsulfinyl group, an arylsulfinyl group, an alkylsulfonyl group, an arylsulfonyl group, an acyl group, an acyloxy group, an amino group, a phosphinyl group, an aminoformyl group or an aminosulfonyl group, ^RX2 represents an alkyl group, an alkenyl group, an alkoxy group, an aryl group, an aryloxy group, a heterocyclic group, a heterocyclic oxy group, an alkylthio group, an arylthio group, an alkylsulfinyl group, an arylsulfinyl group, an alkylsulfonyl group, an arylsulfonyl group, an acyloxy group or an amino group, and ^RX3 to ^RX14 each independently represent a hydrogen atom or a substituent.

Among them, at least one of ^RX10 ~ ^RX14 is an electron-withdrawing group.

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

As specific examples of oxime compounds OX, the compounds described in paragraphs 0083 to 0105 of Japanese Patent No. 4600600 can be cited, and the contents are incorporated into this specification.

As the best oxime compound, there can be cited the oxime compound having a specific substituent shown in Japanese Patent Publication No. 2007-269779 or the oxime compound having a thioaryl group shown in Japanese Patent Publication No. 2009-191061, and the contents are incorporated into this specification.

化合物、苄基二甲基縮酮化合物、α-羥基酮化合物、α-胺基酮化合物、醯基膦化合物、氧化膦化合物、茂金屬化合物、肟化合物、三芳基咪唑二聚體、鎓鹽化合物、苯并噻唑化合物、二苯甲酮化合物、苯乙酮化合物及其衍生物、環戊二烯基-苯-鐵錯合物及其鹽、鹵甲基

二唑化合物、3-芳基取代香豆素化合物之群組中的化合物為較佳。 From the viewpoint of exposure sensitivity, the photo radical polymerization initiator is selected from the group consisting of trihalomethyl tri

compounds, benzyl dimethyl ketal compounds, α-hydroxy ketone compounds, α-amino ketone compounds, acyl phosphine compounds, phosphine oxide compounds, metallocene compounds, oxime compounds, triarylimidazole dimers, onium salt compounds, benzothiazole compounds, benzophenone compounds, acetophenone compounds and their derivatives, cyclopentadienyl-benzene-iron complexes and their salts, halogenated methyl

Compounds from the group consisting of oxadiazole compounds and 3-aryl-substituted coumarin compounds are preferred.

化合物、α-胺基酮化合物、醯基膦化合物、氧化膦化合物、茂金屬化合物、肟化合物、 三芳基咪唑二聚體、鎓鹽化合物、二苯甲酮化合物、苯乙酮化合物，選自包括三鹵甲基三

化合物、α-胺基酮化合物、茂金屬化合物、肟化合物、三芳基咪唑二聚體、二苯甲酮化合物之群組中的至少1種化合物為更進一步較佳，使用茂金屬化合物或肟化合物為又更進一步較佳。 A further preferred photo-radical polymerization initiator is trihalomethyl tris(III)

compounds, α-amino ketone compounds, acyl phosphine compounds, phosphine oxide compounds, metallocene compounds, oxime compounds, triaryl imidazole dimers, onium salt compounds, benzophenone compounds, acetophenone compounds, selected from trihalomethyl tri

It is more preferred that at least one compound selected from the group consisting of a compound, an α-amino ketone compound, a metallocene compound, an oxime compound, a triarylimidazole dimer, and a benzophenone compound be used, and it is even more preferred that a metallocene compound or an oxime compound be used.

In addition, the photo-radical polymerization initiator can also use benzophenone, N,N'-tetraalkyl-4,4'-diaminobenzophenone (Michler's ketone) and other N,N'-tetraalkyl-4,4'-diaminobenzophenone, 2-benzyl-2-dimethylamino-1-(4-morpholinylphenyl)-butanone-1,2-methyl-1-[4-(methylthio)phenyl]-2-morpholinyl-acetone-1 and other aromatic ketones, quinones formed by condensation of alkyl anthraquinone and aromatic rings, benzoin ether compounds such as benzoin alkyl ether, benzoin, benzoin compounds such as alkyl benzoin, benzyl derivatives such as benzyl dimethyl ketal, etc. In addition, the compound represented by the following formula (I) can also be used.

In formula (I), R ¹⁰⁰ is an alkyl group having 1 to 20 carbon atoms, an alkyl group having 2 to 20 carbon atoms interrupted by one or more oxygen atoms, an alkoxy group having 1 to 12 carbon atoms, or a phenyl group, or a phenyl group or a biphenyl group substituted by at least one of an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, a halogen atom, a cyclopentyl group, a cyclohexyl group, an alkenyl group having 2 to 12 carbon atoms, an alkyl group having 2 to 18 carbon atoms interrupted by one or more oxygen atoms, and an alkyl group having 1 to 4 carbon atoms; R ¹⁰¹ is a group represented by formula (II) or a group identical to R ¹⁰⁰ ; and R ¹⁰² to R ¹⁰⁴ are each independently an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, or a halogen atom.

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

In addition, the photoradical polymerization initiator can also use the compounds described in paragraphs 0048 to 0055 of International Publication No. 2015/125469, and the content is incorporated into this specification.

As the photoradical polymerization initiator, a difunctional or trifunctional or higher photoradical polymerization initiator can be used. By using such a photoradical polymerization initiator, two or more radicals are generated from one molecule of the photoradical polymerization initiator, so that good sensitivity can be obtained. In addition, when a compound with an asymmetric structure is used, the crystallinity is reduced and the solubility in a solvent is improved, and it becomes difficult to precipitate over time, thereby improving the stability of the resin composition over time. Specific examples of bifunctional or trifunctional or higher photoradical polymerization initiators include dimers of oxime compounds described in JP-A-2010-527339, JP-A-2011-524436, International Publication No. 2015/004565, paragraphs 0407 to 0412 of JP-A-2016-532675, paragraphs 0039 to 0055 of International Publication No. 2017/033680, and compounds (E) and (G) described in JP-A-2013-522445. ), Cmpd1~7 described in International Publication No. 2016/034963, oxime ester photoinitiator described in paragraph 0007 of Japanese Patent Publication No. 2017-523465, photoinitiator described in paragraphs 0020~0033 of Japanese Patent Publication No. 2017-167399, photopolymerization initiator (A) described in paragraphs 0017~0026 of Japanese Patent Publication No. 2017-151342, oxime ester photoinitiator described in Japanese Patent Publication No. 6469669, etc., and the contents are incorporated into this specification.

When a photopolymerization initiator is included, its content relative to the total solid content of the resin composition of the present invention is preferably 0.1-30 mass%, more preferably 0.1-20 mass%, further preferably 0.5-15 mass%, and further preferably 1.0-10 mass%. The photopolymerization initiator may contain only one type or two or more types. When two or more photopolymerization initiators are contained, the total amount is preferably within the above range.

Furthermore, the photopolymerization initiator sometimes also functions as a thermal polymerization initiator, so sometimes the crosslinking based on the photopolymerization initiator is further carried out by heating in an oven or a heating plate.

[Sensitizer]

The resin composition may include a sensitizer. The sensitizer absorbs specific active radiation and becomes an electronically excited state. The sensitizer in the electronically excited state comes into contact with a thermal radical polymerization initiator, a photoradical polymerization initiator, etc., thereby generating electron transfer, energy transfer, heat, etc. As a result, the thermal radical polymerization initiator and the photoradical polymerization initiator cause chemical changes and decompose, and generate free radicals, acids or bases.

系、吡咯并吡唑偶氮次甲基系、

系、酞菁系、苯并吡喃系、靛藍系等化合物。 As the sensitizer that can be used, ethanolamine series, benzophenone series, michler's ketone series, coumarin series, pyrazole azo series, anilino azo series, triphenylmethane series, anthraquinone series, anthracene series, anthrapyridone series, benzylidene series, oxocyanine series, pyrazolotriazole azo series, pyridone azo series, cyanine series, phenanthridine series,

Series, pyrrolopyrazole azomethine series,

Compounds such as phthalocyanine series, benzopyran series, indigo series, etc.

唑、2-(對二甲基胺基苯乙烯基)苯并噻唑、2-(對二甲基胺基苯乙烯基)萘并(1,2-d)噻唑、2-(對二甲基胺基苯甲醯基)苯乙烯、二苯基乙醯胺、苯甲醯苯胺、N-甲基乙醯苯胺、3’,4’-二甲基乙醯苯胺等。 Examples of the sensitizer include michler's ketone, 4,4'-bis(diethylamino)benzophenone, 2,5-bis(4'-diethylaminobenzylidene)cyclopentane, 2,6-bis(4'-diethylaminobenzylidene)cyclohexanone, 2,6-bis(4'-diethylaminobenzylidene)-4-methylcyclohexanone, 4,4'-bis(dimethylamino)chalcone, 4,4'-bis(diethylamino) Chalcone, p-dimethylaminophenylallylidene dihydroindanone, p-dimethylaminobenzylidene dihydroindanone, 2-(p-dimethylaminophenylbiphenylene)-benzothiazole, 2-(p-dimethylaminophenylvinylene)benzothiazole, 2-(p-dimethylaminophenylvinylene)isonaphthothiazole, 1,3-bis(4'-dimethylaminobenzylidene)acetone, 1,3-bis(4'-diethylaminobenzylidene)acetone, 3-Benzyl-7-dimethylaminocoumarin, 3-ethoxycarbonyl-7-dimethylaminocoumarin, 3-benzyloxycarbonyl-7-dimethylaminocoumarin, 3-methoxycarbonyl-7-diethylaminocoumarin, 3-ethoxycarbonyl-7-diethylaminocoumarin (7-(diethylamino)coumarin) 3-hydroxybenzoic acid ethyl ester), N-phenyl-N'-ethylethanolamine, N-phenyldiethanolamine, N-p-tolyldiethanolamine, N-phenylethanolamine, 4-morpholinylbenzophenone, isoamyl dimethylaminobenzoate, isoamyl diethylaminobenzoate, 2-butylbenzimidazole, 1-phenyl-5-butyltetrazole, 2-butylbenzothiazole, 2-(p-dimethylaminostyryl)benzo

azole, 2-(p-dimethylaminostyryl)benzothiazole, 2-(p-dimethylaminostyryl)naphtho(1,2-d)thiazole, 2-(p-dimethylaminobenzyl)styrene, diphenylacetamide, benzaniline, N-methylacetaniline, 3',4'-dimethylacetaniline, etc.

In addition, other sensitizing pigments can be used.

For details about the sensitizing dye, please refer to paragraphs 0161 to 0163 of Japanese Patent Application No. 2016-027357, and the contents are incorporated into this manual.

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

[Chain transfer agent]

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

In addition, the chain transfer agent can also use the compounds described in paragraphs 0152 to 0153 of International Publication No. 2015/199219, and the content is incorporated into this specification.

When the resin composition of the present invention contains 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 even more preferably 0.5 to 5 parts by mass relative to 100 parts by mass of the total solid content of the resin composition of the present invention. The chain transfer agent may be only one or more than two. When there are more than two chain transfer agents, it is preferred that the total amount is within the above range.

[Photoacid generator]

The resin composition of the present invention preferably contains a photoacid generator.

Photoacid generator refers to a compound that generates at least one of Brünster acid and Lewis acid by irradiation with light of 200nm~900nm. The irradiated light is preferably light with a wavelength of 300nm~450nm, and more preferably light with a wavelength of 330nm~420nm. When the photoacid generator is used alone or used together with a sensitizer, a photoacid generator that can generate acid by photosensitization is preferred.

As examples of the acid generated, preferably hydrogen halides, carboxylic acids, sulfonic acids, sulfinic acids, thiosulfinic acids, phosphoric acids, phosphoric acid monoesters, phosphoric acid diesters, boron derivatives, phosphorus derivatives, antimony derivatives, halogen peroxides, sulfonic acid amides, etc. can be cited.

Examples of photoacid generators used in the resin composition of the present invention include quinone diazide compounds, oxime sulfonate compounds, organic halogenated compounds, organic borate compounds, disulfonic acid compounds, onium salt compounds, etc.

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

Examples of the quinone diazide compound include those obtained by forming a sulfonate bond of quinone diazide with a monovalent or polyvalent hydroxyl compound, those obtained by forming a sulfonate sulfonamide bond of quinone diazide with a monovalent or polyvalent amine compound, and those obtained by forming a sulfonate bond and/or a sulfonamide bond of quinone diazide with a polyhydroxy polyamine compound. All functional groups of the polyhydroxy compounds, polyamine compounds, and polyhydroxy polyamine compounds may not be substituted with quinone diazide, but preferably, 40 mol% or more of the total functional groups are substituted with quinone diazide on average. By containing this quinone diazide compound, a resin composition can be obtained that is sensitive to i-ray (wavelength 365nm), h-ray (wavelength 405nm), and g-ray (wavelength 436nm) of a mercury lamp, which are common ultraviolet rays.

Specific examples of the hydroxyl compound include phenol, trihydroxybenzophenone, 4-methoxyphenol, isopropyl alcohol, octanol, tert-butyl alcohol, cyclohexanol, naphthol, Bis-Z, BisP-EZ, TekP-4HBPA, TrisP-HAP, TrisP-PA, TrisP-SA, TrisOCR-PA, BisOCHP-Z, BisP-MZ, BisP-PZ, BisP-IPZ, BisOCP-IPZ, BisP-CP, BisRS-2P, BisRS-3P, BisP-OCHP, methylene tris-FR-CR, BisRS-2 6X, DML-MBPC, DML-MBOC, DML-OCHP, DML-PCHP, DML-PC, DML-PTBP, DML-34X, DML-EP, DML-POP, dihydroxymethyl-BisOC-P, DML-PFP, DML-PSBP, DML-MTrisPC, TriML-P, TriML-35XL, TML-BP, TML-HQ, TML-pp-BPF, TML-BPA, TMOM-BP, HML-TPPHBA, HML-TPHAP (the above are product names, Honshu Chemical Industry Co., Ltd.), BIR-OC, BIP-PC, BIR-PC, BIR-PTBP, BIR-PCHP, BIP-BIOC-F, 4PC, BIR-BIPC-F, TEP-BIP-A, 46DMOC, 46DMOEP, TM-BIP-A (the above are product names, manufactured by ASAHI YUKIZAI CORPORATION), 2,6-dimethoxymethyl-4-tert-butylphenol, 2,6-dimethoxymethyl-p-cresol, 2,6-diethoxymethyl-p-cresol, naphthol, tetrahydroxybenzophenone, methyl gallate, bisphenol A, bisphenol E, methylene bisphenol, BisP-AP (product name, manufactured by Honshu Chemical Industry Co., Ltd.), novolac resin, etc., but not limited to them.

As amino compounds, specifically, aniline, methylaniline, diethylamine, butylamine, 1,4-phenylenediamine, 1,3-phenylenediamine, 4,4'-diaminodiphenyl ether, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylsulfone, 4,4'-diaminodiphenyl ether, etc. can be cited, but it is not limited to these.

In addition, as polyhydroxy polyamino compounds, specifically, 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane, 3,3'-dihydroxybenzidine, etc. can be cited, but it is not limited to them.

Among them, phenol compounds and esters with 4-naphthoquinone diazide sulfonyl groups are preferred as quinone diazide compounds. This can achieve higher sensitivity and higher resolution for i-ray exposure.

The content of the quinone diazide compound used in the resin composition of the present invention is preferably 1 to 50 parts by mass, and more preferably 10 to 40 parts by mass relative to 100 parts by mass of the resin. By setting the content of the quinone diazide compound within this range, the contrast between the exposed part and the unexposed part can be obtained, thereby achieving higher sensitivity, which is preferred. Furthermore, a sensitizer, etc. can be added as needed.

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

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

In formula (OS-1), X ³ represents an alkyl group, an alkoxy group or a halogen atom. When there are multiple X ³ groups, they may be the same or different. The alkyl group and the alkoxy group in the above X ³ may have a substituent. As the alkyl group in the above X ³ , a linear or branched alkyl group having 1 to 4 carbon atoms is preferred. As the alkoxy group in the above X ³ , a linear or branched alkoxy group having 1 to 4 carbon atoms is preferred. As the halogen atom in the above X ³ , a chlorine atom or a fluorine atom is preferred.

In formula (OS-1), m3 represents an integer of 0 to 3, preferably 0 or 1. When m3 is 2 or 3, the plurality of ^X3 may be the same or different.

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

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

As specific examples of the oxime sulfonate compound represented by formula (OS-1), the following compounds described in paragraphs 0064 to 0068 of Japanese Patent Application Publication No. 2011-209692 and paragraphs 0158 to 0167 of Japanese Patent Application Publication No. 2015-194674 can be exemplified, and these contents are incorporated into this specification.

In formula (OS-103) to formula (OS-105), R ^s1 represents an alkyl group, an aryl group or a heteroaryl group, a plurality of R ^s2s may exist and each independently represents a hydrogen atom, an alkyl group, an aryl group or a halogen atom, a plurality of R ^s6s may exist and each independently represents a halogen atom, an alkyl group, an alkoxy group, a sulfonic acid group, an aminosulfonyl group or an alkoxysulfonyl group, Xs represents O or S, ns represents 1 or 2, and ms represents an integer of 0 to 6.

In formula (OS-103) to formula (OS-105), the ^alkyl group (preferably having 1 to 30 carbon atoms), aryl group (preferably having 6 to 30 carbon atoms) or heteroaryl group (preferably having 4 to 30 carbon atoms) represented by Rs1 may have a known substituent within the range that the effect of the present invention can be obtained.

In formula (OS-103) to formula (OS-105), R ^s2 is preferably a hydrogen atom, an alkyl group (preferably having 1 to 12 carbon atoms) or an aryl group (preferably having 6 to 30 carbon atoms), and a hydrogen atom or an alkyl group is more preferred. In a compound, when there are two or more R ^s2 , preferably one or two are alkyl groups, aryl groups or halogen atoms, more preferably one is an alkyl group, aryl group or halogen atom, and particularly preferably one is an alkyl group and the rest are hydrogen atoms. The alkyl group or aryl group represented by R ^s2 may have a known substituent as long as the effect of the present invention can be obtained.

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

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

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

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

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

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

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

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

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

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

In addition, in the above-mentioned oxime sulfonate compounds, the stereostructure (E, Z) of the oxime may be any one of them or a mixture.

As specific examples of the oxime sulfonate compounds represented by the above formula (OS-103) to formula (OS-105), the compounds described in paragraphs 0088 to 0095 of Japanese Patent Application Publication No. 2011-209692 and paragraphs 0168 to 0194 of Japanese Patent Application Publication No. 2015-194674 can be cited, and these contents are incorporated into this specification.

As other preferred aspects of the oxime sulfonate compound containing at least one oxime sulfonate group, compounds represented by the following formula (OS-101) and formula (OS-102) can be cited.

In formula (OS-101) or formula (OS-102), R ^u9 represents a hydrogen atom, an alkyl group, an alkenyl group, an alkoxy group, an alkoxycarbonyl group, an acyl group, a carbamoyl group, a sulfamoyl group, a sulfo group, a cyano group, an aryl group, or a heteroaryl group. It is more preferred that ^{R u9} is a cyano group or an aryl group, and it is further preferred that R ^u9 is a cyano group, a phenyl group, or a naphthyl group.

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

In formula (OS-101) or formula (OS-102), Xu represents -O-, -S-, -NH-, ^-NRu5- , _-CH2- , ^-CRu6H- or ^CRu6Ru7- , and ^Ru5 to ^Ru7 each independently represent an alkyl ^group or an aryl group.

In formula (OS-101) or formula (OS-102), R ^u1 to R ^u4 independently represent a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, an alkoxy group, an amine group, an alkoxycarbonyl group, an alkylcarbonyl group, an arylcarbonyl group, an amide group, a sulfonyl group, a cyano group or an aryl group. Two of R ^u1 to R ^u4 can be bonded to each other to form a ring. In this case, the ring can be condensed to form a condensed ring together with the benzene ring. As R ^u1 to R ^u4 , a hydrogen atom, a halogen atom or an alkyl group is preferred, and at least two of R ^u1 to R ^u4 are bonded to each other to form an aryl group. Among them, the embodiment in which R ^u1 to R ^u4 are all hydrogen atoms is preferred. The above substituents may also have substituents.

The compound represented by the above formula (OS-101) is more preferably a compound represented by the formula (OS-102).

In addition, in the above-mentioned oxime sulfonate compounds, the stereostructure (E, Z, etc.) of the oxime or benzothiazole ring may be any one of them or a mixture.

As specific examples of the compound represented by formula (OS-101), the compounds described in paragraphs 0102 to 0106 of Japanese Patent Application Publication No. 2011-209692 and paragraphs 0195 to 0207 of Japanese Patent Application Publication No. 2015-194674 can be exemplified, and these contents are incorporated into this specification.

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

[Chemical formula 32]

Commercially available products include WPAG-336 (manufactured by FUJIFILM Wako Pure Chemical Corporation), WPAG-443 (manufactured by FUJIFILM Wako Pure Chemical Corporation), and MBZ-101 (manufactured by Midori Kagaku Co., Ltd.).

In addition, the compounds represented by the following structural formula can also be cited as better examples.

唑化合物：S-三

化合物作為較佳例。 As the organic halogenated compound, specifically, there can be cited Wakabayashi et al., "Bull Chem. Soc Japan" 42, 2924 (1969), U.S. Patent No. 3,905,815, Japanese Patent Publication No. 46-4605, Japanese Patent Publication No. 48-36281, Japanese Patent Publication No. 55-32070, Japanese Patent Publication No. 60-239736, Japanese Patent Publication No. 61-169835, Japanese Patent Publication No. 61-169837, Japanese Patent Publication No. 62-58241, Japanese Patent Publication No. 62-212401, Japanese Patent Publication No. 63-70243, Japanese Patent Publication No. 63-298339, MP Hutt "Jurnal of Heterocyclic Chemistry" 1 (No3), (1970) and the like, and the contents thereof are incorporated into the present specification. In particular, the compounds substituted with a trihalomethyl group can be cited.

Azole compounds: S-triazole

Compounds are preferred examples.

環鍵結而成之s-三

衍生物，具體而言，例如可以舉出2,4,6-三(單氯甲基)-s-三

、2,4,6-三(二氯甲基)-s-三

、2,4,6-三(三氯甲基)-s-三

、2-甲基-4,6-雙(三氯甲基)-s-三

、2-正丙基-4,6-雙(三氯甲基)-s-三

、2-(α,α,β-三氯乙基)-4,6-雙(三氯甲基)-s-三

、2-苯基-4,6-雙(三氯甲基)-s-三

、2-(對甲氧基苯基)-4,6-雙(三氯甲基)-s-三

、2-(3,4-環氧苯基)-4,6-雙(三氯甲基)-s-三

、2-(對氯苯基)-4,6-雙(三氯甲基)-s-三

、2-〔1-(對甲氧基苯基)-2,4-丁二烯基〕-4,6-雙(三氯甲基)-s-三

、2-苯乙烯基-4,6-雙(三氯甲基)-s-三

、2-(對甲氧基苯乙烯基)-4,6-雙(三氯甲基)-s-三

、2-(對異丙氧基苯乙烯基)-4,6-雙(三氯甲基)-s-三

、2-(對甲苯基)-4,6-雙(三氯甲基)-s-三

、2-(4-萘氧基萘基)-4,6-雙(三氯甲基)-s-三

、2-苯硫基-4,6-雙(三氯甲基)-s-三

、2-苄硫基-4,6-雙(三氯甲基)-s-三

、2,4,6-三(二溴甲基)-s-三

、2,4,6-三(三溴甲基)-s-三

、2-甲基-4,6-雙(三溴甲基)-s-三

、2-甲氧基-4,6-雙(三溴甲基)-s-三

等。 More preferably, at least one mono-, di- or tri-halogen-substituted methyl group and s-tri-

Ring bonded s-three

Derivatives, specifically, include 2,4,6-tris(monochloromethyl)-s-tri

, 2,4,6-tris(dichloromethyl)-s-tri

, 2,4,6-tris(trichloromethyl)-s-tri

, 2-methyl-4,6-bis(trichloromethyl)-s-tri

, 2-n-propyl-4,6-bis(trichloromethyl)-s-tri

, 2-(α,α,β-trichloroethyl)-4,6-bis(trichloromethyl)-s-tri

, 2-phenyl-4,6-bis(trichloromethyl)-s-tri

, 2-(p-methoxyphenyl)-4,6-bis(trichloromethyl)-s-tri

, 2-(3,4-epoxyphenyl)-4,6-bis(trichloromethyl)-s-tri

, 2-(p-chlorophenyl)-4,6-bis(trichloromethyl)-s-tri

, 2-〔1-(p-methoxyphenyl)-2,4-butadienyl〕-4,6-bis(trichloromethyl)-s-tri

, 2-phenylvinyl-4,6-bis(trichloromethyl)-s-tri

, 2-(p-methoxyphenylvinyl)-4,6-bis(trichloromethyl)-s-tri

, 2-(p-isopropoxyphenylvinyl)-4,6-bis(trichloromethyl)-s-tri

, 2-(p-tolyl)-4,6-bis(trichloromethyl)-s-tri

, 2-(4-naphthyloxynaphthyl)-4,6-bis(trichloromethyl)-s-tri

, 2-phenylthio-4,6-bis(trichloromethyl)-s-tri

, 2-benzylthio-4,6-bis(trichloromethyl)-s-tri

, 2,4,6-tris(dibromomethyl)-s-tri

, 2,4,6-tris(tribromomethyl)-s-tri

, 2-methyl-4,6-bis(tribromomethyl)-s-tri

, 2-methoxy-4,6-bis(tribromomethyl)-s-tri

wait.

Examples of organic borate compounds include Japanese Patent Publication No. 62-143044, Japanese Patent Publication No. 62-150242, Japanese Patent Publication No. 9-188685, Japanese Patent Publication No. 9-188686, Japanese Patent Publication No. 9-188710, Japanese Patent Publication No. 2000-131837, Japanese Patent Publication No. 2002-107916, Japanese Patent No. 2764769, Japanese Patent Publication No. 2002-116539, and Kunz, Martin "Rad Tech '98. Proceeding April 19-22, 1998, Chicago" etc., organic borate salts described in Japanese Patent Publication No. 6-157623, Japanese Patent Publication No. 6-175564, Japanese Patent Publication No. 6-175561, organic boron-zirconium complexes or organic boron-oxygen-zirconium complexes described in Japanese Patent Publication No. 6-175554, Japanese Patent Publication No. 6-175553, organic boron-zirconium complexes described in Japanese Patent Publication No. 6-175553 The organic boron transition metal coordination complexes described in Japanese Patent Publication No. 9-188710, Japanese Patent Publication No. 6-348011, Japanese Patent Publication No. 7-128785, Japanese Patent Publication No. 7-140589, Japanese Patent Publication No. 7-306527, Japanese Patent Publication No. 7-292014, etc. are taken as specific examples, and the contents are incorporated into this specification.

As disulfide compounds, compounds described in Japanese Patent Publication No. 61-166544, Japanese Patent Application No. 2001-132318, etc. and diazo disulfide compounds can be cited.

Examples of the onium salt compounds include S.I.Schlesinger, Photogr. Sci. Eng., 18, 387 (1974), T.S.Bal et al. al, Polymer, 21, 423 (1980), ammonium salts described in U.S. Patent No. 4,069,055, Japanese Patent Publication No. 4-365049, etc., phosphonium salts described in the specifications of U.S. Patent No. 4,069,055 and U.S. Patent No. 4,069,056, European Patent No. 104,143, U.S. Patent No. 339,049, U.S. Patent No. 410,201, iodonium salts described in Japanese Patent Publication No. 2-150848 and Japanese Patent Publication No. 2-296514, European Patent No. 370,693, European Patent No. 39 0,214, European Patent No. 233,567, European Patent No. 297,443, European Patent No. 297,442, U.S. Patent No. 4,933,377, U.S. Patent No. 161,811, U.S. Patent No. 410,201, U.S. Patent No. 339,049, U.S. Patent No. 4,760,013, U.S. Patent No. 4,734,444, U.S. Patent No. 2,833,827, German Patent No. 2,904,626, German Patent No. 3,604,580, German Patent No. 3,604,581, J.V.Crivello et al, Macromolecules, 10(6), 1307(1977), J.V.Crivello et al, J.Polymer Sci., Polymer Chem.Ed., 17, 1047(1979), arsenic salts, pyridinium salts and other onium salts described in C.S.Wen et al, Teh, Proc.Conf.Rad.Curing ASIA, p478 Tokyo, Oct(1988), and the contents thereof are incorporated into this specification.

As the onium salt, there can be cited onium salts represented by the following general formulas (RI-I) to (RI-III).

In formula (RI-I), Ar ₁₁ represents an aryl group having 20 or less carbon atoms which may have 1 to 6 substituents, and preferred substituents include an alkyl group having 1 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, an alkynyl group having 2 to 12 carbon atoms, an aryl group having 6 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an aryloxy group having 1 to 12 carbon atoms, a halogen atom, an alkylamino group having 1 to 12 carbon atoms, a dialkylamino group having 2 to 12 carbon atoms, an alkylamide group having 1 to 12 carbon atoms, an arylamide group having 6 to 20 carbon atoms, a carbonyl group, a carboxyl group, a cyano group, a sulfonyl group, a thioalkyl group having 1 to 12 carbon atoms, and a thioaryl group having 1 to 12 carbon atoms. Z ₁₁ ^- represents a monovalent anion, which is a halogen ion, a perchlorate ion, a hexafluorophosphate ion, a tetrafluoroborate ion, a sulfonic acid ion, a sulfinic acid ion, a thiosulfonic acid ion, or a sulfate ion. In view of stability, perchlorate ions, hexafluorophosphate ions, tetrafluoroborate ions, sulfonic acid ions, and sulfinic acid ions are preferred. In formula (RI-II), Ar ₂₁ and Ar ₂₂ each independently represent an aryl group having 1 to 20 carbon atoms which may have 1 to 6 substituents. Preferred substituents include an alkyl group having 1 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, an alkynyl group having 2 to 12 carbon atoms, an aryl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an aryloxy group having 1 to 12 carbon atoms, a halogen atom, a monoalkylamino group having 1 to 12 carbon atoms, a dialkylamino group having an alkyl group having 1 to 12 carbon atoms, an alkylamide group or an arylamide group having an alkyl group having 1 to 12 carbon atoms, a carbonyl group, a carboxyl group, a cyano group, a sulfonyl group, a thioalkyl group having 1 to 12 carbon atoms, and a thioaryl group having 1 to 12 carbon atoms. Z ₂₁ ^- represents a monovalent anion, which is a halogen ion, a perchlorate ion, a hexafluorophosphate ion, a tetrafluoroborate ion, a sulfonic acid ion, a sulfinic acid ion, a thiosulfonic acid ion, or a sulfate ion. In view of stability and reactivity, perchlorate ions, hexafluorophosphate ions, tetrafluoroborate ions, sulfonic acid ions, sulfinic acid ions, and carboxylic acid ions are preferred. In formula (RI-III), R ₃₁ , R ₃₂ and R ₃₃ each independently represent an aryl group having 6 to 20 carbon atoms which may have 1 to 6 substituents, or an alkyl group, an alkenyl group or an alkynyl group. Preferably, an aryl group is preferred in view of reactivity and stability. Preferred substituents include an alkyl group having 1 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, an alkynyl group having 2 to 12 carbon atoms, an aryl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an aryloxy group having 1 to 12 carbon atoms, a halogen atom, a monoalkylamino group having 1 to 12 carbon atoms, a dialkylamino group having an alkyl group independently having 1 to 12 carbon atoms, an alkylamide group or an arylamide group having an alkyl group having 1 to 12 carbon atoms, a carbonyl group, a carboxyl group, a cyano group, a sulfonyl group, a thioalkyl group having 1 to 12 carbon atoms, and a thioaryl group having 1 to 12 carbon atoms. Z ₃₁ ^- represents a monovalent anion, which is a halogen ion, a perchlorate ion, a hexafluorophosphate ion, a tetrafluoroborate ion, a sulfonic acid ion, a sulfinic acid ion, a thiosulfonic acid ion, or a sulfate ion. In view of stability and reactivity, perchlorate ions, hexafluorophosphate ions, tetrafluoroborate ions, sulfonic acid ions, sulfinic acid ions, and carboxylic acid ions are preferred.

As specific examples of preferred photoacid generators, the following can be cited.

[Chemical formula 36]

[Chemical formula 37]

[Chemical formula 38]

The photoacid generator is preferably used in an amount of 0.1-20 mass % relative to the total solid content of the resin composition, more preferably 0.5-18 mass %, further preferably 0.5-10 mass %, further preferably 0.5-3 mass %, and even further preferably 0.5-1.2 mass %.

The photoacid generator may be used alone or in combination. When using multiple types in combination, the total amount is preferably within the above range.

In addition, in order to impart photosensitivity to the desired light source, it is also better to use it together with a sensitizer.

<Thermal acid generator>

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

化合物中的至少1種化合物的交聯反應。 The thermal acid generator has the following effect: by heating, it generates an acid to promote the reaction of a compound selected from compounds having a hydroxymethyl group, an alkoxymethyl group or an acyloxymethyl group, an epoxy compound, an oxycyclobutane compound and a benzo[pi]

Cross-linking reaction of at least one of the compounds.

The thermal decomposition starting temperature of the thermal acid generator is preferably 50℃~270℃, and more preferably 50℃~250℃. In addition, if a thermal acid generator is selected that does not generate acid when the composition is applied to the substrate and dried (pre-baking: about 70~140℃), but generates acid when finally heated (hardening: about 100~400℃) after patterning in subsequent exposure and development, it can suppress the decrease in sensitivity during development, so it is better.

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

As equipment used to measure the thermal decomposition start temperature, Q2000 (manufactured by TA Instruments.) and the like can be cited.

The acid generated from the thermal acid generator is preferably a strong acid, such as aromatic sulfonic acids such as p-toluenesulfonic acid and benzenesulfonic acid, alkanesulfonic acids such as methanesulfonic acid, ethanesulfonic acid, and butanesulfonic acid, or halogen sulfonic acids such as trifluoromethanesulfonic acid. Examples of such thermal acid generators include those described in paragraph 0055 of Japanese Patent Publication No. 2013-072935.

Among them, from the viewpoint of less residue in the organic film and less reduction in the physical properties of the organic film, the one that generates alkanesulfonic acid with 1 to 4 carbon atoms or halogen alkanesulfonic acid with 1 to 4 carbon atoms is more preferred. As the thermal acid generator, (4-hydroxyphenyl) dimethyl konjac salt of methanesulfonate, (4-((methoxycarbonyl)oxy)phenyl) dimethyl konjac salt of methanesulfonate, (4-hydroxyphenyl) methyl konjac salt of methanesulfonate, (4-((methoxycarbonyl)oxy)phenyl) methyl konjac salt of methanesulfonate, (4-hydroxyphenyl) methyl ((2-methylphenyl) methyl) konjac salt of methanesulfonate, (4-hydroxy Preferred are trifluoromethanesulfonic acid (4-((methoxycarbonyl)oxy)phenyl)dimethylcoppersulfonate, trifluoromethanesulfonic acid (4-((methoxycarbonyl)oxy)phenyl)methylcoppersulfonate, trifluoromethanesulfonic acid (4-hydroxyphenyl)methylcoppersulfonate, trifluoromethanesulfonic acid (4-((methoxycarbonyl)oxy)phenyl)methylcoppersulfonate, trifluoromethanesulfonic acid (4-hydroxyphenyl)methyl((2-methylphenyl)methyl)coppersulfonate, 3-(5-(((propanesulfonyl)oxy)imino)thiophene-2(5H)-ylidene)-2-(o-tolyl)propionitrile, and 2,2-bis(3-(methylsulfonylamino)-4-hydroxyphenyl)hexafluoropropane.

Furthermore, as a thermal acid generator, the compound described in paragraph 0059 of Japanese Patent Publication No. 2013-167742 is also preferred.

The content of the thermal acid generator is preferably 0.01 parts by mass or more relative to 100 parts by mass of the specific resin, and 0.1 parts by mass or more is more preferred. By containing 0.01 parts by mass or more, the crosslinking reaction is promoted, thereby further improving the mechanical properties and solvent resistance of the organic film. In addition, from the perspective of the electrical insulation of the organic film, 20 parts by mass or less is preferred, 15 parts by mass or less is more preferred, and 10 parts by mass or less is even more preferred.

<Alkali generator>

The resin composition of the present invention may contain an alkali generator. The alkali generator is a compound that can generate an alkali by physical or chemical action. Preferable alkali generators for the resin composition of the present invention include thermal alkali generators and photoalkali generators.

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

The base generator may be an ionic base generator or a non-ionic base generator. Examples of bases generated from the base generator include diamines and tertiary amines.

There is no particular limitation on the alkali generator of the present invention, and known alkali generators can be used. As known alkali generators, for example, aminoformyl oxime compounds, aminoformyl hydroxylamine compounds, aminoformic acid compounds, formamide compounds, acetamide compounds, carbamate compounds, benzylcarbamate compounds, nitrobenzylcarbamate compounds, sulfonic acid amide compounds, imidazole derivative compounds, amine imide compounds, pyridine derivative compounds, α-aminoacetophenone derivative compounds, quaternary ammonium salt derivative compounds, pyridinium salts, α-lactone ring derivative compounds, amine imide compounds, o-phthalimide derivative compounds, acyloxyimide compounds, etc. can be used.

As specific compounds of non-ionic base generators, compounds represented by formula (B1), formula (B2) or formula (B3) can be cited.

In formula (B1) and formula (B2), ^Rb1 , ^Rb2 and ^Rb3 are independently an organic group, a halogen atom or a hydrogen atom that does not have a tertiary amine structure. However, ^Rb1 and ^Rb2 will not be hydrogen atoms at the same time. In addition, ^Rb1 , ^Rb2 and ^Rb3 do not have a carboxyl group. Furthermore, in this specification, a tertiary amine structure refers to a structure in which the three bonds of a trivalent nitrogen atom are covalently bonded to a hydrocarbon carbon atom. Therefore, when the carbon atom to which the bond is formed is a carbon atom that forms a carbonyl group, that is, when an amide group is formed together with a nitrogen atom, it is not limited to this.

In formula (B1) and formula (B2), at least one of ^Rb1 , ^Rb2 and ^Rb3 preferably has a cyclic structure, and at least two of them more preferably have a cyclic structure. The cyclic structure may be either a monocyclic ring or a condensed ring, and a monocyclic ring or a condensed ring formed by condensing two monocyclic rings is preferred. The monocyclic ring is preferably a 5-membered ring or a 6-membered ring, and a 6-membered ring is more preferred. The monocyclic ring is preferably a cyclohexane ring or a benzene ring, and a cyclohexane ring is more preferred.

More specifically, ^Rb1 and ^Rb2 are preferably hydrogen atoms, alkyl groups (preferably having 1 to 24 carbon atoms, more preferably 2 to 18 carbon atoms, and further preferably 3 to 12 carbon atoms), alkenyl groups (preferably having 2 to 24 carbon atoms, more preferably 2 to 18 carbon atoms, and further preferably 3 to 12 carbon atoms), aryl groups (preferably having 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, and further preferably 6 to 10 carbon atoms), or aralkyl groups (preferably having 7 to 25 carbon atoms, more preferably 7 to 19 carbon atoms, and further preferably 7 to 12 carbon atoms). These groups may have substituents within the range in which the effects of the present invention are exerted. ^Rb1 and ^Rb2 may be bonded to each other to form a ring. As the formed ring, a 4-7-membered nitrogen-containing heterocyclic ring is preferred. In particular, ^Rb1 and ^Rb2 are preferably linear, branched or cyclic alkyl groups (preferably having 1 to 24 carbon atoms, more preferably 2 to 18 carbon atoms, and further preferably 3 to 12 carbon atoms) which may have a substituent, more preferably cycloalkyl groups (preferably having 3 to 24 carbon atoms, more preferably 3 to 18 carbon atoms, and further preferably 3 to 12 carbon atoms) which may have a substituent, and further preferably cyclohexyl groups which may have a substituent.

Examples of Rb ³ include alkyl (preferably having 1 to 24 carbon atoms, more preferably 2 to 18 carbon atoms, and more preferably 3 to 12 carbon atoms), aryl (preferably having 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, and more preferably 6 to 10 carbon atoms), alkenyl (preferably having 2 to 24 carbon atoms, more preferably 2 to 12 carbon atoms, and more preferably 2 to 6 carbon atoms), aralkyl (preferably having 7 to 23 carbon atoms, more preferably 7 to 19 carbon atoms, and more preferably 7 to 12 carbon atoms), Aralkenyl (preferably having 8 to 24 carbon atoms, more preferably 8 to 20 carbon atoms, and more preferably 8 to 16 carbon atoms), alkoxy (preferably having 1 to 24 carbon atoms, more preferably 2 to 18 carbon atoms, and more preferably 3 to 12 carbon atoms), aryloxy (preferably having 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, and more preferably 6 to 12 carbon atoms), or aralkyloxy (preferably having 7 to 23 carbon atoms, more preferably 7 to 19 carbon atoms, and more preferably 7 to 12 carbon atoms). Among them, cycloalkyl (preferably having 3 to 24 carbon atoms, more preferably 3 to 18 carbon atoms, and more preferably 3 to 12 carbon atoms), aralkenyl, and aralkyloxy are preferred. ^Rb3 may further have a substituent within the range in which the effect of the present invention is exerted.

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

In the formula, ^Rb11 and ^Rb12 and ^Rb31 and ^Rb32 have the same meanings as ^Rb1 and ^Rb2 in formula (B1), respectively.

^Rb13 is an alkyl group (preferably having 1 to 24 carbon atoms, more preferably 2 to 18 carbon atoms, and more preferably 3 to 12 carbon atoms), an alkenyl group (preferably having 2 to 24 carbon atoms, more preferably 2 to 18 carbon atoms, and more preferably 3 to 12 carbon atoms), an aryl group (preferably having 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, and more preferably 6 to 12 carbon atoms), or an aralkyl group (preferably having 7 to 23 carbon atoms, more preferably 7 to 19 carbon atoms, and more preferably 7 to 12 carbon atoms), and may have a substituent within a range in which the effects of the present invention are exerted. Among them, ^Rb13 is preferably an aralkyl group.

^Rb33 and ^Rb34 are independently a hydrogen atom, an alkyl group (preferably having 1 to 12 carbon atoms, more preferably 1 to 8 carbon atoms, and more preferably 1 to 3 carbon atoms), an alkenyl group (preferably having 2 to 12 carbon atoms, more preferably 2 to 8 carbon atoms, and more preferably 2 to 3 carbon atoms), an aryl group (preferably having 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, and more preferably 6 to 10 carbon atoms), or an aralkyl group (preferably having 7 to 23 carbon atoms, more preferably 7 to 19 carbon atoms, and more preferably 7 to 11 carbon atoms), wherein the hydrogen atom is preferred.

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

Furthermore, it is also preferred that the compound represented by formula (B1-1) is a compound represented by formula (B1-1a).

^Rb11 and ^Rb12 have the same meanings as ^Rb11 and ^Rb12 in formula (B1-1).

^Rb15 and ^Rb16 are hydrogen atoms, alkyl groups (preferably having 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, and more preferably 1 to 3 carbon atoms), alkenyl groups (preferably having 2 to 12 carbon atoms, more preferably 2 to 6 carbon atoms, and more preferably 2 to 3 carbon atoms), aryl groups (preferably having 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, and more preferably 6 to 10 carbon atoms), aralkyl groups (preferably having 7 to 23 carbon atoms, more preferably 7 to 19 carbon atoms, and more preferably 7 to 11 carbon atoms), preferably hydrogen atoms or methyl groups.

Rb ¹⁷ is an alkyl group (preferably having 1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms, and more preferably 3 to 8 carbon atoms), an alkenyl group (preferably having 2 to 12 carbon atoms, more preferably 2 to 10 carbon atoms, and more preferably 3 to 8 carbon atoms), an aryl group (preferably having 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, and more preferably 6 to 12 carbon atoms), or an aralkyl group (preferably having 7 to 23 carbon atoms, more preferably 7 to 19 carbon atoms, and more preferably 7 to 12 carbon atoms), wherein the aryl group is preferred.

In formula (B3), L represents a alkyl group, which is a divalent alkyl group having a saturated alkyl group on the linking chain connecting adjacent oxygen atoms and carbon atoms, and the number of atoms on the linking chain is 3 or more. In addition, ^RN1 and ^RN2 each independently represent a monovalent organic group.

In this specification, "connection chain" refers to an atom chain on a path connecting two atoms or a group of connected atoms that connects the connected objects in the shortest way (with the smallest number of atoms). For example, in the compound represented by the following formula, L is composed of a phenylene ethylene group and has an ethylene group as a saturated alkyl group, the connection chain is composed of 4 carbon atoms, and the number of atoms on the path of the connection chain (that is, the number of atoms constituting the connection chain, hereinafter also referred to as "connection chain length" or "length of the connection chain") is 4.

The number of carbon atoms in L of formula (B3) (including carbon atoms other than carbon atoms in the connecting chain) is preferably 3 to 24. The upper limit is preferably 12 or less, more preferably 10 or less, and particularly preferably 8 or less. The lower limit is more preferably 4 or more. From the viewpoint of rapid progress of the above-mentioned intramolecular cyclization reaction, the upper limit of the connecting chain length of L is preferably 12 or less, more preferably 8 or less, further preferably 6 or less, and particularly preferably 5 or less. In particular, the connecting chain length of L is preferably 4 or 5, and 4 is the most preferred. As specific preferred compounds of the base generator, for example, the compounds described in paragraphs 0102 to 0168 of International Publication No. 2020/066416 and the compounds described in paragraphs 0143 to 0177 of International Publication No. 2018/038002 can also be cited.

Furthermore, it is also preferred that the alkali generator comprises a compound represented by the following formula (N1).

[Chemical formula 44]

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

L is a divalent linking group, preferably a divalent organic group. The linking group has a linking chain length of 1 or more, preferably 2 or more. As the upper limit, 12 or less is preferred, 8 or less is more preferred, and 5 or less is further preferred. The linking chain length is the number of atoms present in the atomic arrangement that forms the shortest distance between the two carbonyl groups in the formula.

In formula (N1), R ^N1 and R ^N2 each independently represent a monovalent organic group (preferably having 1 to 24 carbon atoms, more preferably 2 to 18 carbon atoms, and more preferably 3 to 12 carbon atoms), preferably a alkyl group (preferably having 1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms, and more preferably 1 to 10 carbon atoms), and specifically, an aliphatic alkyl group (preferably having 1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms, and more preferably 1 to 10 carbon atoms) or an aromatic alkyl group (preferably having 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, and more preferably 6 to 10 carbon atoms) can be mentioned, and an aliphatic alkyl group is preferred. When an aliphatic alkyl group is used as R ^N1 and R ^N2 , the alkalinity of the resulting base is high, and therefore, it is preferred. Furthermore, the aliphatic alkyl group and the aromatic alkyl group may have a substituent, and the aliphatic alkyl group and the aromatic alkyl group may have an oxygen atom in the substituent in the aliphatic alkyl chain or in the aromatic ring. In particular, an embodiment in which the aliphatic alkyl group has an oxygen atom in the alkyl chain can be exemplified.

As the aliphatic alkyl group constituting ^RN1 and ^RN2 , there can be mentioned a linear or branched chain alkyl group, a cyclic alkyl group, a group related to a combination of a linear 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 carbon atoms, and even more preferably 3 to 12 carbon atoms. As for the linear or branched chain alkyl group, there can be mentioned, for example, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, an undecyl group, a dodecyl group, an isopropyl group, an isobutyl group, a sec-butyl group, a t-butyl group, an isopentyl group, a neopentyl group, a t-pentyl group, an isohexyl group, and the like.

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

The group related to the combination of chain alkyl and cyclic alkyl is preferably one with 4 to 24 carbon atoms, more preferably 4 to 18 carbon atoms, and even more preferably 4 to 12 carbon atoms. Examples of the group related to the combination of chain alkyl and cyclic alkyl include cyclohexylmethyl, cyclohexylethyl, cyclohexylpropyl, methylcyclohexylmethyl, ethylcyclohexylethyl, etc.

The alkyl group having an oxygen atom in the chain preferably has 2 to 12 carbon atoms, more preferably 2 to 6 carbon atoms, and even more preferably 2 to 4 carbon atoms. The alkyl group having an oxygen atom in the chain may be in the form of a chain or a ring, and may be a straight chain or a branched chain.

Among them, from the viewpoint of raising the boiling point of the base generated by decomposition described later, ^RN1 and ^RN2 are preferably alkyl groups having 5 to 12 carbon atoms. Among them, in a formulation where adhesion to metal (e.g., copper) during layer-by-layer bonding is important, a group having a cyclic alkyl group or an alkyl group having 1 to 8 carbon atoms is preferred.

環、嗎啉環等，可以較佳地舉出吡咯啉環、吡咯啶環、哌啶環、哌

環、嗎啉環。 R ^N1 and R ^N2 may be linked to each other to form a ring structure. When forming a ring structure, an oxygen atom or the like may be contained in the chain. Furthermore, the ring structure formed by R ^N1 and R ^N2 may be a monocyclic ring or a condensed ring, but a monocyclic ring is preferred. As the ring structure formed, a 5-membered ring or a 6-membered ring containing a nitrogen atom in formula (N1) is preferred, for example, a pyrrole ring, an imidazole ring, a pyrazole ring, a pyrroline ring, a pyrrolidine ring, an imidazolidinyl ring, a pyrazolidine ring, a piper ...

Ring, morpholine ring, etc., preferably pyrroline ring, pyrrolidinyl ring, piperidine ring, piperidine ring

Ring, morpholine ring.

R ^C1 represents a hydrogen atom or a protecting group, preferably a hydrogen atom.

As the protecting group, a protecting group that is decomposed by the action of an acid or a base is preferred, and a protecting group that is decomposed by an acid can be preferably exemplified.

As specific examples of the protecting group, chain or cyclic alkyl groups or chain or cyclic alkyl groups having an oxygen atom in the chain can be cited. As chain or cyclic alkyl groups, methyl, ethyl, isopropyl, tert-butyl, cyclohexyl, etc. can be cited. As chain alkyl groups having an oxygen atom in the chain, specifically, alkyloxyalkyl groups can be cited, and more specifically, methoxymethyl (MOM) groups, ethoxyethyl (EE) groups, etc. can be cited. As cyclic alkyl groups having an oxygen atom in the chain, epoxide groups, glycidyl groups, cyclobutylene groups, tetrahydrofuranyl groups, tetrahydropyranyl (THP) groups, etc. can be cited.

There is no particular stipulation as the divalent linking group constituting L, but a alkyl group is preferred, and an aliphatic alkyl group is more preferred. The alkyl group may have a substituent, and may also have atoms other than carbon atoms in the alkyl chain. More specifically, a divalent alkyl linking group having an oxygen atom in the chain is preferred, a divalent aliphatic alkyl group having an oxygen atom in the chain, a divalent aromatic alkyl group, or a group related to a combination of a divalent aliphatic alkyl group having an oxygen atom in the chain and a divalent aromatic alkyl group is more preferred, and a divalent aliphatic alkyl group having an oxygen atom in the chain is further preferred. It is preferred that these groups do not have an oxygen atom.

The divalent hydrocarbon linking group preferably has 1 to 24 carbon atoms, more preferably 2 to 12 carbon atoms, and more preferably 2 to 6 carbon atoms. The divalent aliphatic hydrocarbon group preferably has 1 to 12 carbon atoms, more preferably 2 to 6 carbon atoms, and more preferably 2 to 4 carbon atoms. The divalent aromatic hydrocarbon group preferably has 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, and more preferably 6 to 10 carbon atoms. The group related to the combination of the divalent aliphatic hydrocarbon group and the divalent aromatic hydrocarbon group (e.g., arylalkyl) preferably has 7 to 22 carbon atoms, more preferably 7 to 18 carbon atoms, and more preferably 7 to 10 carbon atoms.

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

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

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

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

The alkylene group having an oxygen atom in the chain can be in the form of a chain or a ring, and can be a straight chain or a branched chain. The alkylene group having an oxygen atom in the chain preferably has 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, and even more preferably 1 to 3 carbon atoms.

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

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

The aryl group preferably has 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, and even more preferably 6 to 10 carbon atoms.

The arylalkylene group preferably has 7 to 23 carbon atoms, more preferably 7 to 19 carbon atoms, and even more preferably 7 to 11 carbon atoms.

Among them, chain alkylene, cyclic alkylene, alkylene having oxygen atoms in the chain, chain alkenylene, arylene, arylene, and alkylene are preferred, and 1,2-ethylene, propanediyl (especially 1,3-propanediyl), cyclohexanediyl (especially 1,2-cyclohexanediyl), vinylene (especially cis-vinylene), phenylene (1,2-phenylene), phenylene methylene (especially 1,2-phenylene methylene), and oxyethylene (especially 1,2-vinyloxy-1,2-ethylene) are more preferred.

The following examples can be cited as alkali generators, but the present invention is not to be construed in a limiting sense by these.

The molecular weight of the non-ionic thermal alkali generator is preferably 800 or less, more preferably 600 or less, and even more preferably 500 or less. As the lower limit, 100 or more is preferred, 200 or more is more preferred, and 300 or more is even more preferred.

As specific preferred compounds for ionic base generators, for example, the compounds described in paragraphs 0148 to 0163 of International Publication No. 2018/038002 can also be cited.

As specific examples of ammonium salts, the following compounds can be cited, but the present invention is not limited to them.

As specific examples of imide salts, the following compounds can be cited, but the present invention is not limited to them.

[Chemical formula 47]

When the resin composition of the present invention contains an alkali generator, the content of the alkali 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 preferably 0.3 parts by mass or more, and 0.5 parts by mass or more is further preferred. The upper limit is preferably 30 parts by mass or less, 20 parts by mass or less is further preferred, and 10 parts by mass or less is further preferred. It can be 5 parts by mass or less, and can also be 4 parts by mass or less.

Alkali generators can be used in one or more types. When using two or more types, the total amount is preferably within the above range.

<Polymerizable compounds>

The resin composition of the present invention may include another polymerizable compound together with compound B.

As polymerizable compounds, free radical crosslinking agents or other crosslinking agents can be cited.

[Free radical cross-linking agent]

The resin composition of the present invention preferably contains a free radical crosslinking agent.

The free radical crosslinking agent is a compound having a free radical polymerizable group. As the free radical polymerizable group, a group containing an ethylenic unsaturated bond is preferred. As the above-mentioned group containing an ethylenic unsaturated bond, there can be cited groups having an ethylenic unsaturated bond such as vinyl, allyl, vinylphenyl, (meth)acryl, butylene diamide, (meth)acrylamide, etc.

Among them, (meth)acryl, (meth)acrylamide, and vinylphenyl are preferred as the above-mentioned group containing an ethylenic unsaturated bond. From the perspective of reactivity, (meth)acryl is more preferred.

The free radical crosslinking agent is preferably a compound having one or more ethylenic unsaturated bonds, but a compound having two or more is more preferred. The free radical crosslinking agent may have three or more ethylenic unsaturated bonds.

As the above-mentioned compound having more than 2 ethylenic unsaturated bonds, a compound having 2 to 15 ethylenic unsaturated bonds is preferred, a compound having 2 to 10 ethylenic unsaturated bonds is more preferred, and a compound having 2 to 6 ethylenic unsaturated bonds is further preferred.

Furthermore, from the perspective of the film strength of the obtained pattern (cured product), it is also preferred that the resin composition of the present invention contains a compound having two ethylenically unsaturated bonds and the above-mentioned compound having three or more ethylenically unsaturated bonds.

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

Specific examples of free radical crosslinking agents include unsaturated carboxylic acids (e.g., acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.) or their esters and amides, preferably esters of unsaturated carboxylic acids and polyol compounds and amides of unsaturated carboxylic acids and polyamine compounds. In addition, addition reaction products of unsaturated carboxylic acid esters or amides having affinity substituents such as hydroxyl groups, amino groups, thiohydrides, etc., and monofunctional or polyfunctional isocyanates or epoxides, and dehydration condensation reaction products of monofunctional or polyfunctional carboxylic acids, etc. can also be preferably used. Furthermore, addition reaction products of unsaturated carboxylates or amides having electrophilic substituents such as isocyanate groups or epoxy groups with monofunctional or polyfunctional alcohols, amines, and thiols, and substitution reaction products of unsaturated carboxylates or amides having dissociative substituents such as halogen groups or tosyloxy groups with monofunctional or polyfunctional alcohols, amines, and thiols are also preferred. Moreover, as another example, a compound group replaced with unsaturated phosphonic acid, vinylbenzene derivatives such as styrene, vinyl ether, allyl ether, etc. can also be used to replace the above-mentioned unsaturated carboxylic acid. As a specific example, the description of paragraphs 0113 to 0122 of Japanese Patent Publication No. 2016-027357 can be referred to, and such contents are incorporated into this specification.

In addition, the radical crosslinking agent is preferably a compound having a boiling point of 100°C or higher under normal pressure. Examples thereof include polyethylene glycol di(meth)acrylate, trihydroxymethylethane tri(meth)acrylate, neopentyl glycol di(meth)acrylate, neopentylthritol tri(meth)acrylate, neopentylthritol tetra(meth)acrylate, dipentylthritol penta(meth)acrylate, dipentylthritol hexa(meth)acrylate, hexanediol di(meth)acrylate, trihydroxymethylpropane tri(acryloxypropyl) ether, tri(acryloxyethyl) isocyanurate, glycerol or trihydroxymethylethane, etc., which are obtained by adding ethylene oxide or propylene oxide to a polyfunctional alcohol and then (meth)acrylating the obtained mixture. Compounds obtained by acidification, such as (meth)acrylic acid urethanes described in Japanese Patent Publication No. 48-041708, Japanese Patent Publication No. 50-006034, Japanese Patent Publication No. 51-037193, polyester acrylates described in Japanese Patent Publication No. 48-064183, Japanese Patent Publication No. 49-043191, Japanese Patent Publication No. 52-030490, epoxy acrylates as reaction products of epoxy resins and (meth)acrylic acid, and multifunctional acrylates or methacrylates, and mixtures thereof. In addition, compounds described in paragraphs 0254 to 0257 of Japanese Patent Publication No. 2008-292970 are also preferred. In addition, polyfunctional (meth)acrylates obtained by reacting compounds having a cyclic ether group and an ethylenically unsaturated bond such as (meth)acrylate with polyfunctional carboxylic acids can also be cited.

Furthermore, as a preferred free radical crosslinking agent other than the above, a compound having a fluorene ring and having two or more groups containing ethylenic unsaturated bonds or a cardo resin described in Japanese Patent Publication No. 2010-160418, Japanese Patent Publication No. 2010-129825, Japanese Patent Publication No. 4364216, etc. can also be used.

Furthermore, as other examples, specific unsaturated compounds described in Japanese Patent Publication No. 46-043946, Japanese Patent Publication No. 01-040337, Japanese Patent Publication No. 01-040336, or vinylphosphonic acid compounds described in Japanese Patent Publication No. 02-025493 can also be cited. In addition, compounds containing perfluoroalkyl groups described in Japanese Patent Publication No. 61-022048 can also be used. Furthermore, those introduced as photopolymerizable monomers and oligomers in "Journal of the Adhesion Society of Japan" vol. 20, No. 7, pp. 300-308 (1984) can also be used.

In addition to the above, the compounds described in paragraphs 0048 to 0051 of Japanese Patent Publication No. 2015-034964 and the compounds described in paragraphs 0087 to 0131 of International Publication No. 2015/199219 can also be preferably used, and these contents are incorporated into this specification.

In addition, in Japanese Patent Publication No. 10-062986, the following compounds described as formula (1) and formula (2) together with their specific examples can also be used as free radical crosslinking agents. The compounds are obtained by adding ethylene oxide or propylene oxide to a polyfunctional alcohol and then performing (meth)acrylic esterification.

Furthermore, the compounds described in paragraphs 0104 to 0131 of Japanese Patent Application No. 2015-187211 can also be used as free radical crosslinking agents, and such contents are incorporated into this specification.

As the radical crosslinking agent, dipentatriol triacrylate (commercially available as KAYARAD D-330; manufactured by Nippon Kayaku Co., Ltd.), dipentatriol tetraacrylate (commercially available as KAYARAD D-320; manufactured by Nippon Kayaku Co., Ltd., A-TMMT: manufactured by Shin-Nakamura Chemical Co., Ltd.), dipentatriol penta(meth)acrylate (commercially available as KAYARAD D-310; manufactured by Nippon Kayaku Co., Ltd.), dipentatriol hexa(meth)acrylate (commercially available as KAYARAD DPHA; manufactured by Nippon Kayaku Co., Ltd., A-DPH; manufactured by Shin-Nakamura Chemical Co., Ltd.) and the structure in which the (meth)acryloyl groups are bonded via ethylene glycol residues or propylene glycol residues is preferred. These oligomer types can also be used.

As commercially available free radical crosslinking agents, for example, SR-494 manufactured by Sartomer Company, Inc., which is a tetrafunctional acrylate having four ethoxy chains, SR-209, 231, 239 manufactured by Sartomer Company, Inc., which is a bifunctional methyl acrylate having four vinyloxy chains, DPCA-60 manufactured by Nippon Kayaku Co., Ltd., which is a hexafunctional acrylate having six pentoxy chains, TPA-330 manufactured by Nippon Kayaku Co., Ltd., which is a trifunctional acrylate having three isobutyloxy chains, urethane oligomers UAS-10 and UAB-140 (manufactured by NIPPON PAPER IN DUSTRIES CO., LTD.), NK ester M-40G, NK ester 4G, NK ester M-9300, NK ester A-9300, UA-7200 (manufactured by Shin-Nakamura Chemical Co., Ltd.), Co., Ltd.), DPHA-40H (Nippon Kayaku Co., Ltd.), UA-306H, UA-306T, UA-306I, AH-600, T-600, AI-600 (Kyoeisha Chemical Co., Ltd.), BLEMMER PME400 (NOF CORPORATION), etc.

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

The free radical crosslinking agent may be a free radical crosslinking agent having an acid group such as a carboxyl group or a phosphoric acid group. The free radical crosslinking agent having an acid group is preferably an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid, and a free radical crosslinking agent having an acid group by reacting a non-aromatic carboxylic acid anhydride with an unreacted hydroxyl group of an aliphatic polyhydroxy compound is more preferably a free radical crosslinking agent having an acid group by reacting a non-aromatic carboxylic acid anhydride with an unreacted hydroxyl group of an aliphatic polyhydroxy compound, wherein the aliphatic polyhydroxy compound is a compound of neopentyl triol or dipentyl triol. As commercially available products, for example, polyacid-modified acrylic oligomers manufactured by TOAGOSEI CO., Ltd. include M-510 and M-520.

The preferred acid value of the free radical crosslinking agent having an acid group is 0.1~300 mgKOH/g, and the most preferred acid value is 1~100 mgKOH/g. As long as the acid value of the free radical crosslinking agent is within the above range, the operability in manufacturing is excellent, and the developing property is excellent. In addition, the polymerization property is good. The above acid value is measured according to the description of JIS K 0070:1992.

From the perspective of pattern resolution and film stretchability, it is better to use bifunctional methacrylate or acrylate as the resin composition.

As specific compounds, triethylene glycol diacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, tetraethylene glycol diacrylate, PEG (polyethylene glycol) 200 diacrylate, PEG200 dimethacrylate, PEG600 diacrylate, PEG600 dimethacrylate, polyethylene glycol diacrylate, polyethylene glycol dimethacrylate, neopentyl glycol diacrylate, neopentyl glycol dimethacrylate, 3-methyl-1,5-pentanediol diacrylate, 1,6-hex ...methacrylate, 1,6-hexanediol diacrylate, 1,6-hexanediol diacrylate, 1,6-hexanediol diacrylate, 1,6-hexanediol diacrylate, 1,6-hexanediol diacrylate, 1,6-hexane Methacrylate, dihydroxymethyltricyclodecane diacrylate, dihydroxymethyltricyclodecane dimethacrylate, bisphenol A EO (ethylene oxide) adduct diacrylate, bisphenol A EO adduct dimethacrylate, bisphenol A PO (propylene oxide) adduct diacrylate, bisphenol A EO adduct dimethacrylate, 2-hydroxy-3-acryloxypropyl methacrylate, isocyanuric acid EO modified diacrylate, isocyanuric acid modified dimethacrylate, other bifunctional acrylates with urethane bonds, bifunctional methacrylates with urethane bonds. Two or more of these can be used in combination as needed.

Furthermore, for example, PEG200 diacrylate refers to polyethylene glycol diacrylate and the formula weight of the polyethylene glycol chain is about 200.

Regarding the resin composition of the present invention, from the viewpoint of suppressing warping along with the elastic modulus control of the pattern (cured product), a monofunctional radical crosslinking agent can be preferably used as the radical crosslinking agent. As monofunctional free radical crosslinking agents, 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-hydroxymethyl (meth)acrylamide, glycidyl (meth)acrylate, polyethylene glycol mono (meth)acrylate, polypropylene glycol mono (meth)acrylate and other (meth)acrylic acid derivatives, N-vinyl pyrrolidone, N-vinyl caprolactam and other N-vinyl compounds, alkenyl glycidyl ether and the like can be preferably used. As monofunctional free radical crosslinking agents, compounds having a boiling point of 100°C or more at normal pressure are also preferred in order to suppress volatility before exposure.

In addition, as free radical crosslinking agents with two or more functional groups, allyl compounds such as diallyl phthalate and triallyl trimellitate can be cited.

In the case of containing a free radical crosslinking agent, its content relative to the total solid content of the resin composition of the present invention is preferably more than 0 mass% and less than 60 mass%. The lower limit is more preferably 5 mass% or more. The upper limit is more preferably less than 50 mass%, and more preferably less than 30 mass%.

The free radical crosslinking agent can be used alone or in combination of two or more. When two or more are used simultaneously, the total amount is preferably within the above range.

[Other crosslinking agents]

It is also preferred that the resin composition of the present invention contains other crosslinking agents different from the above-mentioned free radical crosslinking agents.

In the present invention, other crosslinking agents refer to crosslinking agents other than the above-mentioned free radical crosslinking agents. Preferably, the compound has multiple groups in the molecule that promote the reaction of forming covalent bonds with other compounds in the composition or their reaction products by the photosensitization of the above-mentioned photoacid generator or photoalkali generator. Preferably, the compound has multiple groups in the molecule that promote the reaction of forming covalent bonds with other compounds in the composition or their reaction products by the action of acid or base.

The above-mentioned acid or base is preferably an acid or base generated from a photoacid generator or a photoalkali generator in the exposure step.

As other crosslinking agents, compounds having at least one group selected from the group including acyloxymethyl, hydroxymethyl and alkoxymethyl are preferred, and compounds having a structure in which at least one group selected from the group including acyloxymethyl, hydroxymethyl and alkoxymethyl is directly bonded to a nitrogen atom are more preferred.

As other crosslinking agents, for example, compounds having a structure in which the hydrogen atom of the amino group is substituted by an acyloxymethyl group, a hydroxymethyl group or an alkoxymethyl group by reacting formaldehyde or formaldehyde and alcohol with a compound containing an amino group such as melamine, glycoluril, urea, alkyl urea, benzoguanamine, etc. The production method of these compounds is not particularly limited, as long as the compound has the same structure as the compound produced by the above method. In addition, it can also be an oligomer formed by self-condensation of the hydroxymethyl groups of these compounds.

A crosslinking agent using melamine as the above-mentioned amino group-containing compound is called a melamine-based crosslinking agent, a crosslinking agent using glycoluril, urea or alkyl urea is called a urea-based crosslinking agent, a crosslinking agent using alkyl urea is called an alkyl urea-based crosslinking agent, and a crosslinking agent using benzoguanamine is called a benzoguanamine-based crosslinking agent.

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

上取代之化合物作為結構例。 Examples of the compound containing at least one of the alkoxymethyl group and the acyloxymethyl group of the present invention include an alkoxymethyl group or an acyloxymethyl group directly or trivalently attached to the aromatic group or the nitrogen atom of the following urea structure:

The above-substituted compounds are taken as structural examples.

The alkoxymethyl or acyloxymethyl group in the above-mentioned compound preferably has 2 to 5 carbon atoms, preferably 2 or 3 carbon atoms, and more preferably 2 carbon atoms.

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

The molecular weight of the above compound is preferably below 1500, preferably 180~1200.

R ₁₀₀ represents an alkyl group or an acyl group.

_R101 and _R102 each independently represent a monovalent organic group, and may be bonded to each other to form a ring.

As compounds in which an alkoxymethyl group or an acyloxymethyl group directly substitutes an aromatic group, various compounds of the following general formula can be cited.

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, R ₁₀₃ represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, an aralkyl group, or a group that is decomposed by an acid to generate an alkali-soluble group (for example, a group that is released by an acid, a group represented by -C(R ⁴ ) ₂ COOR ⁵ (R ⁴ independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R ⁵ represents a group that is released by an acid)).

_R105 each independently represents an alkyl group or an alkenyl group, a, b and c each independently represent 1 to 3, d represents 0 to 4, e represents 0 to 3, f represents 0 to 3, a+d represents 5 or less, b+e represents 4 or less, and c+f represents 4 or less.

Examples of R ⁵ in the group which decomposes by the action of an acid to generate an alkali-soluble group, the group which dissociates by the action of an acid, and the group represented by -C(R ⁴ ) ₂ COOR ⁵ include -C(R ₃₆ )(R ₃₇ )(R ₃₈ ), -C(R ₃₆ )(R ₃₇ )(OR ₃₉ ), and -C(R ₀₁ )(R ₀₂ )(OR ₃₉ ).

In the formula, R ₃₆ to R ₃₉ 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 the above-mentioned alkyl group, an alkyl group having 1 to 10 carbon atoms is preferred, and an alkyl group having 1 to 5 carbon atoms is more preferred.

The above alkyl group may be either linear or branched.

As the above-mentioned cycloalkyl group, a cycloalkyl group having 3 to 12 carbon atoms is preferred, and a cycloalkyl group having 3 to 8 carbon atoms is more preferred.

The above-mentioned cycloalkyl group may be a monocyclic structure or a polycyclic structure such as a condensed ring.

The above-mentioned aryl group is preferably an aromatic alkyl group having 6 to 30 carbon atoms, and phenyl is more preferably.

As the above-mentioned aralkyl group, an aralkyl group having 7 to 20 carbon atoms is preferred, and an aralkyl group having 7 to 16 carbon atoms is more preferred.

The above-mentioned aralkyl group refers to an aryl group substituted by an alkyl group, and the preferred embodiments of the alkyl group and the aryl group are the same as the preferred embodiments of the above-mentioned alkyl group and the aryl group.

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.

Furthermore, these groups may have known substituents within the scope of achieving the effects of the present invention.

_R01 and _R02 each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group or an alkenyl group.

As the group that generates an alkali-soluble group by decomposition under the action of an acid or the group that is released by the action of an acid, a tertiary alkyl ester group, an acetal group, a cumyl ester group, an enol ester group, etc. are preferred. A tertiary alkyl ester group and an acetal group are further preferred.

As compounds having an alkoxymethyl group, specifically, the following structures can be cited. As compounds having an acyloxymethyl group, compounds obtained by replacing the alkoxymethyl group of the following compound with an acyloxymethyl group can be cited. As compounds having an alkoxymethyl group or an acyloxymethyl group in the molecule, the following various compounds can be cited, but are not limited to these.

[Chemical formula 51]

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

環上取代之化合物為較佳。 From the viewpoint of heat resistance, the alkoxymethyl or acyloxymethyl group is preferably directly attached to the aromatic ring or the tricyclic ring.

Ring-substituted compounds are preferred.

Specific examples of melamine-based crosslinking agents include hexamethoxymethyl melamine, hexaethoxymethyl melamine, hexapropoxymethyl melamine, hexabutoxybutyl melamine, etc.

Specific examples of urea-based crosslinking agents include monohydroxymethylated glycoluril, dihydroxymethylated glycoluril, trihydroxymethylated glycoluril, tetrahydroxymethylated glycoluril, monomethoxymethylated glycoluril, dimethoxymethylated glycoluril, trimethoxymethylated glycoluril, tetramethoxymethylated glycoluril, monoethoxymethylated glycoluril, diethoxymethylated glycoluril, triethoxymethylated glycoluril, tetraethoxymethylated glycoluril, monopropoxymethylated glycoluril, methyl glycoluril, dipropoxymethyl glycoluril, tripropoxymethyl glycoluril, tetrapropoxymethyl glycoluril, monobutoxymethyl glycoluril, dibutoxymethyl glycoluril, tributoxymethyl glycoluril or tetrabutoxymethyl glycoluril; Urea crosslinking agents such as bismethoxymethyl urea, bisethoxymethyl urea, dipropoxymethyl urea, dibutoxymethyl urea, monohydroxymethyl ethyl urea or dihydroxymethyl urea Ethyl urea, monomethoxymethylated ethyl urea, dimethoxymethylated ethyl urea, monoethoxymethylated ethyl urea, diethoxymethylated ethyl urea, monopropoxymethylated ethyl urea, dipropoxymethylated ethyl urea, monobutoxymethylated ethyl urea or dibutoxymethylated ethyl urea and other ethyl urea-based crosslinking agents, monohydroxymethylated propyl urea, dihydroxymethylated propyl urea, monomethoxymethylated propyl urea, dimethoxymethylated propyl urea, monoethoxymethylated propyl urea, diethoxymethylated propyl urea, monopropoxymethylated propyl urea, dipropoxymethylated propyl urea, monobutoxymethylated propyl urea or dibutoxymethylated propyl urea and other propyl urea-based crosslinking agents, 1,3-bis(methoxymethyl)4,5-dihydroxy-2-imidazolidinone, 1,3-bis(methoxymethyl)-4,5-dimethoxy-2-imidazolidinone, etc.

Specific examples of benzoguanamine crosslinking agents include monohydroxymethylated benzoguanamine, dihydroxymethylated benzoguanamine, trihydroxymethylated benzoguanamine, tetrahydroxymethylated benzoguanamine, monomethoxymethylated benzoguanamine, dimethoxymethylated benzoguanamine, trimethoxymethylated benzoguanamine, tetramethoxymethylated benzoguanamine, monoethoxymethylated benzoguanamine, diethoxymethylated benzoguanamine, triethoxymethylated benzoguanamine, tetraethoxymethylated benzoguanamine, monopropoxymethylated benzoguanamine, dipropoxymethylated benzoguanamine, tripropoxymethylated benzoguanamine, tetrapropoxymethylated benzoguanamine, monobutoxymethylated benzoguanamine, di butoxymethylated benzoguanamine, tributoxymethylated benzoguanamine, tetrabutoxymethylated benzoguanamine, etc.

In addition, as the compound having at least one group selected from the group including hydroxymethyl and alkoxymethyl, a compound having at least one group selected from the group including hydroxymethyl and alkoxymethyl directly bonded to an aromatic ring (preferably a benzene ring) can also be preferably used.

Specific examples of such compounds include benzyl alcohol, bis(hydroxymethyl)cresol, bis(hydroxymethyl)dimethoxybenzene, bis(hydroxymethyl)diphenyl ether, bis(hydroxymethyl)benzophenone, hydroxymethylphenyl hydroxymethylbenzoate, bis(hydroxymethyl)biphenyl, dimethylbis(hydroxymethyl)biphenyl, bis(methoxymethyl)benzene, bis(methoxymethyl)cresol, bis(methoxymethyl)dimethoxybenzene, bis(methoxymethyl)diphenyl ether, bis(methoxymethyl)biphenyl Ketone, methoxymethylphenyl methoxybenzoate, bis(methoxymethyl)biphenyl, dimethylbis(methoxymethyl)biphenyl, 4,4',4"-ethylenetri[2,6-bis(methoxymethyl)phenol], 5,5'-[2,2,2-trifluoro-1-(trifluoromethyl)ethylene]bis[2-hydroxy-1,3-benzenedimethanol], 3,3',5,5'-tetrakis(methoxymethyl)-1,1'-biphenyl-4,4'-diol, etc.

As other crosslinking agents, commercial products may be used. Preferred commercial products include 46DMOC, 46DMOEP (all manufactured by ASAHI YUKIZAI CORPORATION), 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-B PE, TML-BPA, TML-BPAF, TML-BPAP, TMOM-BP, TMOM-BPE, TMOM-BPA, TMOM-BPAF, TMOM-BPAP, HML-TPPHBA, HML-TPHAP, HMOM-TPPHBA, HMOM-TPHAP (all manufactured by Honshu Chemical Industry Co., Ltd.), NIKARAC (registered trademark, hereinafter the same) MX-290, NIKARAC MX-280, NIKARAC MX-270, NIKARAC MX-279, NIKARAC MW-100LM, NIKARAC MX-750LM (all manufactured by Sanwa Chemical Co., Ltd.), etc.

化合物之群組中的至少1種化合物作為其他交聯劑亦較佳。 Furthermore, the resin composition of the present invention comprises a compound selected from epoxy compounds, cyclohexane compounds and benzo

It is also preferred that at least one compound in the group of compounds serves as another crosslinking agent.

-Epoxy compounds (compounds with epoxy groups)-

As the epoxy compound, a compound having two or more epoxy groups in one molecule is preferred. The epoxy group undergoes a crosslinking reaction below 200°C and does not produce a dehydration reaction caused by the crosslinking, so it is not easy to cause film shrinkage. Therefore, containing an epoxy compound is effective in inhibiting the low-temperature curing and warping of the resin composition of the present invention.

The epoxy compound preferably contains a polyethylene oxide group. This further reduces the elastic modulus and can suppress warping. The polyethylene oxide group means that the number of repeating units of ethylene oxide is 2 or more, and the number of repeating units is preferably 2 to 15.

Examples of epoxy compounds include bisphenol A type epoxy resins; bisphenol F type epoxy resins; propylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, ethylene glycol diglycidyl ether, butylene glycol diglycidyl ether, hexamethylene glycol diglycidyl ether, trihydroxymethylpropane triglycidyl ether and other alkylene glycol type epoxy resins or polyol hydrocarbon type epoxy resins; polypropylene glycol diglycidyl ether and other polyalkylene glycol type epoxy resins; epoxy epoxy silicones such as polymethyl (glycidyloxypropyl) siloxane, etc., but are not limited to these. Specifically, we can cite 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, EPICL ON (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 (the above are product names, DIC CORPORATION), 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 (product names, New Japan Chemical Co., Ltd.), EP-4003S, EP-4000S, EP-4088S, EP-3950S (the above are product names, ADEKA CORPORATION), CELLOXIDE (registered trademark) 2021P, CELLOXIDE (registered trademark) 2081, CELLOXIDE (registered trademark) 2000, EHPE3150, EPOLEAD (registered trademark) GT401, EPOLEAD (registered trademark) PB4700, EPOLEAD (registered trademark) PB3600 (the above are product names, Daicel Corporation), NC-3000, NC-3000-L, NC-3000-H, NC-3000-FH-75M, NC-3100, CER-3000-L, NC-2000-L, XD-1000, NC-7000L, NC-7300L, EPPN-501H, EPPN-501HY, EPPN-502H, EOCN-1020, EOCN-102S, EOCN-103S, EOCN-104S, CER-1020, EPPN-201, BREN-S, BREN-10S (the above are product names, manufactured by Nippon Kayaku Co., Ltd.), etc. In addition, the following compounds can also be preferably used.

[Chemical formula 52]

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

In the above structure, from the perspective of both heat resistance and elongation improvement, n is preferably 1~2 and m is preferably 3~7.

-Oxycyclobutane compounds (compounds with cyclobutane groups)-

Examples of cyclooxetane compounds include compounds having two or more cyclooxetane rings in one molecule, 3-ethyl-3-hydroxymethoxycyclobutane, 1,4-bis{[(3-ethyl-3-cyclooxetane)methoxy]methyl}benzene, 3-ethyl-3-(2-ethylhexylmethyl)cyclooxetane, and 1,4-benzenedicarboxylic acid-bis[(3-ethyl-3-cyclooxetane)methyl]ester. As specific examples, ARON OXETANE series (e.g., OXT-121, OXT-221) manufactured by TOAGOSEI CO., LTD. can be preferably used, and these can be used alone or in combination of two or more.

化合物(具有苯并

唑基之化合物)- -Benzo

Compounds (having benzo

Azolyl compounds)

化合物在硬化時不產生脫氣，從而進一步減少熱收縮以抑制產生翹曲，因此為較佳。 Due to the cross-linking reaction caused by the ring-opening addition reaction, benzo

Compounds that do not outgas during hardening, thereby further reducing thermal shrinkage and inhibiting warping, are preferred.

化合物的較佳例，可以舉出P-d型苯并

、F-a型苯并

、(以上為產品名稱，Shikoku Chemicals Corporation製)、聚羥基苯乙烯樹脂的苯并

加成物、酚醛清漆型二氫苯并

化合物。該等可以單獨使用或者混合使用2種以上。 As benzo

A good example of a compound is Pd-type benzo

, Fa type benzo

、(the above are product names, made by Shikoku Chemicals Corporation), benzophenone of polyhydroxystyrene resin

Adduct, novolac type dihydrobenzo

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

The content of other crosslinking agents relative to the total solid content of the resin composition of the present invention is preferably 0.1-30 mass %, more preferably 0.1-20 mass %, further preferably 0.5-15 mass %, and particularly preferably 1.0-10 mass %. Other crosslinking agents may contain only one or more. When containing more than two other crosslinking agents, it is preferred that their total is within the above range.

<Metal adhesion improver>

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

[Silane coupling agent]

As silane coupling agents, for example, there can be cited compounds described in paragraph 0167 of International Publication No. 2015/199219, compounds described in paragraphs 0062 to 0073 of Japanese Patent Publication No. 2014-191002, compounds described in paragraphs 0063 to 0071 of International Publication No. 2011/080992, compounds described in paragraphs 0063 to 0071 of Japanese Patent Publication No. 2014-191252, The compounds described in paragraphs 0060 to 0061 of the Japanese Patent Publication No. 2014-041264, the compounds described in paragraphs 0045 to 0052 of the Japanese Patent Publication No. 2014/097594, and the compounds described in paragraphs 0067 to 0078 of the Japanese Patent Publication No. 2018-173573 are incorporated into this specification. In addition, as described in paragraphs 0050 to 0058 of the Japanese Patent Publication No. 2011-128358, it is also preferred to use two or more different silane coupling agents. In addition, it is also preferred to use the following compounds as silane coupling agents. In the following formula, Me represents a methyl group and Et represents an ethyl group.

[Chemical formula 53]

Examples of other silane coupling agents include vinyl trimethoxysilane, vinyl triethoxysilane, 2-(3,4-epoxyhexyl)ethyl trimethoxysilane, 3-glycidoxypropyl methyl dimethoxysilane, 3-glycidoxypropyl trimethoxysilane, 3-glycidoxypropyl methyl diethoxysilane, 3-glycidoxypropyl triethoxysilane, p-phenylenediyl trimethoxysilane, 3-methacryloxypropyl methyl dimethoxysilane, 3-methacryloxypropyl trimethoxysilane, 3-methacryloxypropyl methyl diethoxysilane, 3-methacryloxypropyl triethoxysilane, 3-acryloxypropyl Trimethoxysilane, N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane, N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N-(1,3-dimethyl-butylene)propylamine, N-phenyl-3-aminopropyltrimethoxysilane, tris-(trimethoxysilylpropyl)isocyanurate, 3-ureidopropyltrialkoxysilane, 3-butylenepropylmethyldimethoxysilane, 3-butylenepropyltrimethoxysilane, 3-isocyanatepropyltriethoxysilane, 3-trimethoxysilylpropylsuccinic anhydride. These can be used alone or in combination of two or more.

[Aluminum-based bonding agent]

As aluminum-based bonding agents, for example, aluminum tri(ethyl acetate)aluminum, aluminum tri(acetylacetone)aluminum, ethyl acetate diisopropyl aluminum, etc. can be cited.

Furthermore, as other metal adhesion improvers, compounds described in paragraphs 0046 to 0049 of Japanese Patent Publication No. 2014-186186 and sulfide compounds described in paragraphs 0032 to 0043 of Japanese Patent Publication No. 2013-072935 can also be used, and these contents are incorporated into this specification.

The content of the metal adhesion improver is preferably 0.01 to 30 parts by mass, more preferably 0.1 to 10 parts by mass, and further preferably 0.5 to 5 parts by mass relative to 100 parts by mass of the specific resin. By setting it above the lower limit, the adhesion between the pattern and the metal layer becomes good, and by setting it below the upper limit, the heat resistance and mechanical properties of the pattern become good. The metal adhesion improver can be only one kind or two or more kinds. When two or more kinds are used, it is better that the total is within the above range.

<Migration inhibitor>

The resin composition of the present invention preferably further contains a migration inhibitor. By containing a migration inhibitor, it is possible to effectively inhibit the migration of metal ions from the metal layer (metal wiring) into the film.

唑環、噻唑環、吡唑環、異

唑環、異噻唑環、四唑環、吡啶環、嗒

環、嘧啶環、吡

環、哌啶環、哌

環、嗎啉環、2H-吡喃環及6H-吡喃環、三

環)之化合物、具有硫脲類及氫硫基之化合物、受阻酚系化合物、水楊酸衍生物系化合物、醯肼衍生物系化合物。尤其，能夠較佳地使用1,2,4-三唑、苯并三唑、3-胺基-1,2,4-三唑、3,5-二胺基-1,2,4-三唑等三唑系化合物、1H-四唑、5-苯基四唑、5-胺基-1H-四唑等四唑系化合物。 The migration inhibitor is not particularly limited, and examples thereof include those having a heterocyclic ring (pyrrole ring, furan ring, thiophene ring, imidazole ring,

Azole, thiazole, pyrazole, iso

Azole ring, isothiazole ring, tetrazole ring, pyridine ring, tantalum

Ring, pyrimidine ring, pyridine

Ring, piperidine ring, piperidine

ring, morpholine ring, 2H-pyran ring and 6H-pyran ring, tri

Compounds having a thiourea group and a thiohydride group, hindered phenol compounds, salicylic acid derivative compounds, and hydrazide derivative compounds. In particular, triazole compounds such as 1,2,4-triazole, benzotriazole, 3-amino-1,2,4-triazole, and 3,5-diamino-1,2,4-triazole, and tetrazole compounds such as 1H-tetrazole, 5-phenyltetrazole, and 5-amino-1H-tetrazole can be preferably used.

Alternatively, an ion scavenger that captures anions such as halogen ions can also be used.

As other migration inhibitors, the rustproofing agent described in paragraph 0094 of Japanese Patent Publication No. 2013-015701, the compounds described in paragraphs 0073 to 0076 of Japanese Patent Publication No. 2009-283711, the compounds described in paragraph 0052 of Japanese Patent Publication No. 2011-059656, the compounds described in paragraphs 0114, 0116 and 0118 of Japanese Patent Publication No. 2012-194520, the compounds described in paragraph 0166 of International Publication No. 2015/199219, etc. can be used, and these contents are incorporated into this specification.

As specific examples of migration inhibitors, the following compounds can be cited.

When the resin composition of the present invention contains a migration inhibitor, the content of the migration inhibitor relative to the total solid content of the resin composition of the present invention is preferably 0.01 to 5.0 mass %, more preferably 0.05 to 2.0 mass %, and even more preferably 0.1 to 1.0 mass %.

There may be only one migration inhibitor or two or more. When there are two or more migration inhibitors, it is preferred that the total amount is within the above range.

<Polymerization inhibitor>

The resin composition of the present invention preferably contains a polymerization inhibitor. Examples of the polymerization inhibitor include phenolic compounds, quinone compounds, amino compounds, N-oxyl radical compounds, nitro compounds, nitroso compounds, heteroaromatic ring compounds, metal compounds, etc.

-2,4,6-(1H，3H，5H)-三酮、4-羥基-2,2,6,6-四甲基哌啶1-氧自由基、2,2,6,6-四甲基哌啶1-氧自由基、吩噻

、啡

、1,1-二苯基-2-吡咯肼、二丁基二硫代碳酸銅(II)、硝基苯、N-亞硝基-N-苯基羥胺鋁鹽、N-亞硝基-N-苯基羥基胺銨鹽等。又，亦能夠使用日本特開201 5-127817號公報的0060段中所記載的聚合抑制劑及國際公開第2015/125469號的0031~0046段中所記載的化合物，並將該內容編入本說明書中。 As specific compounds of the polymerization inhibitor, for example, p-hydroquinone, o-hydroquinone, o-methoxyphenol, p-methoxyphenol, di-tert-butyl-p-cresol, gallol, p-tert-butyl-o-catechol, 1,4-benzoquinone, diphenyl-p-benzoquinone, 4,4'-thiobis(3-methyl-6-tert-butylphenol), 2,2'-methylenebis(4-methyl-6-tert-butylphenol), N-nitrosophenylhydroxylamine first barium salt, N-nitroso-N-phenylhydroxylamine aluminum salt, N-nitrosodiphenylamine, N-phenylnaphthylamine, ethylenediamine, aminetetraacetic acid, 1,2-cyclohexanediaminetetraacetic acid, glycol ether diaminetetraacetic 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-sulfopropylamine)phenol, N-nitroso-N-(1-naphthyl)hydroxylamine ammonium salt, bis(4-hydroxy-3,5-tert-butyl)phenylmethane, 1,3,5-tri(4-tert-butyl-3-hydroxy)-2,6-dimethylbenzyl)-1,3,5-tri(4-tert-butyl-3-hydroxy)-2,6-dimethylbenzyl)-1,3,5-tri(4-tert-butyl-3-hydroxy)-

-2,4,6-(1H,3H,5H)-trione, 4-hydroxy-2,2,6,6-tetramethylpiperidinyl 1-oxyl free radical, 2,2,6,6-tetramethylpiperidinyl 1-oxyl free radical, phenothiazine

,coffee

, 1,1-diphenyl-2-pyrrole hydrazine, dibutyl copper dithiocarbonate (II), nitrobenzene, N-nitroso-N-phenylhydroxylamine aluminum salt, N-nitroso-N-phenylhydroxylamine ammonium salt, etc. In addition, the polymerization inhibitor described in paragraph 0060 of Japanese Patent Publication No. 2015-127817 and the compounds described in paragraphs 0031 to 0046 of International Publication No. 2015/125469 can also be used, and the contents are incorporated into this specification.

When the resin composition of the present invention contains a polymerization inhibitor, the content of the polymerization inhibitor is preferably 0.01 to 20 mass %, more preferably 0.02 to 15 mass %, and even more preferably 0.05 to 10 mass % relative to the total solid content of the resin composition of the present invention.

The polymerization inhibitor may be only one or two or more. When there are two or more polymerization inhibitors, it is preferred that the total amount is within the above range.

<Acid capture agent>

In order to reduce the performance change caused by the time from exposure to heating, the resin composition of the present invention preferably contains an acid scavenger. Among them, the acid scavenger refers to a compound that can capture the generated acid by existing in the system, and a compound with low acidity and high pKa is preferred. As an acid scavenger, a compound with an amine group is preferred, and primary amines, secondary amines, tertiary amines, ammonium salts, tertiary amides, etc. are preferred, primary amines, secondary amines, tertiary amines, and ammonium salts are preferred, and secondary amines, tertiary amines, and ammonium salts are more preferred.

As the acid scavenger, preferably, there can be cited compounds having an imidazole structure, a diazine bicyclic structure, an onium structure, a trialkylamine structure, an aniline structure or a pyridine structure, an alkylamine derivative having a hydroxyl group and/or an ether bond, an aniline derivative having a hydroxyl group and/or an ether bond, etc. In the case of having an onium structure, the acid scavenger is preferably a salt having a cation selected from ammonium, diazo, iodine, coronium, phosphonium, pyridinium, etc. and an anion of an acid having a lower acidity than the acid generated by the acid generator.

Examples of the acid scavenger having an imidazole structure include imidazole, 2,4,5-triphenylimidazole, benzimidazole, and 2-phenylbenzimidazole. Examples of the acid scavenger having a diazabicyclo structure include 1,4-diazabicyclo[2,2,2]octane, 1,5-diazabicyclo[4,3,0]non-5-ene, and 1,8-diazabicyclo[5,4,0]undec-7-ene. Examples of the acid scavenger having an onium structure include tetrabutylammonium hydroxide, triarylcosium hydroxide, benzylmethylcosium hydroxide, cosium hydroxide having a 2-oxoalkyl group, specifically triphenylcosium hydroxide, tri(tert-butylphenyl)cosium hydroxide, bis(tert-butylphenyl)iodonium hydroxide, benzylmethylthiophenium hydroxide, 2-oxopropylthiophenium hydroxide, etc. Examples of the acid scavenger having a trialkylamine structure include tri(n-butyl)amine, tri(n-octyl)amine, etc. Examples of acid scavengers having an aniline structure include 2,6-diisopropylaniline, N,N-dimethylaniline, N,N-dibutylaniline, and N,N-dihexylaniline. Examples of acid scavengers having a pyridine structure include pyridine and 4-methylpyridine. Examples of alkylamine derivatives having a hydroxyl group and/or an ether bond include ethanolamine, diethanolamine, triethanolamine, N-phenyldiethanolamine, and tris(methoxyethoxyethyl)amine. Examples of aniline derivatives having a hydroxyl group and/or an ether bond include N,N-bis(hydroxyethyl)aniline.

、托烷、N-苯基苄胺、1,2-二苯胺基乙烷(dianilinoethane)、2-胺基乙醇、甲苯胺、胺基酚、己基苯胺、伸苯基二胺、苯基乙基胺、二苄胺、吡咯、N-甲基吡咯、胍、胺基吡咯啶、吡唑、吡唑啉、胺基嗎啉、胺基烷基

啉等。 Specific examples of preferred acid scavengers include ethanolamine, diethanolamine, triethanolamine, ethylamine, diethylamine, triethylamine, hexylamine, dodecylamine, cyclohexylamine, cyclohexylmethylamine, cyclohexyldimethylamine, aniline, N-methylaniline, N,N-dimethylaniline, diphenylamine, pyridine, butylamine, isobutylamine, dibutylamine, tributylamine, dicyclohexylamine, DBU (diazabicycloundecane), DABCO (1,4-dihydro-1,2-dione), and the like. N,N-diisopropylethylamine, tetramethylammonium hydroxide, ethylenediamine, 1,5-diaminopentane, N-methylhexylamine, N-methyldicyclohexylamine, trioctylamine, N-ethylethylenediamine, N,N-diethylethylenediamine, N,N,N',N'-tetrabutyl-1,6-hexanediamine, triamine, diaminocyclohexane, bis(2-methoxyethyl)amine, piperidine, methylpiperidine, piperidine

, tropane, N-phenylbenzylamine, 1,2-dianilinoethane, 2-aminoethanol, toluidine, aminophenol, hexylaniline, phenylenediamine, phenylethylamine, dibenzylamine, pyrrole, N-methylpyrrole, guanidine, aminopyrrolidine, pyrazole, pyrazoline, aminopyrrolidine, aminoalkyl

Phylin, etc.

These acid capture agents can be used alone or in combination of two or more.

The composition of the present invention may contain an acid scavenger or may not contain an acid scavenger. However, if it contains an acid scavenger, the content of the acid scavenger is based on the total solid content of the composition, usually 0.001~10% by mass, preferably 0.01~5% by mass.

The ratio of acid generator to acid scavenger is preferably 2.5 to 300. That is, from the perspective of sensitivity and resolution, a molar ratio of 2.5 or more is preferred, and from the perspective of suppressing the reduction in resolution caused by the thickening of the relief pattern over time from exposure to heat treatment, a molar ratio of 300 or less is preferred. The molar ratio of acid generator to acid scavenger is more preferably 5.0 to 200, and further preferably 7.0 to 150.

<Other additives>

The resin composition of the present invention can be formulated with various additives as needed within the scope of obtaining the effects of the present invention, such as surfactants, higher fatty acid derivatives, thermal polymerization initiators, inorganic particles, ultraviolet absorbers, organic titanium compounds, antioxidants, anti-agglomeration agents, phenolic compounds, other polymer compounds, plasticizers and other additives (e.g., defoamers, flame retardants, etc.). By appropriately containing these ingredients, the properties of the film such as physical properties can be adjusted. For these components, for example, reference can be made to paragraphs 0183 and later of Japanese Patent Publication No. 2012-003225 (paragraph 0237 of the corresponding U.S. Patent Application Publication No. 2013/0034812) and paragraphs 0101 to 0104, 0107 to 0109 of Japanese Patent Publication No. 2008-250074, and such contents are incorporated into this specification. When these additives are added, it is preferred that their total amount be set to 3% by weight or less of the solid content of the resin composition of the present invention.

[Surfactant]

As the surfactant, various surfactants such as fluorine-based surfactants, silicone-based surfactants, hydrocarbon-based surfactants, etc. can be used. The surfactant can be a non-ionic surfactant, a cationic surfactant, or an anionic surfactant.

By including a surfactant in the photosensitive resin composition of the present invention, the liquid properties (especially fluidity) when preparing as a coating liquid are further improved, thereby further improving the uniformity of coating thickness or liquid saving. That is, when a film is formed using a coating liquid that applies a composition containing a surfactant, the interfacial tension between the coated surface and the coating liquid is reduced, thereby improving the wettability of the coated surface, thereby improving the coating property of the coated surface. Therefore, it is possible to better form a uniform film with less uneven thickness.

Examples of the fluorine-based surfactant include MEGAFACE F171, MEGAFACE F172, MEGAFACE F173, MEGAFACE F176, MEGAFACE F177, MEGAFACE F141, MEGAFACE F142, MEGAFACE F143, MEGAFACE F144, MEGAFACE R30, MEGAFACE F437, MEGAFACE F475, MEGAFACE F479, MEGAFACE F482, MEGAFACE F554, MEGAFACE F780, RS-72-K (all manufactured by DIC CORPORATION), Fluorad FC430, Fluorad FC431, Fluorad FC171, Novell FC4430, Novell FC4432 (all manufactured by 3M Japan Limited), Surflon S-382, Surflon SC-101, Surflon SC-103, Surflon SC-104, Surflon SC-105, Surflon SC-1068, Surflon SC-381, Surflon SC-383, Surflon S-393, Surflon KH-40 (the above is ASAHI GLASS CO., LTD.), PF636, PF656, PF6320, PF6520, PF7002 (manufactured by OMNOVA Solutions Inc.), etc. The fluorine-based surfactant can also use the compounds described in paragraphs 0015 to 0158 of Japanese Patent Publication No. 2015-117327 and the compounds described in paragraphs 0117 to 0132 of Japanese Patent Publication No. 2011-132503, and these contents are incorporated into this specification. Block polymers can also be used as fluorine-based surfactants. As a specific example, the compounds described in Japanese Patent Publication No. 2011-89090 can be cited, and these contents are incorporated into this specification.

The fluorine-based surfactant can also preferably use a fluorine-containing polymer compound, which contains repeating units from a (meth)acrylate compound having fluorine atoms and repeating units from a (meth)acrylate compound having 2 or more (preferably 5 or more) alkoxy groups (preferably ethyleneoxy and propyleneoxy). The following compounds can also be exemplified as the fluorine-based surfactant used in the present invention.

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

Fluorine-based surfactants can also use fluorine-containing polymers having ethylenically unsaturated groups on the side chains as fluorine-based surfactants. As specific examples, compounds described in paragraphs 0050 to 0090 and paragraphs 0289 to 0295 of Japanese Patent Publication No. 2010-164965 can be cited, and the contents are incorporated into this specification. In addition, as commercially available products, for example, MEGAFACE RS-101, RS-102, RS-718K, etc. manufactured by DIC CORPORATION can be cited.

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. In terms of uniformity of coating thickness or liquid saving, the fluorine-based surfactant with a fluorine content within this range is effective and has good solubility in the composition.

Examples of silicone surfactants include Toray Silicone DC3PA, Toray Silicone SH7PA, Toray Silicone DC11PA, Toray Silicone SH21PA, Toray Silicone SH28PA, Toray Silicone SH29PA, Toray Silicone SH30PA, Toray Silicone SH8400 (all manufactured by Dow Corning Toray Co., Ltd.), TSF-4440, TSF-4300, TSF-4445, TSF-4460, TSF-4452 (all manufactured by Momentive performance Materials Inc.), KP-341, KF6001, KF6002 (all manufactured by Shin-Etsu Chemical Co., Ltd.), BYK307, BYK323, BYK330 (all manufactured by BYK Chemie GmbH), etc.

Examples of hydrocarbon-based surfactants include PIONIN A-76, Newkalgen 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, etc. (all manufactured by TAKEMOTO OIL & FAT CO., LTD.).

Examples of the non-ionic surfactant include glycerin, trihydroxymethylpropane, trihydroxymethylethane, and ethoxylates and propoxylates thereof (e.g., glycerin propoxylate, glycerin 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 esters, and the like. 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 Lubrizol Japan Ltd.), NCW-101, NCW-1001, NCW-1002 (manufactured by FUJIFILM Wako Pure Chemical Corporation), PIONIN D-6112, D-6112-W, D-6315 (manufactured by TAKEMOTO OIL & FAT CO., LTD.), OLFIN E1010, Surfynol 104, 400, 440 (manufactured by Nissin Chemical co., ltd.), etc.

Specific examples of cationic surfactants include organosiloxane polymer KP-341 (manufactured by Shin-Etsu Chemical Co., Ltd.), (meth)acrylic (co)polymer Polyflow No.75, No.77, No.90, No.95 (manufactured by KYOEISHA CHEMICAL Co., LTD.), and W001 (manufactured by Yusho Co., Ltd.).

Specifically, as anionic surfactants, W004, W005, W017 (manufactured by Yusho Co., Ltd.), SANDET BL (manufactured by Sanyo Kasei Co., Ltd.), etc. can be cited.

Only one surfactant may be used, or two or more surfactants may be used in combination.

The content of the surfactant is preferably 0.001~2.0 mass % relative to the total solid content of the composition, and 0.005~1.0 mass % is more preferred.

[Higher fatty acid derivatives]

In order to prevent polymerization hindrance caused by oxygen, a higher fatty acid derivative such as behenic acid or behenic acid amide may be added to the resin composition of the present invention so that it is unevenly present on the surface of the resin composition of the present invention during the drying process after coating.

Furthermore, higher fatty acid derivatives can also use the compounds described in paragraph 0155 of International Publication No. 2015/199219, and the contents are incorporated into this specification.

When the resin composition of the present invention contains higher fatty acid derivatives, the content of the higher fatty acid derivatives is preferably 0.1 to 10% by mass relative to the total solid content of the resin composition of the present invention. The higher fatty acid derivatives may be only one or more than two. When there are more than two higher fatty acid derivatives, their total is preferably within the above range.

[Thermal polymerization initiator]

The resin composition of the present invention may contain a thermal polymerization initiator, and in particular, may contain a thermal free radical polymerization initiator. A thermal free radical polymerization initiator is a compound that generates free radicals by heat energy and starts or promotes the polymerization reaction of a polymerizable compound. By adding a thermal free radical polymerization initiator, the polymerization reaction of the resin and the polymerizable compound can also be carried out, thereby further improving the solvent resistance. In addition, sometimes the above-mentioned photopolymerization initiator also has the function of starting polymerization by heat, and sometimes it can be added as a thermal polymerization initiator.

As thermal radical polymerization initiators, specifically, compounds described in paragraphs 0074 to 0118 of Japanese Patent Application No. 2008-063554 can be cited, and the contents are incorporated into this specification.

When a thermal polymerization initiator is included, its content relative to the total solid content of the resin composition of the present invention is preferably 0.1-30 mass%, more preferably 0.1-20 mass%, and further preferably 0.5-15 mass%. The thermal polymerization initiator may contain only one or more. When containing more than two thermal polymerization initiators, the total amount is preferably within the above range.

[Inorganic particles]

The resin composition of the present invention may contain inorganic particles. Specifically, the inorganic particles may include calcium carbonate, calcium phosphate, silicon dioxide, kaolin, talc, titanium dioxide, aluminum oxide, barium sulfate, calcium fluoride, lithium fluoride, zeolite, molybdenum sulfide, glass, etc.

The average particle size of the inorganic particles is preferably 0.01~2.0μm, more preferably 0.02 ~1.5μm, further preferably 0.03~1.0μm, and particularly preferably 0.04~0.5μm.

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

When it is difficult to perform the above measurements, measurements can also be performed using the centrifugal sedimentation transmission method, X-ray transmission method, and laser diffraction/scattering method.

[Ultraviolet absorber]

系等紫外線吸收劑。 The composition of the present invention may contain an ultraviolet absorber. As the ultraviolet absorber, salicylate-based, benzophenone-based, benzotriazole-based, substituted acrylonitrile-based, tris(III)-based

It is a UV absorber.

Examples of salicylate-based ultraviolet absorbers include phenyl salicylate, p-octylphenyl salicylate, and p-tert-butylphenyl salicylate. Examples of benzophenone-based ultraviolet absorbers include 2,2'-dihydroxy-4-methoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2,2',4,4'-tetrahydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2,4-dihydroxybenzophenone, and 2-hydroxy-4-octyloxybenzophenone. 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-pentyl-5'-isobutylphenyl)-5-chlorobenzotriazole, and 2-(2'-hydroxy-3'-tert-pentyl-5'-isobutylphenyl)-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.

系紫外線吸收劑的例子，可以舉出2-[4-[(2-羥基-3-十二烷氧基丙基)氧基]-2-羥基苯基]-4,6-雙(2,4-二甲基苯基)-1,3,5-三

、2-[4-[(2-羥基-3-十三烷氧基丙基)氧基]-2-羥基苯基]-4,6-雙(2,4-二甲基苯基)-1,3,5-三

、2-(2,4-二羥基苯基)-4,6-雙(2,4-二甲基苯基)-1,3,5-三

等單(羥基苯基)三

化合物；2,4-雙(2-羥基-4-丙氧基苯基)-6-(2,4-二甲基苯基)-1,3,5-三

、2,4-雙(2-羥基-3-甲基-4-丙氧基苯基)-6-(4-甲基苯基)-1,3,5-三

、2,4-雙(2-羥基-3-甲基-4-己氧基苯基)-6-(2,4-二甲基苯基)-1,3,5-三

等雙(羥基苯基)三

化合物；2,4-雙(2-羥基-4-丁氧基苯基)-6-(2,4-二丁氧基苯基)-1,3,5-三

、2,4,6-三(2-羥基-4-辛氧基苯基)-1,3,5-三

、2,4,6-三[2-羥基-4-(3-丁氧基-2-羥基丙氧基)苯基]-1,3,5-三

等三(羥基苯基)三

化合物等。 Examples of substituted acrylonitrile-based ultraviolet absorbers include ethyl 2-cyano-3,3-diphenylacrylate and 2-ethylhexyl 2-cyano-3,3-diphenylacrylate.

Examples of ultraviolet light absorbers include 2-[4-[(2-hydroxy-3-dodecyloxypropyl)oxy]-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine.

, 2-[4-[(2-hydroxy-3-tridecyloxypropyl)oxy]-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-tridecyloxy

, 2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine

Mono(hydroxyphenyl)tri

Compound; 2,4-bis(2-hydroxy-4-propoxyphenyl)-6-(2,4-dimethylphenyl)-1,3,5-tri

, 2,4-bis(2-hydroxy-3-methyl-4-propoxyphenyl)-6-(4-methylphenyl)-1,3,5-tri

, 2,4-bis(2-hydroxy-3-methyl-4-hexyloxyphenyl)-6-(2,4-dimethylphenyl)-1,3,5-tri

Bis(hydroxyphenyl)tris(hydroxyphenyl)

Compound; 2,4-bis(2-hydroxy-4-butoxyphenyl)-6-(2,4-dibutoxyphenyl)-1,3,5-tri

, 2,4,6-tris(2-hydroxy-4-octyloxyphenyl)-1,3,5-tri

, 2,4,6-tris[2-hydroxy-4-(3-butoxy-2-hydroxypropoxy)phenyl]-1,3,5-tris(2-hydroxy-4-(3-butoxy-2-hydroxypropoxy)phenyl)

Tris(hydroxyphenyl)tri ...

Compounds, etc.

In the present invention, the above-mentioned various ultraviolet absorbers can be used alone or in combination of two or more.

The composition of the present invention may contain a UV absorber or may not contain a UV absorber. However, if it is contained, the content of the UV absorber is preferably 0.001% by mass or more and 1% by mass or less, and more preferably 0.01% by mass or more and 0.1% by mass or less relative to the total solid content of the composition of the present invention.

[Organic titanium compounds]

The resin composition of this embodiment may contain an organic titanium compound. Since the resin composition contains an organic titanium compound, a resin layer with excellent chemical resistance can be formed even when hardening is performed at a low temperature.

As usable organic titanium compounds, those in which an organic group is bonded to a titanium atom via a covalent bond or an ionic bond can be cited.

Specific examples of organic titanium compounds are shown in the following I)~VII):

I) Titanium chelate compounds: The resin composition has excellent storage stability and can obtain a good hardening pattern, so titanium chelate compounds with more than 2 alkoxy groups are better. Specific examples are titanium diisopropyl bis(triethanolamine), titanium di(n-butyl alcohol)bis(2,4-pentanedione), titanium diisopropyl bis(2,4-pentanedione), titanium diisopropyl bis(tetramethylheptanedione), titanium diisopropyl bis(ethyl acetylacetate), etc.

II) Tetraalkoxy titanium compounds: for example, titanium tetra(n-butanol), titanium tetraethanol, titanium tetra(2-ethylhexanol), titanium tetraisobutanol, titanium tetraisopropanol, titanium tetramethylol, titanium tetramethoxypropanol, titanium tetramethylphenoxide, titanium tetra(n-nonanol), titanium tetra(n-propanol), titanium tetrastearyl alcohol, titanium tetra[bis{2,2-(allyloxymethyl)butanol}], etc.

III) Titanium cyclopentadienyl compounds: for example, titanium pentamethylcyclopentadienyl 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.

IV) Monoalkoxy titanium compounds: for example, tri(dioctyl phosphate) isopropyl titanium, tri(dodecylphenyl sulfonate) isopropyl titanium, etc.

V) Titanium oxide compounds: for example, titanium bis(pentanedione), titanium bis(tetramethylheptanedione), titanium phthalocyanine oxide, etc.

VI) Titanium tetraacetylacetonate compound: for example, titanium tetraacetylacetonate, etc.

VII) Titanium ester coupling agent: for example, isopropyl tridodecylbenzenesulfonyl titanium salt, etc.

Among them, as an organic titanium compound, from the perspective of exerting better drug resistance, at least one compound selected from the group including I) titanium chelate compounds, II) tetraalkoxy titanium compounds and III) dioctenyl titanium compounds is preferred. In particular, titanium diisopropylate bis(ethyl acetylacetate), titanium tetra(n-butoxide) and bis(η5-2,4-cyclopentadiene-1-yl)bis(2,6-difluoro-3-(1H-pyrrol-1-yl)phenyl)titanium are preferred.

When an organic titanium compound is added, the amount thereof is preferably 0.05 to 10 parts by mass, and more preferably 0.1 to 2 parts by mass, relative to 100 parts by mass of the specific resin. When the amount is 0.05 parts by mass or more, the obtained hardened pattern more effectively exhibits good heat resistance and chemical resistance. On the other hand, when the amount is 10 parts by mass or less, the storage stability of the composition is better.

[Antioxidant]

The composition of the present invention may contain an antioxidant. By containing an antioxidant as an additive, the elongation characteristics of the cured film and the adhesion to the metal material can be improved. As the antioxidant, phenol compounds, phosphite compounds and thioether compounds can be cited. As the phenol compound, any phenol compound known as a phenolic antioxidant can be used. As a preferred phenol compound, a hindered phenol compound can be cited. Compounds having a substituent at a position adjacent to a phenolic hydroxyl group (adjacent position) are preferred. As the above-mentioned substituent, a substituted or unsubstituted alkyl group having 1 to 22 carbon atoms is preferred. In addition, the antioxidant is also preferably a compound having a phenolic group and a phosphite group in the same molecule. In addition, the antioxidant can also preferably use a phosphorus antioxidant. Examples of phosphorus-based antioxidants include tris[2-[[2,4,8,10-tetrakis(1,1-dimethylethyl)dibenzo[d,f][1,3,2]dioxaphosphinocycloheptadien-6-yl]oxy]ethyl]amine, tris[2-[(4,6,9,11-tetrakis-tert-butyldibenzo[d,f][1,3,2]dioxaphosphinocycloheptadien-2-yl)oxy]ethyl]amine, and ethyl bis(2,4-di-tert-butyl-6-methylphenyl)phosphite. As commercially available antioxidants, for example, Adekastab AO-20, Adekastab AO-30, Adekastab AO-40, Adekastab AO-50, Adekastab AO-50F, Adekastab AO-60, Adekastab AO-60G, Adekastab AO-80 and Adekastab AO-330 (all manufactured by ADEKA CORPORATION) can be cited. In addition, the antioxidant can also use the compounds described in paragraphs 0023 to 0048 of Japanese Patent No. 6268967, and the contents are incorporated into this specification. In addition, the composition of the present invention can contain a potential antioxidant as needed. As potential antioxidants, compounds in which the site that exerts antioxidant function is protected by a protecting group can be cited, and the antioxidant function can be exerted by heating at 100 to 250°C or heating at 80 to 200°C in the presence of an acid/base catalyst to remove the protecting group. As potential antioxidants, compounds described in International Publication No. 2014/021023, International Publication No. 2017/030005, and Japanese Patent Publication No. 2017-008219 can be cited, and the contents are incorporated into this specification. As commercially available products that are potential antioxidants, ADEKA ARKLS GPA-5001 (manufactured by ADEKA CORPORATION) and the like can be cited.

As examples of preferred antioxidants, there can be cited 2,2-thiobis(4-methyl-6-tert-butylphenol), 2,6-di-tert-butylphenol and the compound represented by formula (3).

In the general formula (3), ^R5 represents a hydrogen atom or an alkyl group having 2 or more carbon atoms (preferably 2 to 10 carbon atoms), ^R6 represents an alkylene group having 2 or more carbon atoms (preferably 2 to 10 carbon atoms). ^R7 represents an alkylene group having 2 or more carbon atoms (preferably 2 to 10 carbon atoms), and a monovalent to tetravalent organic group containing at least one of an oxygen atom and a nitrogen atom. k represents an integer of 1 to 4.

The compound represented by formula (3) inhibits the oxidative degradation of the aliphatic group and phenolic hydroxyl group of the resin. In addition, it can inhibit metal oxidation by its anti-rust effect on metal materials.

It can act on the resin and the metal material at the same time, so k is preferably an integer of 2 to 4. R ⁷ includes alkyl, cycloalkyl, alkoxy, alkyl ether, alkyl silyl, alkoxy silyl, aryl, aryl ether, carboxyl, carbonyl, allyl, vinyl, heterocyclic, -O-, -NH-, -NHNH-, combinations thereof, and the like, and may have a substituent. Among them, from the viewpoint of solubility in a developer and metal adhesion, alkyl ether and -NH- are preferred, and from the viewpoint of interaction with the resin and metal adhesion during metal complex formation, -NH- is more preferred.

Regarding the compounds represented by general formula (3), the following can be cited as examples, but they are not limited to the following structures.

[Chemical formula 57]

[Chemical formula 58]

[Chemical formula 59]

[Chemical formula 60]

The amount of antioxidant added is preferably 0.1 to 10 parts by mass relative to the resin, and 0.5 to 5 parts by mass is more preferred. By setting the added amount to 0.1 parts by mass or more, it is easy to obtain the effect of improving the elongation characteristics or the adhesion to the metal material even in a high temperature and high humidity environment, and by setting the added amount to 10 parts by mass or less, for example, the sensitivity of the resin composition can be improved by interaction with the photosensitizer. Only one antioxidant can be used, or two or more antioxidants can be used. When two or more antioxidants are used, the total amount is preferably within the above range.

[Anti-agglomerating agent]

The resin composition of this embodiment may contain an anti-agglomeration agent as needed. Examples of the anti-agglomeration agent include sodium polyacrylate and the like.

In the present invention, the anti-agglomerating agent may be used alone or in combination of two or more.

The composition of the present invention may contain an anti-agglomerating agent or may not contain an anti-agglomerating agent. However, if it is contained, the content of the anti-agglomerating agent is preferably 0.01% by mass or more and 10% by mass or less, and more preferably 0.02% by mass or more and 5% by mass or less relative to the total solid content of the composition of the present invention.

[Phenol compounds]

The resin composition of this embodiment may contain a phenolic compound as needed. Examples of the phenolic compound include Bis-Z, BisP-EZ, TekP-4HBPA, TrisP-HAP, TrisP-PA, BisOCHP-Z, BisP-MZ, BisP-PZ, BisP-IPZ, BisOCP-IPZ, BisP-CP, BisRS-2P, BisRS-3P, BisP-OCHP, methylenetri-FR-CR, BisRS-26X (the above are product names, manufactured by Honshu Chemical Industry Co., Ltd.), BIP-PC, BIR-PC, BIR-PTBP, BIR-BIPC-F (the above are product names, manufactured by ASAHI YUKIZAI CORPORATION), etc.

In the present invention, the phenolic compound may be used alone or in combination of two or more.

The composition of the present invention may contain phenolic compounds or not, but when it does, the content of phenolic compounds is preferably 0.01% by mass or more and 30% by mass or less, and more preferably 0.02% by mass or more and 20% by mass or less relative to the total solid content of the composition of the present invention.

[Other polymer compounds]

As other polymer compounds, there can be cited silicone resins, (meth)acrylic acid polymers obtained by copolymerizing (meth)acrylic acid, novolac resins, cresol resins, polyhydroxystyrene resins and copolymers thereof. Other polymer compounds may be modified products into which crosslinking groups such as hydroxymethyl, alkoxymethyl, and epoxy groups are introduced.

In the present invention, other polymer compounds may be used alone or in combination of two or more.

The composition of the present invention may or may not contain other polymer compounds, but if contained, the content of other polymer compounds relative to the total solid content of the composition of the present invention is preferably 0.01% by mass or more and 30% by mass or less, and more preferably 0.02% by mass or more and 20% by mass or less.

<Characteristics of resin composition>

The viscosity of the resin composition of the present invention can be adjusted by adjusting the solid content concentration of the resin composition. From the perspective of coating film thickness, 1,000 mm ² /s to 12,000 ^{mm 2} /s is preferred, 2,000 mm ² /s to 10,000 ^{mm 2} /s is more preferred, and 3,000 mm ² /s to 8,000 mm ² /s is further preferred. Within the above range, a highly uniform coating film can be easily obtained. When the viscosity is less than 1,000 mm ² /s, it is difficult to apply the film with the required film thickness as a redistribution insulating film, for example, and when the viscosity is more than 12,000 ^{mm 2} /s, the coating surface morphology may deteriorate.

<Regarding restrictions on substances contained in resin compositions>

The moisture content of the resin composition of the present invention is preferably less than 2.0 mass %, more preferably less than 1.5 mass %, and even more preferably less than 1.0 mass %. When it is more than 2.0%, the storage stability of the resin composition may be impaired.

As a method of maintaining the water content, it is possible to cite adjusting the humidity in the storage conditions and reducing the porosity of the storage container during storage.

From the perspective of insulation, the metal content of the resin composition of the present invention is preferably less than 5 mass ppm (parts per million), more preferably less than 1 mass ppm, and further preferably less than 0.5 mass ppm. As metals, sodium, potassium, magnesium, calcium, iron, copper, chromium, nickel, etc. can be cited, but metals contained as complexes of organic compounds and metals are excluded. In the case of containing multiple metals, the total of the metals is preferably within the above range.

In addition, as a method for reducing the metal impurities accidentally contained in the resin composition of the present invention, the following methods can be cited: selecting a raw material with a low metal content as a raw material constituting the resin composition of the present invention; filtering the raw material constituting the resin composition of the present invention with a filter; lining polytetrafluoroethylene or the like in the device to perform distillation under conditions that suppress contamination as much as possible.

If the resin composition of the present invention is used as a semiconductor material, from the perspective of wiring corrosion, the halogen atom content is preferably less than 500 mass ppm, more preferably less than 300 mass ppm, and even more preferably less than 200 mass ppm. Among them, the halogen ion content is preferably less than 5 mass ppm, more preferably less than 1 mass ppm, and even more preferably less than 0.5 mass ppm. As halogen atoms, chlorine atoms and bromine atoms can be cited. It is preferred that the total of chlorine atoms and bromine atoms or chlorine ions and bromine ions are respectively within the above ranges.

As a method for adjusting the content of halogen atoms, ion exchange treatment can be preferably cited.

As a storage container for the resin composition of the present invention, a previously known storage container can be used. In addition, as a storage container, in order to suppress the mixing of impurities into the raw materials or the resin composition of the present invention, it is also preferable to use a multi-layer bottle with 6 layers of 6 resins as the inner wall of the container, or a bottle with 6 resins formed into a 7-layer structure. As such a container, for example, the container described in Japanese Patent Publication No. 2015-123351 can be cited.

<Hardened resin composition>

By hardening the resin composition of the present invention, a hardened product of the resin composition can be obtained.

The hardened material of the present invention is a hardened material obtained by hardening the resin composition of the present invention.

The resin composition is preferably cured by heating, and the heating temperature is preferably in the range of 120°C to 400°C, further preferably in the range of 140°C to 380°C, and particularly preferably in the range of 170°C to 350°C. The shape of the cured product of the resin composition is not particularly limited, and can be selected to be a film, a rod, a sphere, a granule, etc. according to the purpose. In the present invention, the cured product is preferably in the form of a film. In addition, by patterning the resin composition, the shape of the cured product can be selected according to the purpose of forming a protective film on the wall surface, forming a hole (Beer Hall) for conduction, adjusting impedance or electrostatic capacitance or internal stress, and imparting a heat release function. The film thickness of the cured product (film formed by the cured product) is preferably greater than 0.5 μm and less than 150 μm.

The shrinkage rate of the resin composition of the present invention when hardened is preferably 50% or less, 45% or less is more preferably, and 40% or less is further preferably. The shrinkage rate refers to the percentage of volume change of the resin composition before and after hardening, and can be calculated by the following formula.

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

<Characteristics of cured resin composition>

The imidization reaction rate of the cured product of the resin composition of the present invention is preferably 70% or more, more preferably 80% or more, and even more preferably 90% or more. When it is less than 70%, the mechanical properties of the cured product may be poor.

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

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

<Preparation of resin composition>

The resin composition of the present invention can be prepared by mixing the above-mentioned components. The mixing method is not particularly limited and can be performed by a previously known method.

Mixing can be performed by mixing with a stirring blade, mixing with a ball mill, mixing by rotating the tank itself, etc.

The temperature during mixing is preferably 10~30℃, and more preferably 15~25℃.

Furthermore, in order to remove foreign matter such as dust or particles in the resin composition of the present invention, it is preferred to perform filtering using a filter. Regarding the pore size of the filter, for example, 5 μm or less can be cited, 1 μm or less is preferred, 0.5 μm or less is more preferred, and 0.1 μm or less is further preferred. The material of the filter is preferably polytetrafluoroethylene, polyethylene or nylon. In the case where the material of the filter is polyethylene, HDPE (high-density polyethylene) is more preferred. The filter can be pre-cleaned with an organic solvent. In the filtering step of the filter, multiple filters can also be connected in series or in parallel for use. When using multiple filters, filters with different pore sizes or materials can be used in combination. For example, a connection state can be given in which a 1μm HDPE filter is used as the first stage and a 0.2μm HDPE filter is used as the second stage in series. In addition, various materials can be filtered multiple times. When filtering multiple times, it can be cycle filtering. In addition, filtering can also be performed after pressurization. When filtering is performed under pressure, the pressure of the pressurization may be, for example, 0.01MPa or more and 1.0MPa or less, 0.03MPa or more and 0.9MPa or less is preferred, 0.05MPa or more and 0.7MPa or less is more preferred, and 0.05MPa or more and 0.5MPa or less is further preferred.

In addition to filtering using a filter, impurity removal using an adsorbent can also be performed. Filtering using a filter and impurity removal using an adsorbent can also be combined. As the adsorbent, a known adsorbent can be used. For example, inorganic adsorbents such as silica gel and zeolite, and organic adsorbents such as activated carbon can be cited.

Furthermore, after filtering using a filter, the resin composition filled in the bottle may be placed in a depressurized state and degassed.

(Method for manufacturing hardened material)

The method for manufacturing the cured product of the present invention preferably includes a film forming step of applying the resin composition to a substrate to form a film.

Furthermore, it is more preferable that the method for manufacturing the cured product of the present invention includes the above-mentioned film forming step, an exposure step of selectively exposing the film formed by the film forming step, and a developing step of using a developer to develop the film exposed by the exposure step to form a pattern.

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

Furthermore, it is also preferred that the manufacturing method of the present invention includes the above-mentioned film forming step and the step of heating the above-mentioned film.

The following describes the details of each step.

<Membrane formation step>

The resin composition of the present invention can be used in a film forming step for forming a film on a substrate.

The method for manufacturing the cured product of the present invention preferably includes a film forming step of applying the resin composition to a substrate to form a film.

[Base material]

The type of substrate can be appropriately set according to the purpose, but there is no particular limitation. Examples include semiconductor substrates such as silicon, silicon nitride, polycrystalline silicon, silicon oxide, and amorphous silicon, quartz, glass, optical films, ceramic materials, evaporated films, magnetic films, reflective films, metal substrates such as Ni, Cu, Cr, and Fe (for example, any one of a substrate formed of metal and a substrate having a metal layer formed by electroplating or evaporation, etc.), paper, SOG (Spin On Glass), TFT (Thin Film Transistor) array substrate, mold substrate, and electrode plates of plasma display panels (PDP). In the present invention, semiconductor substrates are particularly preferred, and silicon substrates, Cu substrates, and mold substrates are more preferred.

In addition, a bonding layer and an oxide layer made of hexamethyldisilazane (HMDS) or the like may be provided on the surface of the substrate.

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

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

Furthermore, as the substrate, for example, a plate-shaped substrate (substrate) or preferably a panel-shaped substrate can be used.

Furthermore, when a resin composition is applied to the surface of a resin layer (e.g., a layer formed of a hardened material) or the surface of a metal layer to form a film, the resin layer or the metal layer becomes a base material.

As a method of applying the resin composition of the present invention to a substrate, coating is preferred.

As the applicable method, specifically, there can be exemplified dip coating, air knife coating, curtain coating, wire bar coating, gravure coating, extrusion coating, spray coating, spin coating, slit coating, ink jet coating, etc. From the viewpoint of uniformity of film thickness, spin coating, slit coating, spray coating, or ink jet coating is more preferred, and from the viewpoint of uniformity of film thickness and productivity, spin coating and slit coating are preferred. By adjusting the solid content concentration of the resin composition or the coating conditions according to the method, a film of the desired thickness can be obtained. In addition, the coating method can be appropriately selected according to the shape of the substrate. If it is a circular substrate such as a wafer, spin coating, spray coating, inkjet method, etc. are preferred. If it is a rectangular substrate, slit coating, spray coating, inkjet method, etc. are preferred. In the case of spin coating, for example, it can be applied at a rotation speed of 500~3,500rpm for about 10 seconds to 3 minutes.

Furthermore, a method of transferring a coating film formed by pre-imparting the coating film onto a pseudo-support body by the above-mentioned imparting method onto a substrate can also be applied.

Regarding the transfer method, the present invention can also preferably use the production method described in paragraphs 0023, 0036 to 0051 of Japanese Patent Publication No. 2006-023696 or paragraphs 0096 to 0108 of Japanese Patent Publication No. 2006-047592.

In addition, a step of removing excess film at the end of the substrate can be performed. Examples of such a step include edge bead rinsing (EBR) and back rinse (Back rinse).

In addition, a pre-wetting step may be used, in which various solvents are applied to the substrate to improve the wettability of the substrate before the resin composition is applied to the substrate, and then the resin composition is applied.

<Drying Steps>

After the film forming step (layer forming step), the above-mentioned film can be subjected to a step (drying step) of drying the formed film (layer) in order to remove the solvent.

That is, the method for manufacturing the hardened material of the present invention may include a drying step of drying the film formed by the film forming step.

Furthermore, the above-mentioned drying step is preferably performed after the film forming step and before the exposure step.

The drying temperature of the film in the drying step is preferably 50-150°C, more preferably 70-130°C, and even more preferably 90-110°C. In addition, drying can also be performed by reducing pressure. As for the drying time, 30 seconds to 20 minutes can be exemplified, 1 minute to 10 minutes is preferred, and 2 minutes to 7 minutes is more preferred.

<Exposure steps>

The above film can be used in an exposure step for selectively exposing the film.

That is, the method for manufacturing a hardened product of the present invention may include an exposure step for selectively exposing the film formed by the film forming step.

Selective exposure means exposing a portion of the film. In addition, by selective exposure, an exposed area (exposed area) and an unexposed area (non-exposed area) are formed on the film.

There is no particular restriction on the exposure amount as long as the resin composition of the present invention can be cured. For example, an exposure energy of 50 to 10,000 mJ/cm ² at a wavelength of 365 nm is preferred, and 200 to 8,000 mJ/cm ² is more preferred.

The exposure wavelength can be appropriately set within the range of 190~1,000nm, with 240~550nm being the best.

Regarding the exposure wavelength, if we explain it in terms of its relationship with the light source, we can cite (1) semiconductor lasers (wavelengths of 830nm, 532nm, 488nm, 405nm, 375nm, 355nm) etc.), (2) metal halide lamp, (3) high pressure mercury lamp, g-ray (wavelength 436nm), h-ray (wavelength 405nm), i-ray (wavelength 365nm), broadband (3 wavelengths of g, h, and i-ray), (4) excimer laser, KrF excimer laser (wavelength 248nm), ArF excimer laser (wavelength 193nm), F2 excimer laser (wavelength 157nm), (5) extreme ultraviolet ray; EUV (wavelength 13.6nm), (6) electron beam, (7) second harmonic 532nm and third harmonic 355nm of YAG laser, etc. With regard to the resin composition of the present invention, exposure based on a high pressure mercury lamp is particularly preferred, and exposure based on i-ray is particularly preferred. This allows for particularly high exposure sensitivity.

Furthermore, it is also preferred that the exposure light used for exposure includes light with a wavelength of 405nm.

Furthermore, the exposure method is not particularly limited as long as it is a method of exposing at least a portion of the film formed by the resin composition of the present invention, but examples thereof include exposure using a photomask, exposure based on a laser direct imaging method, and the like.

<Post-exposure heating step>

The above film can be provided in a step of heating after exposure (post-exposure heating step).

That is, the method for manufacturing a hardened product of the present invention may include a post-exposure heating step, wherein the post-exposure heating step heats the film exposed by the exposure step.

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

The heating temperature in the post-exposure heating step is preferably 50℃~140℃, and more preferably 60℃~120℃.

The heating time in the post-exposure heating step is preferably 30 seconds to 300 minutes, and more preferably 1 minute to 10 minutes.

Regarding the heating rate in the post-exposure heating step, 1~12℃/minute from the temperature at the start of heating to the highest heating temperature is preferred, 2~10℃/minute is more preferred, and 3~10℃/minute is even more preferred.

In addition, the heating rate can be appropriately changed during the heating process.

There is no particular limitation on the heating mechanism used in the post-exposure heating step, and a known heating plate, oven, infrared heater, etc. can be used.

Furthermore, it is also preferable to perform the process in an environment with low oxygen concentration by flowing an inert gas such as nitrogen, helium, or argon during heating.

<Development steps>

The film after exposure can be used in a developing step of using a developer to form a pattern.

That is, the method for manufacturing a hardened product of the present invention may include a developing step, in which a developing solution is used to develop the film exposed by the exposing step to form a pattern. The developing step removes one of the exposed portion and the non-exposed portion of the film to form a pattern.

Among them, the development of the non-exposed part of the film removed by the development step is called negative development, and the development of the exposed part of the film removed by the development step is called positive development.

〔Developer〕

As the developer used in the developing step, an alkaline aqueous solution or a developer containing an organic solvent can be cited.

In the case where the developer is an alkaline aqueous solution, examples of alkaline compounds that can be contained in the alkaline aqueous solution include inorganic bases, primary amines, secondary amines, tertiary amines, 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 (Tetrapropylammonium hydroxide) Hydroxide), tetrabutylammonium hydroxide, tetrapentylammonium hydroxide, tetrahexylammonium hydroxide, tetraoctylammonium hydroxide, ethyltrimethylammonium hydroxide, butyltrimethylammonium hydroxide, methyltripentylammonium hydroxide, dibutyldipentylammonium hydroxide, dimethylbis(2-hydroxyethyl)ammonium hydroxide, trimethylphenylammonium hydroxide, trimethylbenzylammonium hydroxide, triethylbenzylammonium hydroxide, pyrrole, and piperidine are preferred, and TMAH is more preferred. For example, when using TMAH, the content of alkaline compounds in the developer is preferably 0.01-10 mass % of the total mass of the developer, more preferably 0.1-5 mass %, and even more preferably 0.3-3 mass %.

When the developer contains an organic solvent, the organic solvent may be preferably esters such as ethyl acetate, n-butyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, γ-butyrolactone, ε-caprolactone, δ-valerolactone, alkyl alkoxy acetates (e.g., methyl alkoxy acetate, ethyl alkoxy acetate, butyl alkoxy acetate (e.g., methyl methoxy acetate, ethyl methoxy acetate, butyl methoxy acetate, methyl ethoxy acetate, ethyl ethoxy acetate, etc.)), alkyl 3-alkoxy propionates (e.g., 3- Alkoxy propionic acid methyl esters, 3-alkoxy propionic acid ethyl esters, etc. (for example, 3-methoxy propionic acid methyl ester, 3-methoxy propionic acid ethyl ester, 3-ethoxy propionic acid methyl ester, 3-ethoxy propionic acid ethyl ester, etc.)), 2-alkoxy propionic acid alkyl esters (for example, 2-alkoxy propionic acid methyl ester, 2-alkoxy propionic acid ethyl ester, 2-alkoxy propionic acid propyl ester, etc. (for example, 2-methoxy propionic acid methyl ester, 2-methoxy propionic acid ethyl ester, 2-methoxy propionic acid propyl ester, 2-ethoxy propionic acid methyl ester, 2-ethoxy propionic acid ethyl ester)), 2-alkoxy-2-methyl propionic acid methyl ester and 2-alkoxy-2-methyl propionic acid ethyl ester (for example, 2-methoxy-2-methyl propionic acid methyl ester Ester, ethyl 2-ethoxy-2-methylpropionate, etc.), methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetylacetate, ethyl acetylacetate, methyl 2-oxobutyrate, ethyl 2-oxobutyrate, etc., and as ethers, for example, diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl solvent acetate, ethyl solvent acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether (PGME), propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, etc., and as Ketones, for example, preferably methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, N-methyl-2-pyrrolidone, etc., and cyclic hydrocarbons, for example, preferably toluene, xylene, anisole and other aromatic hydrocarbons, cyclic terpenes such as limonene, etc., as sulfoxides, preferably dimethyl sulfoxide, and as alcohols, preferably methanol, ethanol, propanol, isopropanol, butanol, pentanol, octanol, diethylene glycol, propylene glycol, methyl isobutyl carbinol, triethylene glycol, etc., and as amides, preferably N-methylpyrrolidone, N-ethylpyrrolidone, dimethylformamide, etc.

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

When the developer contains an organic solvent, the content of the organic solvent relative to the total mass of the developer is preferably 50 mass% or more, 70 mass% or more is more preferred, 80 mass% or more is further preferred, and 90 mass% or more is particularly preferred. In addition, the above content may be 100 mass%.

The developer may further contain other ingredients.

As other components, for example, well-known surfactants and well-known defoaming agents can be cited.

[Developer supply method]

There is no particular limitation on the method of supplying the developer as long as the desired pattern can be formed. There are methods of immersing the substrate with the film formed in the developer, using a nozzle to supply the developer to the film formed on the substrate to perform rotary immersion development, or continuously supplying the developer. There is no particular limitation on the type of nozzle, and examples include vertical nozzles, shower nozzles, and mist nozzles.

From the perspective of developer permeability, non-image removal, and manufacturing efficiency, it is better to use a vertical nozzle to supply developer or a spray nozzle to continuously supply developer. From the perspective of developer permeability to the image area, it is better to use a spray nozzle to supply developer.

In addition, the substrate may be rotated to remove the developer from the substrate after continuously supplying the developer using a vertical nozzle, and then the developer may be continuously supplied using a vertical nozzle again after rotation and drying, and then the substrate may be rotated to remove the developer from the substrate. This step may be repeated multiple times.

In addition, as a method for supplying the developer in the developing step, there can be adopted a step of continuously supplying the developer to the substrate, a step of keeping the developer in a substantially static state on the substrate, a step of vibrating the developer on the substrate using ultrasound or the like, and a step combining these.

As for the developing time, 10 seconds to 10 minutes is preferred, and 20 seconds to 5 minutes is more preferred. There is no particular regulation on the temperature of the developing solution during the developing process, but it can be preferably carried out at 10 to 45°C, and more preferably at 18 to 30°C.

In the developing step, after the processing with the developer, the pattern can be further cleaned (rinsed) with a rinse solution. Alternatively, a method can be adopted in which the rinse solution is supplied before the developer in contact with the pattern is completely dried.

[Rinsing fluid]

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

When the rinsing liquid contains an organic solvent, the organic solvent may be preferably esters such as ethyl acetate, n-butyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, γ-butyrolactone, ε-caprolactone, δ-valerolactone, alkyl alkoxy acetates (e.g., methyl alkoxy acetate, ethyl alkoxy acetate, butyl alkoxy acetate (e.g., methyl methoxy acetate, ethyl methoxy acetate, butyl methoxy acetate, methyl ethoxy acetate, ethyl ethoxy acetate, etc.)), alkyl 3-alkoxy propionates (e.g., 3-alkoxy Methyl propionate, ethyl 3-alkoxypropionate, etc. (e.g., methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, etc.)), alkyl 2-alkoxypropionates (e.g., methyl 2-alkoxypropionate, ethyl 2-alkoxypropionate, propyl 2-alkoxypropionate, etc. (e.g., methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate)), methyl 2-alkoxy-2-methylpropionate and ethyl 2-alkoxy-2-methylpropionate (e.g., methyl 2-methoxy-2-methylpropionate, As ethers, for example, diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl solvent acetate, ethyl solvent acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether (PGME), propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, etc., and as ketones, for example, diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl solvent acetate, ethyl solvent acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether (PGME), propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, etc. can be preferably mentioned. , for example, methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, N-methyl-2-pyrrolidone, etc. can be preferably cited, and as cyclic hydrocarbons, for example, aromatic hydrocarbons such as toluene, xylene, anisole, cyclic terpenes such as limonene can be preferably cited, as sulfoxides, dimethyl sulfoxide can be preferably cited, and as alcohols, methanol, ethanol, propanol, isopropanol, butanol, pentanol, octanol, diethylene glycol, propylene glycol, methyl isobutyl carbinol, triethylene glycol, etc. can be preferably cited, and as amides, N-methylpyrrolidone, N-ethylpyrrolidone, dimethylformamide, etc. can be preferably cited.

When the rinse solution 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, dimethyl sulfoxide, N-methylpyrrolidone, cyclohexanone, PGMEA, and PGME are particularly preferred, cyclopentanone, γ-butyrolactone, dimethyl sulfoxide, PGMEA, and PGME are more preferred, and cyclohexanone and PGMEA are further preferred.

When the rinse liquid contains an organic solvent, it is preferred that the rinse liquid contains at least 50% by mass of the organic solvent, more preferably at least 70% by mass of the organic solvent, and even more preferably at least 90% by mass of the organic solvent. In addition, the rinse liquid may contain 100% by mass of the organic solvent.

The rinse may further comprise other ingredients.

As other components, for example, well-known surfactants and well-known defoaming agents can be cited.

[How to supply the flushing fluid]

There is no particular limitation on the method of supplying the rinse liquid as long as the desired pattern can be formed. There are methods of immersing the substrate in the rinse liquid, supplying the rinse liquid to the substrate via a liquid pan, supplying the rinse liquid to the substrate in a spraying manner, and continuously supplying the rinse liquid to the substrate via a mechanism such as a vertical nozzle.

From the perspective of the permeability of the rinse liquid, the removability of the non-image area, and the efficiency in manufacturing, there are methods of supplying the rinse liquid using a shower nozzle, a vertical nozzle, a spray nozzle, etc. The method of continuous supply using a spray nozzle is preferred. From the perspective of the permeability of the rinse liquid to the image area, the method of supplying using a spray nozzle is more preferred. The type of nozzle is not particularly limited, and examples thereof include vertical nozzles, shower nozzles, spray nozzles, etc.

That is, the rinsing step is preferably a step of supplying or continuously supplying the rinsing liquid to the above-mentioned exposed film through a vertical nozzle, and it is more preferably a step of supplying the rinsing liquid through a spray nozzle.

In addition, as a method for supplying the rinsing liquid in the rinsing step, a step of continuously supplying the rinsing liquid to the substrate, a step of keeping the rinsing liquid in a substantially static state on the substrate, a step of vibrating the rinsing liquid on the substrate using ultrasound or the like, and a combination of these steps can be adopted.

As for the rinsing time, 10 seconds to 10 minutes is preferred, and 20 seconds to 5 minutes is more preferred. There is no particular regulation on the temperature of the rinsing liquid during rinsing, but it can be preferably performed at 10 to 45°C, and more preferably at 18 to 30°C.

<Heating steps>

The pattern obtained by the developing step (the pattern after washing in the case of washing step) can be used in the heating step of heating the pattern obtained by the above-mentioned developing step.

That is, the method for manufacturing a hardened product of the present invention may include a heating step, wherein the heating step heats the pattern obtained by the developing step.

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

In the heating step, the resin such as the polyimide precursor is cyclized to become the resin such as the polyimide.

In addition, the crosslinking of unreacted crosslinking groups in the specific resin or the crosslinking agent other than the specific resin is also performed.

As the heating temperature (maximum heating temperature) in the heating step, 50~450℃ is preferred, 150 ~350℃ is more preferred, 150~250℃ is further preferred, 160~250℃ is further preferred, and 160~230℃ is particularly preferred.

The heating step is preferably a step of promoting the cyclization reaction of the polyimide precursor in the above-mentioned pattern by heating the alkali generated from the above-mentioned alkali generator.

Regarding the heating in the heating step, it is better to perform the heating at a heating rate of 1~12℃/min from the temperature at the start of heating to the maximum heating temperature. The above heating rate is more preferably 2~10℃/min, and more preferably 3~10℃/min. By setting the heating rate to more than 1℃/min, it is possible to ensure productivity while preventing excessive volatilization of acid or solvent, and by setting the heating rate to less than 12℃/min, it is possible to alleviate the residual stress of the hardened material.

In addition, in the case of an oven capable of rapid heating, it is preferred to increase the temperature from the start temperature to the maximum heating temperature at a rate of 1 to 8°C/second, more preferably 2 to 7°C/second, and even more preferably 3 to 6°C/second.

The temperature at the start of heating is preferably 20°C to 150°C, more preferably 20°C to 130°C, and even more preferably 25°C to 120°C. The temperature at the start of heating refers to the temperature at the start of the step of heating to the maximum heating temperature. For example, when the resin composition of the present invention is applied to a substrate and then dried, it is the temperature of the dried film (layer), for example, it is preferred to start heating from a temperature 30 to 200°C lower than the boiling point of the solvent contained in the resin composition of the present invention.

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

In particular, when forming a multi-layer laminate, from the perspective of inter-layer adhesion, the heating temperature is preferably 30°C or higher, more preferably 80°C or higher, even more preferably 100°C or higher, and particularly preferably 120°C or higher.

The upper limit of the above heating temperature is preferably below 350°C, more preferably below 250°C, and even more preferably below 240°C.

Heating can be performed in stages. For example, the following steps can be performed: heating from 25°C to 120°C at 3°C/min and maintaining at 120°C for 60 minutes, and heating from 120°C to 180°C at 2°C/min and maintaining at 180°C for 120 minutes. In addition, as described in the specification of U.S. Patent No. 9159547, it is also preferred to perform the treatment while irradiating with ultraviolet rays. By this pretreatment step, the properties of the membrane can be improved. The pretreatment step can be performed in a short time of about 10 seconds to 2 hours, and 15 seconds to 30 minutes is more preferred. The pretreatment can be a step of more than two stages. For example, the first stage pretreatment step can be carried out in the range of 100~150℃, and then the second stage pretreatment step can be carried out in the range of 150~200℃.

Furthermore, cooling can be performed after heating, and the cooling speed at this time is preferably 1~5℃/minute.

In terms of preventing the decomposition of specific resins, it is better to conduct the heating step in a low oxygen concentration environment by flowing an inert gas such as nitrogen, helium, or argon and conducting the heating step under reduced pressure. The oxygen concentration is preferably 50 ppm (volume ratio) or less, and more preferably 20 ppm (volume ratio) or less.

The heating mechanism in the heating step is not particularly limited, and examples thereof include a heating plate, an infrared furnace, an electric oven, a hot air oven, an infrared oven, etc.

<Post-development exposure step>

Instead of or in addition to the above-mentioned heating step, the pattern obtained by the developing step (the pattern after washing in the case of the washing step) can also be used in the post-development exposure step of the pattern after the exposure and development step.

That is, the method for manufacturing a hardened product of the present invention may include a post-development exposure step, which exposes the pattern obtained by the development step. The method for manufacturing a hardened 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, it is possible to promote the cyclization reaction of polyimide precursors by photosensitization of a photoalkali generator or the separation reaction of acid-degradable groups by photosensitization of a photoacid generator.

In the post-development exposure step, it is sufficient to expose at least a portion of the pattern obtained in the development step, but it is preferred to expose the entire pattern.

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

The post-development exposure step can be performed using the light source in the above exposure step, preferably broadband light.

<Metal layer formation step>

The pattern obtained by the development step (preferably the pattern used in at least one of the heating step and the post-exposure development step) can be used in the metal layer forming step of forming a metal layer on the pattern.

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

There is no particular limitation on the metal layer, and existing metal types can be used, including copper, aluminum, nickel, vanadium, titanium, chromium, cobalt, gold, tungsten, tin, silver, and alloys containing these metals. Copper and aluminum are more preferred, and copper is further preferred.

The method for forming the metal layer is not particularly limited, and existing methods can be applied. For example, methods described in Japanese Patent Publication No. 2007-157879, Japanese Patent Publication No. 2001-521288, Japanese Patent Publication No. 2004-214501, Japanese Patent Publication No. 2004-101850, U.S. Patent No. 7888181B2, and U.S. Patent No. 9177926B2 can be used. For example, photolithography, PVD (physical evaporation), CVD (chemical vapor deposition), stripping, electrolytic plating, electroless plating, etching, printing, and a combination of these methods can be considered. More specifically, there are patterning methods that combine sputtering, photolithography, and etching, and patterning methods that combine photolithography and electrolytic plating. As a preferred example of electroplating, there is electrolytic plating using copper sulfate or copper cyanide plating solution.

As for the thickness of the metal layer, the thickest wall thickness is preferably 0.01~50μm, and 1~10μm is more preferred.

<Purpose>

Examples of the manufacturing method of the cured product of the present invention or the field of the cured product of the present invention include insulating films for electronic components, interlayer insulating films for redistribution layers, stress buffer films, etc. In addition, examples include sealing films, substrate materials (base films or cover films, interlayer insulating films for flexible printed circuit boards), or situations where patterns are formed by etching insulating films for actual mounting purposes such as the above. For such uses, for example, you can refer to Science & Technology Co., Ltd. "High-functionalization and application technology of polyimide" April 2008, Kakimoto Masaaki/supervised, CMC Technical Library "Basics and development of polyimide materials" November 2011, Japan Polyimide/Aromatic Polymer Research Association/ed. "Latest polyimide foundation and application" NTS, August 2010, etc.

Furthermore, the manufacturing method of the hardened material of the present invention or the hardened material of the present invention can also be used in the manufacturing of offset printing plates or screen plates, the use of etching forming components, the manufacturing of protective varnishes and dielectric layers in electronics, especially microelectronics, etc.

(Laminar body and method for manufacturing the laminated body)

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

The laminate of the present invention is a laminate including two or more layers formed by hardened materials, and can also be a laminate including three or more layers.

At least one of the two or more layers formed by the hardened material included in the laminate is a layer formed by the hardened material of the present invention. From the perspective of suppressing the shrinkage of the hardened material or the deformation of the hardened material accompanying the shrinkage, it is also preferred that all the layers formed by the hardened material included in the laminate are layers formed by the hardened material of the present invention.

That is, it is preferred that the method for manufacturing the laminate of the present invention includes the method for manufacturing the hardened product of the present invention, and it is even more preferred that the method for manufacturing the hardened product of the present invention is repeated several times.

The laminate of the present invention includes two or more layers formed by a hardened material, and preferably includes a metal layer between any of the layers formed by the hardened material. The metal layer is preferably formed by the metal layer forming step.

That is, the manufacturing method of the laminate of the present invention further includes a metal layer forming step of forming a metal layer on a layer formed by the hardened material during the manufacturing method of the hardened material performed multiple times. The preferred embodiment of the metal layer forming step is as described above.

As the above-mentioned laminate, for example, a laminate having a layered structure including at least three layers stacked in sequence, namely, a first layer formed of a hardened material, a metal layer, and a second layer formed of a hardened material, can be cited as a preferred one.

It is preferred that the first layer formed by the hardened material and the second layer formed by the hardened material are both layers formed by the hardened material of the present invention. The resin composition of the present invention used to form the first layer formed by the hardened material and the resin composition of the present invention used to form the second layer formed by the hardened material may be the same composition or different composition. The metal layer in the laminate of the present invention may be preferably used as metal wiring such as a redistribution layer.

<Layering steps>

The manufacturing method of the laminate of the present invention preferably includes a lamination step.

The lamination step is a series of steps including (a) film formation step (layer formation step), (b) exposure step, (c) development step, (d) heating step and at least one of post-development exposure step, which are performed again in sequence on the surface of the pattern (resin layer) or metal layer. Among them, it can also be a state of repeating (a) film formation step and (d) heating step and post-development exposure step. Moreover, after at least one of (d) heating step and post-development exposure step, (e) metal layer formation step can also be included. It goes without saying that the above-mentioned drying step can be further appropriately included in the lamination step.

When a further layering step is performed after the layering step, a surface activation treatment step may be further performed after the exposure step, after the heating step, or after the metal layer forming step. As the surface activation treatment, plasma treatment may be exemplified. The details of the surface activation treatment will be described later.

The above-mentioned layering step is preferably performed 2 to 20 times, and 2 to 9 times is more preferably performed.

For example, in the structure of resin layer/metal layer/resin layer/metal layer/resin layer/metal layer, it is preferable to set the resin layer to have more than 2 layers and less than 20 layers, and it is further preferable to set the resin layer to have more than 2 layers and less than 9 layers.

The composition, shape and film thickness of the above layers can be the same or different.

In the present invention, it is particularly preferred that the cured product (resin layer) of the resin composition of the present invention is formed by further covering the metal layer after the metal layer is provided. Specifically, there can be cited an embodiment in which (a) a film forming step, (b) an exposure step, (c) a developing step, (d) a heating step and at least one of a post-development exposure step, and (e) a metal layer forming step are sequentially repeated, or an embodiment in which (a) a film forming step, (d) a heating step and at least one of a post-development exposure step, and (e) a metal layer forming step are sequentially repeated. By alternately performing the step of laminating the resin composition layer (resin layer) of the present invention and the step of forming the metal layer, the resin composition layer (resin layer) of the present invention and the metal layer can be alternately laminated.

(Surface activation treatment step)

The method for manufacturing the laminate of the present invention preferably includes a surface activation treatment step of performing surface activation treatment on at least a portion of the above-mentioned metal layer and resin composition layer.

The surface activation treatment step is usually performed after the metal layer forming step, but the metal layer forming step can also be performed after the above-mentioned development step by performing the surface activation treatment step on the resin composition layer.

The surface activation treatment may be performed only on at least a portion of the metal layer, or only on at least a portion of the resin composition layer after exposure, or may be performed on at least a portion of both the metal layer and the resin composition layer after exposure. It is preferred to perform the surface activation treatment on at least a portion of the metal layer, and it is preferred to perform the surface activation treatment on a portion or all of the area of the metal layer where the resin composition layer is formed on the surface. In this way, by performing the surface activation treatment on the surface of the metal layer, the adhesion with the resin composition layer (film) disposed on the surface can be improved.

Furthermore, it is preferable to perform surface activation treatment on part or all of the resin composition layer (resin layer) after exposure. In this way, by performing surface activation treatment on the surface of the resin composition layer, the adhesion between the metal layer and the resin layer provided on the surface after surface activation treatment can be improved. In particular, when the resin composition layer is hardened by negative development, it is not easily damaged by the surface treatment, so that the adhesion is easily improved.

Specifically, the surface activation treatment includes plasma treatment using various raw material gases (oxygen, hydrogen, argon, nitrogen, nitrogen/hydrogen mixed gas, argon/oxygen mixed gas, etc.), corona discharge treatment, etching treatment based on _CF4 / _O2 , _NF3 / _O2 , _SF6 , _NF3 , _NF3 / _O2 , surface treatment based on ultraviolet (UV) ozone method, immersion treatment in an organic surface treatment agent containing a compound having at least one amino group and a thiol group after immersion in an aqueous hydrochloric acid solution to remove an oxide film, and mechanical roughening treatment using a brush. Plasma treatment is preferred, and oxygen plasma treatment using oxygen as the raw material gas is particularly preferred. When performing corona discharge treatment, the energy is preferably 500~200,000J/ ^m2 , more preferably 1000~100,000J/ ^m2 , and most preferably 10,000~50,000J/ ^m2 .

(Manufacturing method of electronic components)

Furthermore, the present invention also discloses a semiconductor device comprising the hardened material of the present invention or the laminate of the present invention.

In addition, the present invention also discloses a method for manufacturing a semiconductor element including a method for manufacturing a cured product of the present invention or a method for manufacturing a laminate of the present invention. As a specific example of a semiconductor element in which the resin composition of the present invention is used to form an interlayer insulating film for a redistribution layer, reference can be made to paragraphs 0213 to 0218 and FIG. 1 of Japanese Patent Publication No. 2016-027357, and such contents are incorporated into this specification.

[Implementation example]

The following examples are given to explain the present invention in more detail. The materials, usage amounts, proportions, processing contents, processing steps, etc. shown in the following examples can be appropriately changed as long as they do not deviate from the purpose of the present invention. Therefore, the scope of the present invention is not limited to the specific examples shown below. Unless otherwise specified, "parts" and "%" are mass standards.

<Synthesis Example A-1>

[Synthesis of polyamide A-1 (polyimide precursor A-1) from oxydiphthalic anhydride, diethylene glycol monomethyl ether and 4,4'-diaminodiphenyl ether]

In a dry reactor equipped with a flat-bottomed joint equipped with a stirrer, a capacitor and an internal thermometer, 20.0 g (64.5 mmol) of oxydiphthalic dianhydride was suspended in 140 ml of diethylene glycol dimethyl ether while removing water. 15.5 g (129 mmol), 0.05 g of hydroquinone and 10.7 g (135 mmol) of pyridine were added successively, and stirred at 60°C for 18 hours. Then, after the mixture was cooled to -20°C, 16.1 g (135.5 mmol) of thionyl chloride was added dropwise over 90 minutes. A white precipitate of pyridine hydrochloride was obtained. Next, the mixture was heated to room temperature (25°C) and stirred for 2 hours, and then 9.7 g (123 mmol) of pyridine and 25 ml of N-methylpyrrolidone (NMP) were added to obtain a transparent solution. Next, 11.8 g (58.7 mmol) of 4,4'-diaminodiphenyl ether was dissolved in 100 ml of NMP and added dropwise to the above transparent solution over 1 hour. During the addition of 4,4'-diaminodiphenyl ether, the viscosity increased. Next, the mixture was stirred for 2 hours. Next, the polyimide proto-driver resin was precipitated in 4 liters of water, and the water-polyimide proto-driver resin mixture was stirred at 5000 rpm for 15 minutes. The polyimide precursor resin was removed by filtration, stirred again in 4 liters of water for 30 minutes and filtered again. Then, the obtained polyimide precursor resin was dried at 45°C for 3 days under reduced pressure to obtain polyimide precursor A-1.

The weight average molecular weight of the obtained A-1 (polystyrene conversion value by gel permeation chromatography (eluent: NMP (N-methyl-2-pyrrolidone)) is 31,000.

The measurement conditions are as follows.

Column: TSKguardcolumn SuperAW-H (4.6mmID.×35mm) 1 piece

A.TSK SuperAWM-H (6.0mmID.×150mm) 2 pieces

Development solvent: NMP (10mmol/L lithium bromide, 10mmol/L phosphoric acid solution)

Column temperature: 50℃

Flow rate: 0.35mL/min

Sample injection volume: 20μL

Sample concentration: 0.1 mass%

Device name: HLC-8220GPC (made by TOSOH CORPORATION)

Calibration curve base resin: polystyrene

<Synthesis Example A-2>

[Synthesis of polyamide A-2 (polyimide precursor A-2) from oxydiphthalic anhydride, 2-hydroxyethyl methacrylate and 4,4'-diaminodiphenyl ether]

In a dry reactor equipped with a flat-bottomed joint equipped with a stirrer, a capacitor and an internal thermometer, 20.0 g (64.5 mmol) of oxydiphthalic anhydride was suspended in 140 ml of diethylene glycol dimethyl ether while removing water. 16.8 g (129 mmol) of 2-hydroxyethyl methacrylate, 0.05 g of hydroquinone and 10.7 g (135 mmol) of pyridine were added and stirred at 60°C for 18 hours. Then, after the mixture was cooled to -20°C, 16.1 g (135.5 mmol) of thionyl chloride was added dropwise over 90 minutes. A white precipitate of pyridine hydrochloride was obtained. Next, the mixture was heated to room temperature and stirred for 2 hours, and then 9.7 g (123 mmol) of pyridine and 25 ml of N-methylpyrrolidone (NMP) were added to obtain a transparent solution. Next, 11.8 g (58.7 mmol) of 4,4'-diaminodiphenyl ether was dissolved in 100 ml of NMP and added dropwise to the above transparent solution over 1 hour. During the addition of 4,4'-diaminodiphenyl ether, the viscosity increased. Next, the mixture was stirred for 2 hours. Next, the polyimide proto-driver resin was precipitated in 4 liters of water, and the water-polyimide proto-driver resin mixture was stirred at 5000 rpm for 15 minutes. The polyimide precursor resin was removed by filtration, stirred again in 4 liters of water for 30 minutes and filtered again. Then, the obtained polyimide precursor resin was dried at 45°C for 3 days under reduced pressure to obtain polyimide precursor A-2. Mw is 31000.

<Synthesis Example A-3>

[Synthesis of polyamide A-3 (polyimide precursor A-3) from 3,3',4,4'-biphenyltetracarboxylic dianhydride, 2-hydroxyethyl methacrylate and 4,4'-diaminodiphenyl ether]

In a dry reactor equipped with a flat-bottomed joint equipped with a stirrer, a capacitor and an internal thermometer, 19.0 g (64.5 mmol) of 3,3',4,4'-biphenyltetracarboxylic dianhydride was suspended in 140 ml of diethylene glycol dimethyl ether while removing water. 16.8 g (129 mmol) of 2-hydroxyethyl methacrylate, 0.05 g of hydroquinone and 10.7 g (135 mmol) of pyridine were added and stirred at 60°C for 18 hours. Then, after the mixture was cooled to -20°C, 16.1 g (135.5 mmol) of thionyl chloride was added dropwise over 90 minutes. A white precipitate of pyridine hydrochloride was obtained. Next, the mixture was heated to room temperature and stirred for 2 hours, and then 9.7 g (123 mmol) of pyridine and 25 ml of N-methylpyrrolidone (NMP) were added to obtain a transparent solution. Next, 11.8 g (58.7 mmol) of 4,4'-diaminodiphenyl ether was dissolved in 100 ml of NMP and added dropwise to the above transparent solution over 1 hour. During the addition of 4,4'-diaminodiphenyl ether, the viscosity increased. Next, the mixture was stirred for 2 hours. Next, the polyimide proto-driver resin was precipitated in 4 liters of water, and the water-polyimide proto-driver resin mixture was stirred at 5000 rpm for 15 minutes. The polyimide precursor resin was removed by filtration, stirred again in 4 liters of water for 30 minutes and filtered again. Then, the obtained polyimide precursor resin was dried at 45°C for 3 days under reduced pressure to obtain polyimide precursor A-3. Mw is 31000.

<Synthesis Example A-4>

[Synthesis of polyamide A-4 (polyimide precursor A-4) from oxydiphthalic dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, 2-hydroxyethyl methacrylate and 4,4'-diaminodiphenyl ether]

In a dry reactor equipped with a flat-bottomed joint equipped with a stirrer, a capacitor, and an internal thermometer, 10.0 g (32.2 mmol) of oxydiphthalic dianhydride and 9.47 g (32.3 mmol) of 3,3',4,4'-biphenyltetracarboxylic dianhydride were suspended in 140 ml of diethylene glycol dimethyl ether while removing water. 16.8 g (129 mmol) of 2-hydroxyethyl methacrylate, 0.05 g of hydroquinone, and 10.7 g (135 mmol) of pyridine were added, and stirred at 60°C for 18 hours. Then, after the mixture was cooled to -20°C, 16.1 g (135.5 mmol) of thionyl chloride was added dropwise over 90 minutes. A white precipitate of pyridine hydrochloride was obtained. Then, the mixture was heated to room temperature and stirred for 2 hours, and then 9.7 g (123 mmol) of pyridine and 25 ml of N-methylpyrrolidone (NMP) were added to obtain a transparent solution. Then, 11.8 g (58.7 mmol) of 4,4'-diaminodiphenyl ether was dissolved in 100 ml of NMP and added dropwise to the above transparent solution over 1 hour. During the addition of 4,4'-diaminodiphenyl ether, the viscosity increased. Then, the mixture was stirred for 2 hours. Then, the polyimide proto-driver resin was precipitated in 4 liters of water, and the water-polyimide proto-driver resin mixture was stirred at 5000 rpm for 15 minutes. The polyimide precursor resin was removed by filtration, stirred again in 4 liters of water for 30 minutes and filtered again. Then, the obtained polyimide precursor resin was dried at 45°C for 3 days under reduced pressure to obtain polyimide precursor A-4. Mw is 30,000.

<Synthesis Example A-5>

[Synthesis of polyamide A-5 (polyimide precursor A-5) from oxydiphthalic anhydride, 2-hydroxyethyl methacrylate and 2,2'-bis(trifluoromethyl)benzidine]

In a dry reactor equipped with a flat-bottomed joint equipped with a stirrer, a capacitor and an internal thermometer, 20.0 g (64.5 mmol) of oxydiphthalic dianhydride was suspended in 55 ml of γ-butyrolactone while removing water. 16.8 g (129 mmol) of 2-hydroxyethyl methacrylate, 0.05 g of hydroquinone and 10.7 g (135 mmol) of pyridine were added successively, and stirred at 60°C for 18 hours.

Next, after cooling the mixture in an ice bath, a solution obtained by dissolving 26.6 g (129 mmol) of dicyclohexylcarbodiimide in 23 mL of γ-butyrolactone was added over 40 minutes. Next, a mixed solution obtained by mixing 18.8 g (58.7 mmol) of 2,2'-bis(trifluoromethyl)benzidine and 45 mL of γ-butyrolactone was added to the reaction solution over 1 hour. Next, the mixture was heated to room temperature and stirred for 2 hours, 2 mL of ethanol was added and stirred for 1 hour, and 50 mL of γ-butyrolactone was added. Next, the precipitate generated in the reaction mixture was removed by filtration, and a precipitate was generated in 500 mL of ethanol and filtered out, and then dissolved in 250 mL of tetrahydrofuran. The obtained solution was added dropwise to 4 liters of water to precipitate the polyimide precursor resin, and the water-polyimide precursor resin mixture was stirred at a speed of 5000 rpm for 15 minutes, and the polyimide precursor was filtered out. Then, under reduced pressure, the obtained polyimide precursor resin was dried at 45°C for 3 days to obtain polyimide precursor A-5. Mw is 30000.

<Synthesis Example A-6>

[Synthesis of polyamide A-6 (polyimide precursor A-6) from oxydiphthalic acid dianhydride, 3,3',4,4'-biphenyltetracarboxylic acid dianhydride and 4,4'-diaminodiphenyl ether]

In a dry reactor equipped with a flat-bottomed joint equipped with a stirrer, a capacitor and an internal thermometer, 11.8 g (58.7 mmol) of 4,4'-diaminodiphenyl ether was dissolved in 20 g of NMP. Then, 10.0 g (32.2 mmol) of oxydiphthalic dianhydride and 9.47 g (32.3 mmol) of 3,3',4,4'-biphenyltetracarboxylic dianhydride were added. After heating to 60°C and stirring for 3 hours, the mixture was cooled to room temperature. The obtained polyimide precursor resin was obtained as an NMP solution. Mw was 32000.

<Synthesis Example A-7>

唑前驅物A-7〕 [Synthesis of polybenzoic acid from 2,2'-bis(3-amino-4-hydroxyphenyl)hexafluoropropane and 4,4'-oxydiphenylformyl chloride]

Azole prodrug A-7〕

唑前驅物樹脂在6升的水中沉澱，並將水-聚苯并

唑前驅物樹脂混合物以500rpm的速度攪拌了15分鐘。過濾去除聚苯并

唑前驅物樹脂，在6升的水中再次攪拌30分鐘並再次進行了過濾。接著，在減壓狀態下，將所獲得之聚苯并

唑前驅物樹脂在45℃下乾燥3天，從而獲得了聚苯并

唑前驅物A-7。Mw為28000。 In a dry reactor equipped with a flat-bottomed joint equipped with a stirrer, a capacitor, and an internal thermometer, 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. Then, 12.1 g (153 mmol) of pyridine was added, and while the temperature was maintained at -10 to 0°C, a solution obtained by dissolving 20.7 g (70.1 mmol) of 4,4'-oxydiphenylformyl chloride in 75 g of diethylene glycol dimethyl ether was added dropwise over 1 hour. After stirring for 30 minutes, 1.00 g (12.7 mmol) of acetyl chloride was added, and further stirred for 60 minutes. Then, polyphenylene glycol was added.

The azole precursor resin was precipitated in 6 liters of water and the water-polybenzoic acid

The azole precursor resin mixture was stirred at 500 rpm for 15 minutes.

The azole precursor resin was stirred again in 6 liters of water for 30 minutes and filtered again.

The precursor resin was dried at 45 °C for 3 days to obtain polyphenylene glycol

Azole prodrug A-7. Mw is 28000.

<Synthesis Example B-1>

Add 15.23 g (120 mmol) of oxalyl chloride and tetrahydrofuran (THF, 200 mL) to a three-necked flask equipped with a magnetic stirrer, a capacitor, and an internal thermometer, and ice-cool while stirring. Then, dissolve 15.2 g (150 mmol) of triethylamine and 31.3 g (240 mmol) of 2-hydroxyethyl methacrylate in 200 mL of THF, and add dropwise to the reaction solution. After 30 minutes, warm to room temperature and stir for another 30 minutes. Filter out insoluble matter, add 1000 mL of ethyl acetate to the filtrate, wash the organic phase with 1N (1 mol/L) hydrochloric acid, and then wash with water three times. After adding magnesium sulfate to the organic phase and drying it, the insoluble matter was filtered out, 4-hydroxy-TEMPO (0.05 g) was added to the filtrate, and the solvent was distilled off under reduced pressure to obtain 33.6 g (yield 89%) of compound B-1. The structure of the obtained B-1 was confirmed by ¹ H-NMR to be the structure represented by the following chemical formula.

<Synthesis Example B-2>

To a three-necked flask equipped with a magnetic stirrer, a capacitor, and an internal thermometer, add 15.23 g (120 mmol) of oxalyl chloride and THF (200 mL), and ice-cool while stirring. Next, dissolve 15.2 g (150 mmol) of triethylamine and 15.6 g (120 mmol) of 2-hydroxyethyl methacrylate in 200 mL of THF, and add the mixture dropwise to the reaction solution. Next, add 5.53 g (120 mmol) of ethanol dropwise to the reaction solution. After 30 minutes, warm the mixture to room temperature and stir for another 30 minutes. Filter out the insoluble matter, add 1000 mL of ethyl acetate to the filtrate, wash the organic phase with 1N (1 mol/L) hydrochloric acid, and then wash it three times with water. After adding magnesium sulfate to the organic phase and drying it, the insoluble matter was filtered out, 4-hydroxy-TEMPO (0.05 g) was added to the filtrate, and the solvent was distilled off under reduced pressure to obtain 24.0 g (yield 87%) of compound B-2. The structure of the obtained B-2 was confirmed by ¹ H-NMR to be the structure represented by the following chemical formula.

<Synthesis Example B-3>

Add 15.23 g (120 mmol) of oxalyl chloride and THF (200 mL) to a three-necked flask equipped with a magnetic stirrer, a capacitor, and an internal thermometer, and ice-cool while stirring. Then, dissolve 15.2 g (150 mmol) of triethylamine and 27.9 g (240 mmol) of 2-hydroxyethyl acrylate in 200 mL of THF, and add dropwise to the reaction solution. After 30 minutes, warm to room temperature and stir for another 30 minutes. Filter out insoluble matter, add 1000 mL of ethyl acetate to the filtrate, wash the organic phase with 1N (1 mol/L) hydrochloric acid, and then wash with water three times. After adding magnesium sulfate to the organic phase and drying it, the insoluble matter was filtered out, 4-hydroxy-TEMPO (0.05 g) was added to the filtrate, and the solvent was distilled off under reduced pressure to obtain 30.9 g (yield 90%) of compound B-3. The structure of the obtained B-3 was confirmed by ¹ H-NMR to be a structure represented by the following chemical formula.

<Synthesis Example B-4>

Add 15.23 g (120 mmol) of oxalyl chloride and THF (200 mL) to a three-necked flask equipped with a magnetic stirrer, a capacitor, and an internal thermometer, and ice-cool the mixture while stirring. Then, dissolve 15.2 g (150 mmol) of triethylamine and 15.6 g (120 mmol) of 2-hydroxyethyl methacrylate in 200 mL of THF, and drop the mixture into the reaction solution. Then, drop 13.9 g (120 mmol) of 2-hydroxyethyl acrylate into the reaction solution. After 30 minutes, heat the mixture to room temperature and stir for another 30 minutes. The insoluble matter was filtered out, 1000 mL of ethyl acetate was added to the filtrate, and the organic phase was washed with 1N (1 mol/L) hydrochloric acid, and then washed with water three times. Magnesium sulfate was added to the organic phase and dried, and the insoluble matter was filtered out. 4-Hydroxy-TEMPO (0.05 g) was added to the filtrate, and the solvent was distilled off under reduced pressure to obtain 33.4 g (yield 91%) of compound B-4. The structure of the obtained B-4 was confirmed by ¹ H-NMR to be the structure represented by the following chemical formula.

<Synthesis Example B-5>

Add 15.23 g (120 mmol) of oxalyl chloride and THF (200 mL) to a three-necked flask equipped with a magnetic stirrer, a capacitor, and an internal thermometer, and ice-cool while stirring. Then, dissolve 15.2 g (150 mmol) of triethylamine and 34.6 g (240 mmol) of hydroxypropyl methacrylate in 200 mL of THF, and add dropwise to the reaction solution. After 30 minutes, warm to room temperature and stir for another 30 minutes. Filter out insoluble matter, add 1000 mL of ethyl acetate to the filtrate, wash the organic phase with 1N (1 mol/L) hydrochloric acid, and then wash with water three times. After adding magnesium sulfate to the organic phase and drying it, the insoluble matter was filtered out, 4-hydroxy-TEMPO (0.05 g) was added to the filtrate, and the solvent was distilled off under reduced pressure to obtain 38.2 g (yield 93%) of compound B-5. The structure of the obtained B-5 was confirmed by ¹ H-NMR to be the structure represented by the following chemical formula.

<Synthesis Example B-6>

In a three-necked flask equipped with a magnetic stirrer, a capacitor, and an internal thermometer, 15.23 g (120 mmol) of oxalyl chloride and THF (200 mL) were added, and the mixture was ice-cooled while stirring. Next, 15.2 g (150 mmol) of triethylamine and 15.6 g (120 mmol) of 2-hydroxyethyl methacrylate were dissolved in 200 mL of THF, and the mixture was added dropwise to the reaction solution. Next, 14.3 g (120 mmol) of 4-aminostyrene was added dropwise to the reaction solution. After 30 minutes, the mixture was heated to room temperature and stirred for another 30 minutes. The insoluble matter was filtered out, 1000 mL of ethyl acetate was added to the filtrate, and the organic phase was washed with 1N hydrochloric acid (1 mol/L), and then washed with water three times. Magnesium sulfate was added to the organic phase and dried, and the insoluble matter was filtered out. 4-Hydroxy-TEMPO (0.05 g) was added to the filtrate and the solvent was distilled off under reduced pressure to obtain 32.8 g (yield 90%) of compound B-6.

<Synthesis Example B-8>

Add 15.23 g (120 mmol) of oxalyl chloride and THF (200 mL) to a three-necked flask equipped with a magnetic stirrer, a capacitor, and an internal thermometer, and ice-cool while stirring. Then, dissolve 15.2 g (150 mmol) of triethylamine and 18.6 g (240 mmol) of 4-aminostyrene in 200 mL of THF, and add the mixture dropwise to the reaction solution. After 30 minutes, warm the mixture to room temperature and stir for another 30 minutes. Filter out the insoluble matter, add 1000 mL of ethyl acetate to the filtrate, wash the organic phase with 1N hydrochloric acid (1 mol/L), and then wash it three times with water. After adding magnesium sulfate to the organic phase and drying it, the insoluble matter was filtered out, 4-hydroxy-TEMPO (0.05 g) was added to the filtrate, and the solvent was distilled off under reduced pressure to obtain 28.4 g (yield 81%) of compound B-8. The structure of the obtained B-8 was confirmed by ¹ H-NMR to be the structure represented by the following chemical formula.

<Implementation examples and comparative examples>

In each embodiment, the components listed in the following table were mixed to obtain each curable resin composition. In addition, in each comparative example, the components listed in the following table were mixed to obtain each comparative composition.

Specifically, the content of components other than the solvents listed in the table is set to the amount (parts by mass) listed in each "Amount Added" column in the table.

Furthermore, A-6 was added so that the solid content in the solution became the amount (mass fraction) listed in "Amount added" in the table.

The obtained curable resin composition and the comparative composition were filtered under pressure through a polytetrafluoroethylene filter with a pore width of 0.8μm.

In the table, "-" indicates that the corresponding component is not contained.

In the table, for columns other than "Solvent", for example, A-2/A-3=50/50 means that A-2 and A-3 are contained in the ratio of A-2:50 parts by mass and A-3:50 parts by mass.

In the table, for example, the entry of NMP/EL=80/20 in the "Solvent" column indicates that NMP and EL are contained in a ratio of NMP:EL=80:20 (mass ratio). In addition, the entry of "Amount added" in the "Solvent" indicates the total content (mass parts) of the mixed solvent with the above content ratio.

The details of each ingredient listed in the table are as follows.

〔Resin〕

．A-1~A-7: A-1~A-7 synthesized in the above synthesis example

[Compound B]

． B-1~B-6, B-8: Compounds B-1~B-6, B-8 synthesized in the above synthesis examples

． B-7: Dibenzyl oxalate (for comparison)

． Compounds B-1~B-6 and compound B-8 are compounds corresponding to the above-mentioned compound B.

[Solvent]

．NMP: N-methylpyrrolidone

．EL: Ethyl lactate

．GBL: γ-butyrolactone

．DMSO: dimethyl sulfoxide

[Photopolymerization initiator]

．C-1~C-3: Compounds with the following structures

[Sensitizer]

．E-1~E-2: Compounds with the following structures

[Chemical formula 68]

[Crosslinking agent (polymerizable compound)]

． F-1~F-3: Compounds with the following structures

[Polymerization inhibitor]

．G-1~G-4: Compounds with the following structures.

[Chemical formula 70]

[Metal adhesion improver]

．H-1~H-2: Compounds with the following structures

[Migration inhibitor]

．I-1~I-2: Compounds with the following structures

[Thermoalkali generator]

．J-1~J-4: Compounds with the following structures

〔Evaluation〕

<Evaluation of membrane strength>

The curable resin composition or comparative composition prepared in each embodiment and comparative example was applied to a silicon wafer by spin coating to form a resin composition layer. The silicon wafer to which the obtained resin composition layer was applied was dried on a heating plate at 100°C for 5 minutes to obtain a resin composition layer with a uniform thickness of about 15 μm on the silicon wafer. For the example in which the composition contained a photopolymerization initiator, the resin composition layer was fully exposed using a stepper (Nikon NSR 2005 i9C) at an exposure energy of 500 mJ/ ^cm2 . For the example in which the composition did not contain a photopolymerization initiator, no exposure was performed. In a nitrogen environment, the obtained resin composition layer (resin layer) was heated at a rate of 10°C/min using a box oven, and after reaching the temperature listed in the "Curing temperature (°C)" in the table, the temperature was maintained for 3 hours. The cured resin layer (cured material) was immersed in a 4.9 mass% hydrofluoric acid solution, and the cured material was peeled off from the silicon wafer. The peeled cured material was made into a test piece with a width of 3mm and a sample length of 30mm using a punching machine. The obtained test piece was measured in accordance with JIS-K625 1: 2017 at a crosshead speed of 300 mm/min in the long direction of the film using a tensile tester (Tensilon) at 25°C and 65% RH (relative humidity). The evaluation was performed 5 times, and the arithmetic mean of the elongation at break (elongation at break) of the film was used as the index value.

The evaluation is conducted according to the following criteria, and the evaluation results are recorded in the "Membrane Strength" column in the table. It can be said that the greater the elongation at break (the above index value), the higher the membrane strength.

-Evaluation criteria-

A The above index value is above 65%.

B The above index value is more than 60% and less than 65%.

C The above index value is above 55% and less than 60%.

D The above index value is greater than 50% and less than 55%.

E The above index value is less than 50%.

<Drug resistance>

The curable resin composition or comparative composition prepared in each embodiment and comparative example was applied to a silicon wafer by spin coating to form a resin composition layer. The silicon wafer to which the obtained resin composition layer was applied was dried on a heating plate at 100°C for 5 minutes to obtain a resin composition layer with a uniform thickness of about 15 μm on the silicon wafer. For the example in which the composition contained a photopolymerization initiator, the resin composition layer was fully exposed using a stepper (Nikon NSR 2005 i9C) at an exposure energy of 500 mJ/ ^cm2 . For the example in which the composition did not contain a photopolymerization initiator, no exposure was performed. In a nitrogen environment, the obtained resin composition layer (resin layer) was heated at a heating rate of 10°C/min using a box oven, and after reaching the temperature described in the "Curing temperature (°C)" in the table, the temperature was maintained for 3 hours, thereby forming a cured product on the silicon wafer.

Without peeling the hardened material from the silicon wafer, the hardened material and the silicon wafer were immersed in the following solution under the following conditions, and the dissolution rate was calculated.

Drug solution: a mixture of 90:10 (mass ratio) of dimethyl sulfoxide (DMSO) and 25 mass% tetramethylammonium hydroxide (TMAH) aqueous solution

Evaluation conditions: Immerse the resin layer in a 75°C solution for 15 minutes, compare the film thickness before and after immersion, and calculate the dissolution rate (nm/minute).

The evaluation is conducted according to the following evaluation criteria, and the evaluation results are recorded in the "Drug Resistance" column in the table. It can be said that the smaller the dissolution rate, the better the drug resistance.

-Evaluation criteria-

A dissolution rate is less than 200nm/min.

B The dissolution rate is greater than 200nm/min and less than 300nm/min.

C The dissolution rate is greater than 300nm/min and less than 400nm/min.

D The dissolution rate is greater than 400nm/min and less than 500nm/min.

E The dissolution rate is above 500nm/min.

<Analysis>

The hardening resin composition or the comparative composition prepared in each embodiment and comparative example was applied to a silicon wafer by spin coating to form a resin composition layer. The silicon wafer to which the obtained resin composition layer was applied was dried at 100°C for 5 minutes on a heating plate to obtain a uniform resin composition layer of about 15 μm in thickness on the silicon wafer. The resin composition layer on the silicon wafer was exposed by i-ray at an exposure energy of 500 mJ/ ^cm2 using a stepper (Nikon NSR 2005 i9C). The exposure was performed through a mask (a binary mask with a line width of 1 μm and a line width of 1:1 and a line width of 5 to 20 μm). After the exposure, cyclopentanone was used for development for 60 seconds and propylene glycol monomethyl ether acetate (PGMEA) was used for 20 seconds to obtain the line and space pattern of the resin composition layer. After that, the obtained resin composition layer was heated at a heating rate of 10°C/min in a box oven in a nitrogen environment. After reaching the temperature recorded in the "hardening temperature (°C)" in the table, the temperature was maintained for 3 hours, thereby forming a hardened material with a line and space pattern on the silicon wafer. The obtained pattern was observed using a scanning electron microscope at a magnification of 5000 times, and the minimum size at which the line and space pattern could be resolved without any residue was set as the resolution. It can be said that the smaller the resolution, the better the resolution.

Furthermore, for the examples with "-" in the column of analytical evaluation results, analytical evaluation will not be performed.

-Evaluation criteria-

A The minimum size analyzed is less than 7μm.

B The minimum size analyzed is greater than 7μm and less than 10μm.

C The minimum size analyzed is greater than 10μm and less than 15μm.

D The minimum size analyzed is above 15μm.

<Implementation Example 51>

In Example 1, the heating mechanism used for heating in the "hardening temperature (°C)" in the table was changed from a box oven to an "infrared lamp heating device (made by ADVANCE RIKO, Inc., RTP-6)", and the above-mentioned film strength, chemical resistance and analytical properties were evaluated by the same method as in Example 1.

The specific heating conditions are as follows: in a nitrogen environment, the temperature is raised at a rate of 10°C/min, and after reaching the temperature listed in the "hardening temperature (°C)" in the table, the temperature is maintained for 3 hours, etc.

The evaluation results of membrane strength, chemical resistance and analytical properties in Example 51 are the same as those in Example 1.

<Implementation Example 52>

In Example 18, analytical evaluation was performed in the same manner as in Example 18 except that the exposure light source was changed from a stepper (Nikon NSR 2005 i9C) to a direct exposure device (ADTEC DE-6UH III). Exposure was performed at a wavelength of 405 nm, and laser direct imaging exposure was performed such that the exposure portion became a line portion in a 1:1 line and space pattern with a line width of 5 to 20 μm and a scale of 1 μm. The exposure amount was set to 500 mJ/cm ² .

The analytical evaluation results in Example 52 are the same as those in Example 18.

<Implementation Example 53>

In Example 18, the exposure based on i-rays was changed to exposure based on light with a wavelength of 405nm. In addition, the evaluation of the above-mentioned film strength, chemical resistance and analytical properties was carried out by the same method as in Example 18.

The evaluation results of membrane strength, chemical resistance and analytical properties in Example 53 are the same as those in Example 18.

From the above results, it can be seen that the hardened material obtained from the hardening resin composition of the present invention has excellent chemical resistance.

The comparative compositions of Comparative Examples 1 to 3 do not contain compound B.

It can be seen that the hardened material obtained from this comparative composition has poor chemical resistance.

<Implementation Example 101>

The curable resin composition used in Example 1 was applied in layers on the surface of a resin substrate having a thin copper layer formed on the surface by spin coating, and dried at 100°C for 4 minutes to form a resin composition layer with a film thickness of 20μm. Then, exposure was performed using a stepper (Nikon Co., Ltd., NSR1505 i6). The exposure was performed at a wavelength of 365nm through a mask (a binary mask with a pattern of 1:1 line and space and a line width of 10μm). After exposure, heating was performed at 100°C for 4 minutes. After the above heating, development was performed with cyclohexanone for 2 minutes and rinsing with PGMEA for 30 seconds to obtain a layer pattern.

Next, the temperature was raised at a rate of 10°C/min in a nitrogen environment. After reaching 230°C, it was maintained at 230°C for 3 hours to form an interlayer insulating film for the redistribution layer. The interlayer insulating film for the redistribution layer has excellent insulation properties.

Furthermore, semiconductor devices were manufactured using the interlayer insulating film for the redistribution layer, and normal operation was confirmed.

without.

Claims (12)

A curable resin composition comprising a pre-driving agent selected from polyimide and polybenzoic acid

At least one resin from the group of oxalic acid proto-initiators and a compound B having at least one structure selected from the group consisting of an oxalic acid monoester structure, an oxalic acid diester structure, an oxalic acid monoamide structure, an oxalic acid diamide structure and an oxalate amide structure and a polymerizable group, wherein the compound B is a compound represented by the following formula (1):

^X1 and ^X2 are independently -O- or -NZ-, Z is a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms, ^R2 is a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms, and ^R1 represents a monovalent organic group including a polymerizable group. The curable resin composition as described in claim 1, wherein the aforementioned polymerizable group is a free radical polymerizable group. The curable resin composition as described in claim 1 further comprises at least one of a photopolymerization initiator and a thermal polymerization initiator. The curable resin composition as described in claim 1 further comprises a photopolymerization initiator. The curable resin composition as claimed in claim 1, wherein the resin comprises a repeating unit represented by formula (2),

In formula (2), ^A1 and ^A2 each independently represent an oxygen atom or -NH-, ^R111 represents a divalent organic group, ^R115 represents a tetravalent organic group, and ^R113 and ^R114 each independently represent a hydrogen atom or a monovalent organic group. The curable resin composition as described in claim 1 is used to form an interlayer insulating film for a redistribution layer. A hardened material, which is formed by hardening the hardening resin composition described in claim 1. A laminate comprising two or more layers formed by the hardened material described in claim 7, and comprising a metal layer between any of the layers formed by the hardened material. A method for manufacturing a hardened product, comprising a film forming step of applying the hardening resin composition described in claim 1 to a substrate to form a film. The method for manufacturing a hardened product as described in claim 9 includes an exposure step of selectively exposing the aforementioned film and a development step of developing the aforementioned film using a developer to form a pattern. The method for manufacturing a cured product as described in claim 9 includes a heating step of heating the aforementioned film at 50-450°C. A semiconductor device comprising the hardener described in claim 7.