WO2021075305A1

WO2021075305A1 - Negative curable composition, cured film, laminate, method for manufacturing cured film, and semiconductor device

Info

Publication number: WO2021075305A1
Application number: PCT/JP2020/037800
Authority: WO
Inventors: 雄一郎榎本; 青島　俊栄; 健太山▲ざき▼
Original assignee: 富士フイルム株式会社
Priority date: 2019-10-18
Filing date: 2020-10-06
Publication date: 2021-04-22
Also published as: JP7319381B2; TW202116874A; JPWO2021075305A1

Abstract

Provided are: a negative curable composition wherein the obtained cured film has excellent chemical resistance; a cured film obtained by curing said negative curable composition; a laminate including said cured film; a method for manufacturing said cured film; and a semiconductor device including said cured film or said laminate.　This negative curable composition contains an alkali-soluble polyimide, multiple kinds of crosslinking agents having different crosslinking groups, and a silane coupling agent, wherein the silane coupling agent has: an alkoxy group e-1 directly bonded to a silicon atom; and a group e-2 which is different from e-1 and can form a covalent bond with at least one among the multiple kinds of crosslinking agents. This cured film is obtained by curing the negative curable composition. This laminate includes the cured film. This semiconductor device includes the cured film or the laminate. This method for manufacturing the cured film includes a step for applying the negative curable composition to a substrate to form a film.

Description

Negative curable composition, cured film, laminate, method for manufacturing cured film, and semiconductor device

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

Polyimide resin is applied to various applications because it has excellent heat resistance and insulating properties. The above application is not particularly limited, and examples of a semiconductor device for mounting include use as a material for an insulating film and a sealing material, or as a protective film. It is also used as a base film and coverlay for flexible substrates.

For example, in the above-mentioned applications, the polyimide resin is used in the form of a negative curable composition containing an alkali-soluble polyimide resin.
Such a negative curable composition can be applied to a substrate by, for example, coating, and then exposed, developed, heated, etc., if necessary, to form a cured resin on the substrate. it can.
Since the negative curable composition can be applied by a known coating method or the like, for example, there is a high degree of freedom in designing the shape, size, application position, etc. of the applied negative curable composition at the time of application. It can be said that it has excellent manufacturing adaptability. In addition to the high performance of polyimide and the like, from the viewpoint of excellent adaptability in manufacturing, industrial application development of a negative curable composition containing an alkali-soluble polyimide is expected more and more.

For example, Patent Document 1 states that it contains an alkali-soluble polyimide (a), an unsaturated bond-containing compound (b), a heat-crosslinkable compound (c), and a photopolymerization initiator (d) having a specific structure. A characteristic photosensitive resin composition is described.

International Publication No. 2018/173840

In a negative curable composition containing an alkali-soluble polyimide, it is desired to provide a negative curable composition having excellent chemical resistance of the obtained cured product.

The present invention relates to a negative curable composition having excellent chemical resistance of the obtained cured film, a cured film obtained by curing the negative curable composition, a laminate containing the cured film, and a method for producing the cured film. , And a semiconductor device including the cured film or the laminate.

Examples of typical embodiments of the present invention are shown below.
<1> Alkali-soluble polyimide,
Multiple types of cross-linking agents with different cross-linking groups, and
Contains silane coupling agent,
The silane coupling agent has a covalent bond between the alkoxy group e-1 directly bonded to the silicon atom and a group different from the e-1 and at least one of the plurality of types of cross-linking agents. A negative curable composition having a possible group e-2.
<2> The above-mentioned plurality of types of cross-linking agents have a cross-linking agent having a radically polymerizable group in which the cross-linking reaction proceeds by the action of a radical as a cross-linking group, and an acid cross-linking property in which the cross-linking reaction proceeds by the action of an acid as a cross-linking group. The negative curable composition according to <1>, which comprises a cross-linking agent having a group.
<3> The negative curable composition according to <1> or <2>, wherein the alkali-soluble polyimide has a fluorine atom.
<4> The negative curable composition according to any one of <1> to <3>, wherein the alkali-soluble polyimide has a silicon atom.
<5> The negative curable composition according to any one of <1> to <4>, wherein the alkali-soluble polyimide has an ethylenically unsaturated bond.
<6> The negative curable composition according to any one of <1> to <5>, wherein the alkali-soluble polyimide has a phenolic hydroxy group.
<7> The negative curable composition according to any one of <1> to <6>, which comprises a compound having at least one structure selected from the group consisting of a sulfonamide structure and a thiourea structure.
<8> The negative curable composition according to any one of <1> to <7>, which contains a radical generator having an oxime structure.
<9> The negative curability according to any one of <1> to <8>, which comprises a compound having 3 to 6 ethylenically unsaturated bonds as at least one of the plurality of types of cross-linking agents. Composition.
<10> The negative curable composition according to any one of <1> to <9>, which contains a neutralized salt-type thermoacid generator.
<11> The negative curable composition according to any one of <1> to <10>, which is used for forming an interlayer insulating film for a rewiring layer.
<12> A cured film obtained by curing the negative curable composition according to any one of <1> to <11>.
<13> A laminate containing two or more layers of the cured film according to <12> and containing a metal layer between any of the cured films.
<14> A method for producing a cured film, which comprises a film forming step of applying the negative curable composition according to any one of <1> to <11> to a substrate to form a film.
<15> The method for producing a cured film according to <14>, which comprises an exposure step of exposing the film and a developing step of developing the exposed film.
<16> The method for producing a cured film according to <14> or <15>, which comprises a heating step of heating the film at 50 to 450 ° C.
<17> A semiconductor device comprising the cured film according to <12> or the laminate according to <13>.

According to the present invention, a negative type curable composition having excellent chemical resistance of the obtained cured film, a cured film obtained by curing the negative type curable composition, a laminate containing the cured film, and the cured film. A manufacturing method and a semiconductor device including the cured film or the laminate are provided.

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

(Negative curable composition)
The negative curable composition of the present invention contains an alkali-soluble polyimide, a plurality of cross-linking agents having different cross-linking groups, and a silane coupling agent, and the above-mentioned silane coupling agent is an alkoxy group directly bonded to a silicon atom. It has e-1 and a group e-2 which is different from the above e-1 and can form a covalent bond with at least one of the above-mentioned plurality of types of cross-linking agents.
Hereinafter, in the present invention, the silane coupling agent having the above e-1 and the above e-2 is also referred to as a "specific silane coupling agent".

As a result of diligent studies, the present inventors have found that a cured film obtained from a negative curable composition containing an alkali-soluble polyimide, a plurality of cross-linking agents having different cross-linking groups, and a specific silane coupling agent is resistant. It was found to be excellent in chemical properties.
According to the negative curable composition of the present invention, for example, a polar solvent such as dimethyl sulfoxide (DMSO) or N-methylpyrrolidone (NMP), an alkaline aqueous solution such as a tetramethylammonium hydroxide (TMAH) aqueous solution, or the above polar solvent. It is considered that a cured film having excellent chemical resistance is provided in which the solubility in a chemical such as a mixed solution of the above alkaline aqueous solution is suppressed.
When a cured film having excellent chemical resistance is used for a product or the like that may come into contact with chemicals such as a solvent during use, storage, manufacturing, etc., a composition containing a solvent is further applied on the cured film. In this case, it is considered to be useful because the dissolution and dispersion of the cured film in a chemical such as a solvent are suppressed when the film formed on the cured film is subjected to solvent development.
The mechanism by which the above effect is obtained is unknown, but it is presumed as follows.
The specific silane coupling agent has the above e-1 and the above e-2. Therefore, in the cured film of the negative curable composition, the reaction between the e-2 and the cross-linking agent causes the compound after cross-linking of the cross-linking agent to contain the siloxane structure derived from the e-1. Conceivable.
That is, the crosslinked compound becomes a compound having a siloxane structure. It is presumed that the cured film contains a compound after cross-linking having such a siloxane structure, so that the chemical resistance of the film is excellent.
Further, it is considered that the compound after the cross-linking has the siloxane structure, so that the mechanical properties (break elongation) and the adhesion of the cured film are easily excellent.

Here, Patent Document 1 does not describe or suggest that the chemical resistance of the cured film is improved by using the specific silane coupling agent.
Hereinafter, the components contained in the negative curable composition of the present invention will be described in detail.

<Alkali-soluble polyimide>
The negative curable composition of the present invention contains an alkali-soluble polyimide.
In the present specification, the alkali-soluble polyimide means a polyimide that dissolves 0.1 g or more at 23 ° C. in 100 g of a 2.38 mass% tetramethylammonium aqueous solution, and 0.5 g or more from the viewpoint of pattern forming property. A polyimide that dissolves is preferable, and a polyimide that dissolves 1.0 g or more is more preferable. The upper limit of the dissolution amount is not particularly limited, but is preferably 100 g or less.
Further, the alkali-soluble polyimide is preferably a polyimide having a plurality of imide structures in the main chain from the viewpoint of breaking elongation and insulating property of the obtained cured film.
In the present specification, the "main chain" refers to the relatively longest binding chain among the molecules of the polymer compound constituting the resin, and the "side chain" refers to other binding chains.

[Fluorine atom]
From the viewpoint of breaking elongation of the obtained cured film, the alkali-soluble polyimide preferably has a fluorine atom.
The fluorine atom is, for example, R ^{115 in} ^{the structure represented by the formula (1-1) described later, R 132} in the repeating unit represented by the formula (2-1) described later, or the formula (2-1) described later. ) Is preferably included in R ¹³¹ ^{in the repeating unit, R 115 in} the structure represented by the formula (1-1) described later, and R in the repeating unit represented by the formula (2-1) described later. It is more preferable that it is contained as an alkyl fluoride group in ¹³² ^{or R 131} in the repeating unit represented by the formula (2-1) described later.
The amount of fluorine atoms with respect to the total mass of the alkali-soluble polyimide is preferably 1 to 50 mol / g, and more preferably 5 to 30 mol / g.

[Silicon atom]
From the viewpoint of the elongation at break of the obtained cured film, the alkali-soluble polyimide preferably has a silicon atom.
The silicon atom is ^{preferably contained in R 131} in the repeating unit represented by the formula (2-1) described later, and will be described later ^{in R 131} in the repeating unit represented by the formula (2-1) described later. It is more preferably contained as an organically modified (poly) siloxane structure.
Further, the silicon atom or the organically modified (poly) siloxane structure may be contained in the side chain of the alkali-soluble polyimide, but is preferably contained in the main chain of the alkali-soluble polyimide.
The amount of silicon atoms with respect to the total mass of the alkali-soluble polyimide is preferably 0.01 to 5 mol / g, more preferably 0.05 to 1 mol / g.

[Ethylene unsaturated bond]
From the viewpoint of the elongation at break of the obtained cured film, the alkali-soluble polyimide preferably has an ethylenically unsaturated bond.
The alkali-soluble polyimide may have an ethylenically unsaturated bond at the end of the main chain or at the side chain, but it is preferably provided at the side chain.
The ethylenically unsaturated bond preferably has radical polymerization property.
^{The ethylenically unsaturated bond is R 115 in} the structure represented by the formula (1-1) ^{described later, R 132} in the repeating unit represented by the formula (2-1) described later, or the formula (2-2-) described later. ^{It is preferably contained in R 131} in the repeating unit represented by 1), and is preferably contained in the formula (1-) described later.
^{Ethylene in R 115 in} the structure represented by 1), ^{R 132} in the repeating unit represented ^{by the formula (2-1) described later, or R 131} in the repeating unit represented by the formula (2-1) described later. It is more preferably contained as a group having a sex unsaturated bond.
Among these, the ethylenically unsaturated bond is ^{preferably contained in R 131} in the repeating unit represented by the formula (2-1) described later, and in the repeating unit represented by the formula (2-1) described later. It is more preferable that R ¹³¹ is contained as a group having an ethylenically unsaturated bond.
Examples of the group having an ethylenically unsaturated bond include a group having a vinyl group which may be substituted, which is directly bonded to an aromatic ring such as a vinyl group, an allyl group and a vinylphenyl group, a (meth) acrylamide group, and a (meth) group. Examples thereof include an acryloyloxy group and a group represented by the following formula (III).

In formula (III), ^R200 represents a hydrogen atom or a methyl group, and a methyl group is preferable.

In formula (III), R ²⁰¹ is an alkylene group having 2 to 12 carbon atoms, -O-CH ₂ CH (OH) CH _2- , -C (= O) O-, -O (C = O) NH-. , (Poly) oxyalkylene group having 2 to 30 carbon atoms (the alkylene group preferably has 2 to 12 carbon atoms, more preferably 2 to 6 carbon atoms, particularly preferably 2 or 3; the number of repetitions is preferably 1 to 12 and 1 ~ 6 is more preferable, and 1 to 3 are particularly preferable), or a group in which two or more of these are combined is represented.
The (poly) oxyalkylene group means an oxyalkylene group or a polyoxyalkylene group.

Among these, R ²⁰¹ is preferably a group represented by any of the following formulas (R1) to (R3), and more preferably a group represented by the formula (R1).

In the formulas (R1) to (R3), L represents a single bond, an alkylene group having 2 to 12 carbon atoms, a (poly) oxyalkylene group having 2 to 30 carbon atoms, or a group in which two or more of these are bonded, and X. Indicates an oxygen atom or a sulfur atom, * represents a binding site with another structure, and ● represents a binding site with an oxygen atom to which ^{R 201 in the formula (III) is bonded.}
In the formulas (R1) to (R3), a preferred embodiment of the alkylene group having 2 to 12 carbon atoms in L or the (poly) oxyalkylene group having 2 to 30 carbon atoms is the above-mentioned R ²⁰¹ having 2 to 12 carbon atoms. This is the same as the preferred embodiment of the 12 alkylene group or the (poly) oxyalkylene group having 2 to 30 carbon atoms.
In formula (R1), X is preferably an oxygen atom.
In formulas (R1) to (R3), * is synonymous with * in formula (III), and the preferred embodiment is also the same.
The structure represented by the formula (R1) comprises, for example, a polyimide having a hydroxy group such as a phenolic hydroxy group and a compound having an isocyanato group and an ethylenically unsaturated bond (for example, 2-isocyanatoethyl methacrylate). Obtained by reacting.
The structure represented by the formula (R2) is obtained, for example, by reacting a polyimide having a carboxy group with a compound having a hydroxy group and an ethylenically unsaturated bond (for example, 2-hydroxyethyl methacrylate, etc.).
The structure represented by the formula (R3) is obtained by reacting, for example, a polyimide having a hydroxy group such as a phenolic hydroxy group with a compound having a glycidyl group and an ethylenically unsaturated bond (for example, glycidyl methacrylate). can get.

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

The amount of the ethylenically unsaturated bond with respect to the total mass of the alkali-soluble polyimide is preferably 0.05 to 10 mol / g, more preferably 0.1 to 5 mol / g.

[Crosslinkable groups other than ethylenically unsaturated bonds]
The alkali-soluble polyimide may have a crosslinkable group other than the ethylenically unsaturated bond.
Examples of the crosslinkable group other than the ethylenically unsaturated bond include a cyclic ether group such as an epoxy group and an oxetanyl group, an alkoxymethyl group such as a methoxymethyl group, and a methylol group.
The crosslinkable group other than the ethylenically unsaturated bond is preferably contained ^{in R 131} in the repeating unit represented by the formula (2-1) described later, for example.
The amount of the crosslinkable group other than the ethylenically unsaturated bond with respect to the total mass of the alkali-soluble polyimide is preferably 0.05 to 10 mol / g, more preferably 0.1 to 5 mol / g.

[Acid value]
From the viewpoint of improving developability, the acid value of the alkali-soluble polyimide is preferably 30 mgKOH / g or more, more preferably 50 mgKOH / g or more, and further preferably 70 mgKOH / g or more.
The acid value is preferably 500 mgKOH / g or less, more preferably 400 mgKOH / g or less, and even more preferably 200 mgKOH / g or less.
The acid value is measured by a known method, for example, by the method described in JIS K 0070: 1992.
Further, as the acid group contained in the alkali-soluble polyimide, an acid group having a pKa of 0 to 10 is preferable, and an acid group having a pKa of 3 to 8 is more preferable, from the viewpoint of achieving both storage stability and developability.
The pKa is a dissociation reaction in which hydrogen ions are released from an acid, and its equilibrium constant Ka is expressed by its negative common logarithm pKa. In the present specification, pKa is a value calculated by ACD / ChemSketch (registered trademark) unless otherwise specified. Alternatively, the values published in "Revised 5th Edition Chemistry Handbook Basics" edited by the Chemical Society of Japan may be referred to.
When the acid group is a polyvalent acid such as phosphoric acid, the pKa is the first dissociation constant.
As such an acid group, the alkali-soluble polyimide preferably contains at least one selected from the group consisting of a carboxy group and a phenolic hydroxy group, and more preferably contains a phenolic hydroxy group.

[Phenolic hydroxy group]
From the viewpoint of making the development speed with an alkaline developer appropriate, the alkali-soluble polyimide preferably has a phenolic hydroxy group.
The alkali-soluble polyimide may have a phenolic hydroxy group at the end of the main chain or at the side chain.
The phenolic hydroxy group is, for example, R ^{115 in} ^{the structure represented by the formula (1-1) described later, R 132} in the repeating unit represented by the formula (2-1) described later, or the formula (2) described later. It is preferably contained ^{in R 131} in the repeating unit represented by -1).
The amount of the phenolic hydroxy group with respect to the total mass of the alkali-soluble polyimide is preferably 0.1 to 30 mol / g, and more preferably 1 to 20 mol / g.

[Structure represented by equation (1-1)]
Further, the alkali-soluble polyimide preferably has a structure represented by the following formula (1-1), and preferably has a structure represented by the following formula (1-1) in the main chain.

In formula (1-1), R ¹¹⁵ represents a tetravalent organic group.

-R ^115-
In the above formula (1-1), R ¹¹⁵ is preferably a tetravalent organic group containing an aromatic ring, and more preferably a group represented by the following formula (1-2) or formula (1-3).

In formula (1-2), R ¹¹² is a divalent linking group, which is an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be substituted with a single bond or a fluorine atom, —O—, -C (= O)-, -S-, -S (= O) _2- , -NHC (= O)-, or a group in which two or more of these are combined is preferable, and a single bond or a fluorine atom is used. More preferably, it is a group selected from an alkylene group having 1 to 3 carbon atoms which may be substituted, —O—, −C (= O) −, —S— and S (= O) _2−. Divalent selected from the group consisting of _{-CH 2-} , -O-, -S-, -S (= O) _2- , -C (CF ₃ ) _2- , and -C (CH ₃ ) _2- It is more preferable that it is a group of. * Each independently represents a binding site with another structure.

^{Specific examples of the tetravalent organic group represented by R 115} in the formula (1-1) include a tetracarboxylic acid residue remaining after removing the acid dianhydride group from the tetracarboxylic dianhydride. .. Only one type of tetracarboxylic dianhydride may be used, or two or more types may be used. The tetracarboxylic dianhydride is preferably a compound represented by the following formula (1-4).

In formula (1-4), R ¹¹⁵ represents a tetravalent organic group. R ¹¹⁵ has the same meaning as ^{R 115} in formula (1-1), preferable embodiments thereof are also the same.

Specific examples of the tetracarboxylic dianhydride include pyromellitic acid, pyromellitic dianhydride (PMDA), 3,3', 4,4'-biphenyltetracarboxylic dianhydride, 3,3', 4 , 4'-diphenylsulfide tetracarboxylic dianhydride, 3,3', 4,4'-diphenylsulfonetetracarboxylic dianhydride, 3,3', 4,4'-benzophenonetetracarboxylic dianhydride, 3,3', 4,4'-diphenylmethanetetracarboxylic dianhydride, 2,2', 3,3'-diphenylmethanetetracarboxylic dianhydride, 2,3,3', 4'-biphenyltetracarboxylic acid Dichloride, 2,3,3', 4'-benzophenonetetracarboxylic dianhydride, 4,4'-oxydiphthalic acid dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 1 , 4,5,7-naphthalenetetracarboxylic dianhydride, 2,2-bis (3,4-dicarboxyphenyl) propane dianhydride, 2,2-bis (2,3-dicarboxyphenyl) propanedian Anhydroide, 2,2-bis (3,4-dicarboxyphenyl) hexafluoropropane dianhydride, 1,3-diphenylhexafluoropropane-3,3,4,54-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-phenanthenetetracarboxylic dianhydride, 1,1- Bis (2,3-dicarboxyphenyl) ethane dianhydride, 1,1-bis (3,4-dicarboxyphenyl) ethane dianhydride, 1,2,3,4-benzenetetracarboxylic dianhydride, In addition, at least one selected from these alkyl derivatives having 1 to 6 carbon atoms and alkoxy derivatives having 1 to 6 carbon atoms is exemplified.

Further, the tetracarboxylic dianhydrides (DAA-1) to (DAA-5) shown below are also mentioned as preferable examples.

[Repeating unit represented by equation (2-1)]
Further, the alkali-soluble polyimide preferably has a repeating unit represented by the following formula (2-1), and preferably has a repeating unit represented by the following formula (2-1) in the main chain.

In formula (2-1), R ¹³¹ represents a divalent organic group and R ¹³² represents a tetravalent organic group.

-R ^131-
In the formula (2-1), the ^{divalent organic group represented by R 131} includes a linear or branched aliphatic group, a cyclic aliphatic group, an aromatic group, an organically modified (poly) siloxane structure or. Examples of a group in which two or more of these are combined are a linear aliphatic group having 2 to 20 carbon atoms, a branched aliphatic group having 3 to 20 carbon atoms, a cyclic aliphatic group having 3 to 20 carbon atoms, and a cyclic aliphatic group having 3 to 20 carbon atoms. An aromatic hydrocarbon group of 6 to 20, an organically modified (poly) siloxane structure, or a group in which two or more of these are combined is preferable, and an aromatic hydrocarbon group having 6 to 20 carbon atoms is more preferable.
The linear or branched aliphatic group, the cyclic aliphatic group, or the aromatic group may have a substituent, and the substituent includes an alkyl group, a hydroxy group, a thiol group, and the like. Examples thereof include a carboxy group, a group having the above-mentioned ethylenically unsaturated bond, and a crosslinkable group other than the above-mentioned ethylenically unsaturated bond.
The organically modified (poly) siloxane structure includes both an organically modified siloxane structure containing only one siloxane structure and an organically modified polysiloxane structure containing two or more siloxane structures.
As the organically modified (poly) siloxane structure, a structure represented by the following formula (SI-1) is preferable.

In formula (SI-1), ^RS independently represents a hydrogen atom or an organic group, ^{at least one of RS} represents an organic group, n represents an integer of 1 or more, and * represents an integer or more independently. , Represents a binding site with another structure.

In the formula (SI-1), ^RS is preferably a hydrogen atom, an alkyl group or an aryl group, respectively, and more preferably an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 20 carbon atoms. Alkyl groups or phenyl groups having 1 to 4 carbon atoms are more preferable, methyl groups or phenyl groups are particularly preferable, and methyl groups are most preferable.
Also, represents at least one organic group among structured R ^S, it is preferable that at least one of the two structured R ^S binding to each of the plurality of Si in the formula (SI-1) is an organic group of formula ( it is more preferable that all of the SI-1) in structured R ^S is an organic group.
In the formula (SI-1), n represents an integer of 1 or more, preferably an integer of 1 to 11, more preferably an integer of 1 to 3, and even more preferably 1 or 2. It is particularly preferably 0.

When R ¹³¹ contains an organically modified (poly) siloxane structure, ^{it is preferable that R 131} has a structure represented by the following formula (SI-2).

In formula (SI-2), ^RS independently represents a hydrogen atom or an organic group, ^{at least one of RS} represents an organic group, and L ¹ is a linear or branched aliphatic aliphatic group. Represents a group, a cyclic aliphatic group, an aromatic group, or a group in which two or more of these are combined, and L ² is -Si ( ^RS ) _2- , a linear or branched aliphatic group, or a cyclic fat. It represents a group group, an aromatic group, or a group in which two or more of these are combined, n represents an integer of 1 or more, and * represents a bonding site with another structure independently.
Wherein (SI-2), ^{R S} and n have the same meanings as ^{R S} and n in the above formula (SI-1), a preferable embodiment thereof is also the same.
In formula (SI-2), L ¹ is a linear aliphatic group having 2 to 20 carbon atoms, a branched aliphatic group having 3 to 20 carbon atoms, a cyclic aliphatic group having 3 to 20 carbon atoms, and carbon. An aromatic hydrocarbon group having a number of 6 to 20 or a group in which two or more of these are combined is preferable, and a linear aliphatic group having 2 to 20 carbon atoms is more preferable.
In formula (SI-2), L ² is a linear aliphatic group having 2 to 20 carbon atoms, a branched aliphatic group having 3 to 20 carbon atoms, a cyclic aliphatic group having 3 to 20 carbon atoms, and carbon. An aromatic hydrocarbon group having a number of 6 to 20 or a group in which two or more of these are combined is preferable, and a linear aliphatic group having 2 to 20 carbon atoms is more preferable.
Further, L ² is also preferably a group represented by ^{* 1-} Si ( ^RS ) _2- L ^3- * ^2. ^RS is as described above, * ¹ represents a binding site with an oxygen atom in the formula (Si-2), L ³ ^{is synonymous with L 1} described above, and the preferred embodiment is also the same, * ² Is synonymous with * in which ^{L 2} in equation (SI-2) is bound.

^{R 131} in formula (2-1) is preferably derived from diamine. Examples of the diamine used in the production of the alkali-soluble polyimide include linear or branched aliphatic, cyclic aliphatic or aromatic diamines, and two * in the structure represented by the above formula (SI-2). In each case, a compound that binds to an amino group and the like can be mentioned. Only one kind of diamine may be used, or two or more kinds of diamines may be used.

Specifically, the diamine is a linear aliphatic group having 2 to 20 carbon atoms, a branched or cyclic aliphatic group having 3 to 20 carbon atoms, an aromatic group having 6 to 20 carbon atoms, and an organic modification (poly). ) A diamine having a siloxane structure or a group containing two or more of these is preferable, and a diamine containing an aromatic group having 6 to 20 carbon atoms is more preferable.
The linear or branched aliphatic group, the cyclic aliphatic group, or the aromatic group may have a substituent, and the substituent includes an alkyl group, a hydroxy group, a thiol group, and the like. Examples thereof include a carboxy group, a group having the above-mentioned ethylenically unsaturated bond, and a crosslinkable group other than the above-mentioned ethylenically unsaturated bond. Further, the group having an ethylenically unsaturated bond is a group that reacts with the above functional group after producing polyimide or a precursor compound thereof using a diamine having a functional group such as a hydroxy group, a thiol group or a carboxy group (for example). , Isocyanato group, hydroxy group, epoxy group, etc.) and a compound having an ethylenically unsaturated bond may be introduced by reacting with the above-mentioned polyimide or a precursor compound thereof.
Examples of aromatic groups include:

In the formula, A is an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be replaced with a single bond or a fluorine atom, —O—, —C (= O) −, —S—, —S. (= O) _2- , -NHC (= O)-, or a group obtained by combining two or more of these is preferable, and a single bond, an alkylene group having 1 to 3 carbon atoms which may be substituted with a fluorine atom. , -O-, -C (= O)-, -S- and S (= O) _2- , more preferably, -CH _2- , -O-, -S-,- It is more preferably a divalent group selected from the group consisting of S (= O) _2- , -C (CF ₃ ) _2- , and -C (CH ₃ ) _2-.

Further, in the above AR-1 to the above AR-10, a structure in which at least one hydrogen atom bonded to the benzene ring is substituted with a hydroxy group or a thiol group is also preferably mentioned.
Among these, among the hydrogen atoms bonded to the benzene ring in AR-1 to AR-3, one or two have been substituted with a hydroxy group or a thiol group, or two in AR-5 to AR-10. Among the benzene rings, a structure in which one of the hydrogen atoms bonded to one benzene ring and one of the hydrogen atoms bonded to the other benzene ring are substituted with a hydroxy group or a thiol group is preferable.

Specific examples of the diamine include 1,2-diaminoethane, 1,2-diaminopropane, 1,3-diaminopropane, 1,4-diaminobutane, 1,6-diaminohexane; 1,2- or 1 , 3-Diaminocyclopentane, 1,2-, 1,3- or 1,4-diaminocyclohexane, 1,2-, 1,3- or 1,4-bis (aminomethyl) cyclohexane, bis- (4-) Aminocyclohexyl) methane, bis- (3-aminocyclohexyl) methane, 4,4'-diamino-3,3'-dimethylcyclohexylmethane or isophoronediamine; meta or paraphenylenediamine, 2,5-dihydroxy-p-phenylenediamine , 2,5-Dimercapto-p-phenylenediamine, diaminotoluene, 4,4'-or 3,3'-diaminobiphenyl, 4,4'-diaminodiphenyl ether, 3,3-diaminodiphenyl ether, 4,4'-or 3,3'-diaminodiphenylmethane, 4,4'-or 3,3'-diaminodiphenylsulfone, 4,4'-or 3,3'-diaminodiphenylsulfide, 4,4'-or 3,3'-diamino Benzophenone, 3,3'-dimethyl-4,4'-diaminobiphenyl, 2,2'-dimethyl-4,4'-diaminobiphenyl (4,4'-diamino-2,2'-dimethylbiphenyl), 3, 3'-dimethoxy-4,4'-diaminobiphenyl, 2,2-bis (4-aminophenyl) propane, 2,2-bis (4-aminophenyl) hexafluoropropane, 2,2-bis (3-hydroxy) -4-Aminophenyl) propane, 2,2-bis (3-hydroxy-4-aminophenyl) hexafluoropropane, 2,2-bis (3-amino-4-hydroxyphenyl) propane, 2,2-bis ( 3-Amino-4-hydroxyphenyl) hexafluoropropane, bis (3-amino-4-hydroxyphenyl) sulfone, bis (4-amino-3-hydroxyphenyl) sulfone, 4,4'-diaminoparatelphenyl, 4 , 4'-bis (4-aminophenoxy) biphenyl, bis [4- (4-aminophenoxy) phenyl] sulfone, bis [4- (3-aminophenoxy) phenyl] sulfone, bis [4- (2-aminophenoxy) phenyl] ) Phenyl] sulfone, 1,4-bis (4-aminophenoxy) benzene, 9,10-bis (4-aminophenyl) anthracene, 3,3'-dimethyl-4,4 '-Diaminodiphenylsulfone, 1,3-bis (4-aminophenoxy) benzene, 1,3-bis (3-aminophenoxy) benzene, 1,3-bis (4-aminophenyl) benzene, 3,3'- Diethyl-4,4'-diaminodiphenylmethane, 3,3'-dimethyl-4,4'-diaminodiphenylmethane, 4,4'-diaminooctafluorobiphenyl, 2,2-bis [4- (4-aminophenoxy) phenyl ] Propane, 2,2-bis [4- (4-aminophenoxy) phenyl] hexafluoropropane, 9,9-bis (4-aminophenyl) -10-hydroanthracene, 3,3', 4,4'- Tetraaminobiphenyl, 3,3', 4,4'-tetraaminodiphenyl ether, 1,4-diaminoanthraquinone, 1,5-diaminoanthraquinone, 3,3-dihydroxy-4,4'-diaminobiphenyl, 9,9' -Bis (4-aminophenyl) fluorene, 4,4'-dimethyl-3,3'-diaminodiphenylsulfone, 3,3', 5,5'-tetramethyl-4,4'-diaminodiphenylmethane, 2-( 3', 5'-diaminobenzoyloxy) ethyl methacrylate, 2,4- or 2,5-diaminocumene, 2,5-dimethyl-paraphenylenediamine, acetoguanamine, 2,3,5,6-tetramethyl-para Phenylenediamine, 2,4,6-trimethyl-methphenylenediamine, 1,3-bis (3-aminopropyl) tetramethyldisiloxane, 2,7-diaminofluorene, 2,5-diaminopyridine, 1,2-bis (4-Aminophenyl) ethane, diaminobenzanilide, ester of diaminobenzoic acid, 1,5-diaminonaphthalene, diaminobenzotrifluoride, 1,3-bis (4-aminophenyl) hexafluoropropane, 1,4-bis (4-Aminophenyl) Octafluorobutane, 1,5-bis (4-aminophenyl) decafluoropentane, 1,7-bis (4-aminophenyl) tetradecafluoroheptane, 2,2-bis [4- (4- (4-aminophenyl) 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, Parabis (4-amino-2-trifluoromethylphenoxy) benzene, 4,4'-bis (4-amino-2-trifluoromethylphenoxy) biphenyl, 4,4'-bis (4-4'-bis) Amino-3-trifluoromethylphenoxy) Biphenyl, 4,4'-bis (4-amino-2-trifluoromethylphenoxy) diphenylsulfone, 4,4'-bis (3-amino-5-trifluoromethylphenoxy) Diphenylsulfone, 2,2-bis [4- (4-amino-3-trifluoromethylphenoxy) phenyl] hexafluoropropane, 3,3', 5,5'-tetramethyl-4,4'-diaminobiphenyl, Selected from 4,4'-diamino-2,2'-bis (trifluoromethyl) biphenyl, 2,2', 5,5', 6,6'-hexafluorotrizine and 4,4'-diaminoquaterphenyl Included are at least one diamine.

Further, the diamines (DA-1) to (DA-18) shown below are also preferable.

Further, a diamine having at least two alkylene glycol units in the main chain is also mentioned as a preferable example. A diamine containing two or more of one or both of an ethylene glycol chain and a propylene glycol chain in one molecule is preferable, and a diamine containing no aromatic ring is preferable. Specific examples include Jeffamine (registered trademark) KH-511, Jeffamine (registered trademark) ED-600, Jeffamine (registered trademark) ED-900, Jeffamine (registered trademark) ED-2003, and Jeffamine (registered trademark). ) EDR-148, Jeffamine® EDR-176, D-200, D-400, D-2000, D-4000 (trade name, manufactured by HUNTSMAN), 1- (2- (2- (2)) -Aminopropoxy) ethoxy) propoxy) propane-2-amine, 1- (1- (1- (2-aminopropoxy) propoxy-2-yl) oxy) propane-2-amine, etc., but are limited to these. Not done.

Jeffamine® KH-511, Jeffamine® ED-600, Jeffamine® ED-900, Jeffamine® ED-2003, Jeffamine® EDR-148, The structure of Jeffamine® EDR-176 is shown below.

In the above, x, y, and z are arithmetic mean values.

^{R 131} in the formula (2-1) is preferably represented by ^{−Ar 0} −L ⁰ −Ar ⁰ − from the viewpoint of the flexibility of the obtained cured film. Ar ⁰ is independently an aromatic hydrocarbon group (preferably 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, particularly preferably 6 to 10 carbon atoms), and a phenylene group is preferable. L ⁰ is an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be replaced with a single bond or a fluorine atom, −O−, −C (= O) −, −S−, −S (=). _O) 2 -, - NHCO-, or represent these two or more combined groups. The preferred range of L ⁰ is synonymous with A above.

^{R 131} in the formula (2-1) is preferably a divalent organic group represented by the following formula (51) or the formula (61) from the viewpoint of i-ray transmittance. In particular, a divalent organic group represented by the formula (61) is more preferable from the viewpoint of i-ray transmittance and availability.

In formula (51), R ⁵⁰ to R ⁵⁷ are independently hydrogen atoms, fluorine atoms or monovalent organic groups, and ^{at least one of R 50} to R ⁵⁷ is a fluorine atom, a methyl group or a fluoromethyl group. It is a difluoromethyl group, a trifluoromethyl group, a phenolic hydroxy group, or a thiol group, and * independently represents a binding site with another structure.

The ^{monovalent organic group of R 50} to R ⁵⁷ includes an unsubstituted alkyl group having 1 to 10 carbon atoms (preferably 1 to 6 carbon atoms) and 1 to 10 carbon atoms (preferably 1 to 6 carbon atoms). Examples thereof include an alkyl fluoride group, a phenolic hydroxy group and a thiol group.

In formula (61), R ⁵⁸ and R ⁵⁹ are independently fluorine atoms, fluoromethyl groups, difluoromethyl groups, or trifluoromethyl groups, respectively.

Examples of the diamine compound giving the structure of the formula (51) or (61) include dimethyl-4,4'-diaminobiphenyl, 2,2'-bis (trifluoromethyl) -4,4'-diaminobiphenyl, 2,2. Examples thereof include'-bis (fluoro) -4,4'-diaminobiphenyl and 4,4'-diaminooctafluorobiphenyl. One of these may be used, or two or more thereof may be used in combination.

-R ^132-
In the formula (2-1), ^{as the tetravalent organic group represented by R 132} ^{, the same group as R 115} in the above formula (1-1) is exemplified, and the preferable range is also the same.

-Content-
The alkali-soluble polyimide may have only one type of repeating unit represented by the formula (2-1), or may have two or more types.
As one embodiment of the alkali-soluble polyimide in the present invention, 50 mol% or more, more 70 mol% or more, particularly 90 mol% or more of all the repeating units is the alkali which is the repeating unit represented by the formula (2-1). Soluble polyimide is exemplified. As an upper limit, 100 mol% or less is practical.

[Molecular weight]
The weight average molecular weight (Mw) of the alkali-soluble polyimide is preferably 2,000 to 500,000, more preferably 2,500 to 100,000, and even more preferably 3,000 to 50,000. The number average molecular weight (Mn) is preferably 800 to 250,000, more preferably 1,500 to 50,000, and even more preferably 2,000 to 25,000.

The degree of dispersion of the molecular weight of the alkali-soluble polyimide is preferably 1.5 to 3.5, more preferably 2 to 3.
In the present specification, the degree of molecular weight dispersion means a value obtained by dividing the weight average molecular weight by the number average molecular weight (weight average molecular weight / number average molecular weight).

〔Concrete example〕
Examples of the alkali-soluble polyimide include, but are not limited to, the alkali-soluble polyimide used in the examples.

[Synthesis method]
The alkali-soluble polyimide can be obtained, for example, by the method described in Examples.
Specifically, an alkali-soluble polyimide can be obtained by reacting a dicarboxylic acid or a dicarboxylic acid derivative with a diamine to obtain a precursor compound, and then heating the compound. Further, an alkali-soluble polyimide can be obtained by halogenating a dicarboxylic acid or a dicarboxylic acid derivative with a halogenating agent and then heating the precursor compound obtained by reacting with a diamine.
When the precursor compound or polyimide has a functional group such as a hydroxy group, a thiol group, or a carboxy group, a group that reacts with the functional group (for example, an isocyanato group, a hydroxy group, or an epoxy group) with respect to the precursor compound or polyimide. Etc.) and a compound having an ethylenically unsaturated bond is reacted with the above-mentioned polyimide or a precursor compound thereof, and in the case of a precursor compound, this is cyclized by heating or the like to obtain a polyimide having an ethylenically unsaturated bond. Be done.

[Imidization rate (ring closure rate)]
The imidization rate (also referred to as “ring closure rate”) of the alkali-soluble polyimide is preferably 70% or more, and more preferably 80% or more, from the viewpoint of breaking elongation of the obtained cured film, insulating property, and the like. It is preferably 90% or more, and more preferably 90% or more.
The upper limit of the imidization rate is not particularly limited, and may be 100% or less.
The imidization rate is measured by, for example, the following method.
The infrared absorption spectrum of the alkali-soluble polyimide is measured to determine the peak intensity P1 near ^{1377 cm -1, which is the absorption peak derived from the imide structure.} Next, the alkali-soluble polyimide is heat-treated at 350 ° C. for 1 hour, and then the infrared absorption spectrum is measured again to obtain a peak intensity P2 in the vicinity of ^{1377 cm -1.} Using the obtained peak intensities P1 and P2, the imidization rate of the alkali-soluble polyimide can be determined based on the following formula.
Imidization rate (%) = (peak intensity P1 / peak intensity P2) × 100

〔Content〕
The content of the alkali-soluble polyimide in the negative curable composition of the present invention is preferably 20% by mass or more, more preferably 30% by mass or more, based on the total solid content of the negative curable composition. It is more preferably 40% by mass or more, and even more preferably 50% by mass or more. The content of the alkali-soluble polyimide in the negative curable composition of the present invention is preferably 99.5% by mass or less, preferably 99% by mass or less, based on the total solid content of the negative curable composition. It is more preferably 98% by mass or less, further preferably 97% by mass or less, and even more preferably 95% by mass or less.
The negative curable composition of the present invention may contain only one type of alkali-soluble polyimide, or may contain two or more types of alkali-soluble polyimide. When two or more kinds are included, the total amount is preferably in the above range.

<Multiple types of cross-linking agents with different cross-linking groups>
The negative curable composition of the present invention contains a plurality of types of cross-linking agents having different cross-linking groups.
The above-mentioned alkali-soluble polyimide or the compound corresponding to the specific silane coupling agent described later shall not correspond to the above-mentioned cross-linking agent.
Examples of the crosslinkable group in the above-mentioned cross-linking agent include a (meth) acryloxy group, a (meth) acrylamide group, a vinyl group, an allyl group, a vinylphenyl group and other groups containing an ethylenically unsaturated bond, an epoxy group, an oxetanyl group and the like cyclic groups. Examples thereof include an alkoxymethyl group such as an ether group and a methoxymethyl group, a methylol group, and a benzoxazolyl group.
In the present invention, the negative curable composition contains a plurality of types of cross-linking agents having different cross-linking groups, that is, the negative curable composition includes a cross-linking agent having a certain cross-linking group A and the cross-linking group A. Means that it contains a cross-linking agent having a different kind of cross-linking group B.
The different crosslinkable groups may mean that the crosslinkable groups have different structures, but they are selected from the group consisting of the above-mentioned group containing an ethylenically unsaturated bond, a cyclic ether group, an alkoxymethyl group, and a methylol group. A combination of one type and another type selected from the above group is preferable.
Hereinafter, a cross-linking agent having a group containing the ethylenically unsaturated bond as a cross-linking group is referred to as a "ethylene unsaturated bond-containing cross-linking agent", and a cross-linking agent containing the above-mentioned cyclic ether group as a cross-linking group is referred to as a "cyclic ether group-containing cross-linking agent". "Agent", the cross-linking agent having the alkoxymethyl group as the cross-linking group is "alkoxymethyl group-containing cross-linking agent", the cross-linking agent having the methylol group as the cross-linking group is "methylol group-containing cross-linking agent", and the cross-linking group is described above. A cross-linking agent having a benzoxazolyl group is also referred to as a "benzoxazolyl group-containing cross-linking agent".

From the viewpoint of chemical resistance and elongation at break, the negative curable composition of the present invention preferably contains an ethylenically unsaturated bond-containing crosslinker as at least one of the above-mentioned plurality of crosslinkers, and is ethylenically. It is more preferable to contain a compound having 3 to 15 unsaturated bonds, and further preferably to contain a compound having 3 to 6 ethylenically unsaturated bonds.
From the viewpoint of developability, the cross-linking agent is particularly preferably a compound having two ethylenically unsaturated bonds.

Further, for example, the negative curable composition according to the present invention includes an ethylenically unsaturated bond-containing cross-linking agent, a cyclic ether group-containing cross-linking agent, an alkoxymethyl group-containing cross-linking agent, a methylol group-containing cross-linking agent, and a benzoxazoli. It is preferable to contain at least two kinds of cross-linking agents selected from the group consisting of cross-linking agents containing ru groups, and it is preferable to contain cross-linking agents containing ethylenically unsaturated bonds, cross-linking agents containing cyclic ether groups, cross-linking agents containing alkoxymethyl groups, and methylol. It is more preferable to contain at least two kinds of cross-linking agents selected from the group consisting of group-containing cross-linking agents, and the ethylenically unsaturated bond-containing cross-linking agent, the cyclic ether group-containing cross-linking agent, the alkoxymethyl group-containing cross-linking agent, and It is more preferable to include at least one cross-linking agent selected from the group consisting of methylol group-containing cross-linking agents.

Further, in the negative curable composition according to the present invention, a cross-linking agent having a radically polymerizable group in which the cross-linking reaction proceeds by the action of a radical as a cross-linking group and the cross-linking reaction proceed by the action of an acid as a cross-linking group. It is preferable to include a cross-linking agent having an acid cross-linking group. The radical is supplied by, for example, a photoradical polymerization initiator described later or a thermal radical polymerization initiator.
Further, the acid is supplied by, for example, a photoacid generator or a thermoacid generator, which will be described later.
Examples of the radically polymerizable group include the above-mentioned group having an ethylenically unsaturated bond, and examples of the acid crosslinkable group include the above-mentioned cyclic ether group, alkoxymethyl group, methylol group, benzoxazolyl group and the like. ..

[Ethylene unsaturated bond-containing cross-linking agent]
The negative curable composition of the present invention preferably contains an ethylenically unsaturated bond-containing cross-linking agent.
Examples of the group containing an ethylenically unsaturated bond in the ethylenically unsaturated bond-containing cross-linking agent include a vinyl group, an allyl group, a vinylphenyl group, and a (meth) acryloyl group.
Among these, the (meth) acryloyl group is preferable as the group containing the ethylenically unsaturated bond, and the (meth) acryloyl group is more preferable from the viewpoint of reactivity.
Further, the ethylenically unsaturated bond-containing cross-linking agent is preferably a compound having radical polymerization property.

The crosslinker containing an ethylenically unsaturated bond may be a compound having one or more ethylenically unsaturated bonds, but a compound having two or more ethylenically unsaturated bonds is more preferable.
The compound having two ethylenically unsaturated bonds is preferably a compound having two groups containing the above ethylenically unsaturated bonds.
Further, from the viewpoint of the film strength of the obtained cured film, the negative curable composition of the present invention may contain a compound having three or more ethylenically unsaturated bonds as an ethylenically unsaturated bond-containing cross-linking agent. preferable. As the compound having 3 or more ethylenically unsaturated bonds, a compound having 3 to 15 ethylenically unsaturated bonds is preferable, and a compound having 3 to 10 ethylenically unsaturated bonds is more preferable, and 3 to 6 compounds are more preferable. The compound having is more preferable.
The compound having 3 or more ethylenically unsaturated bonds is preferably a compound having 3 or more groups containing the ethylenically unsaturated bond, and more preferably a compound having 3 to 15 ethylenically unsaturated bonds. A compound having 3 to 10 is more preferable, and a compound having 3 to 6 is particularly preferable.
From the viewpoint of the film strength of the obtained cured film, the negative curable composition of the present invention comprises a compound having two ethylenically unsaturated bonds and a compound having three or more ethylenically unsaturated bonds. It is also preferable to include.

The molecular weight of the ethylenically unsaturated bond-containing cross-linking agent is preferably 2,000 or less, more preferably 1,500 or less, and even more preferably 900 or less. The lower limit of the molecular weight of the ethylenically unsaturated bond-containing cross-linking agent is preferably 100 or more.

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

Further, as the ethylenically unsaturated bond-containing cross-linking agent, a compound having a boiling point of 100 ° C. or higher under normal pressure is also preferable. Examples are polyethylene glycol di (meth) acrylate, trimethyl ethanetri (meth) acrylate, neopentyl glycol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol. Penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, hexanediol (meth) acrylate, trimethylpropantri (acryloyloxypropyl) ether, tri (acryloyloxyethyl) isocyanurate, glycerin, trimethylolethane, etc. A compound obtained by adding ethylene oxide or propylene oxide to a functional alcohol and then (meth) acrylated, is described in JP-A-48-041708, JP-A-50-006034, and JP-A-51-0371993. Urethane (meth) acrylates, such as those described in JP-A-48-064183, JP-A-49-043191, and JP-A-52-030490, the polyester acrylates, epoxy resins and (meth) acrylics. Examples thereof include polyfunctional acrylates and methacrylates such as epoxy acrylates which are reaction products with acids, and mixtures thereof. Further, the compounds described in paragraphs 0254 to 0257 of JP-A-2008-292970 are also suitable. Further, a polyfunctional (meth) acrylate obtained by reacting a polyfunctional carboxylic acid with a cyclic ether group such as glycidyl (meth) acrylate and a compound having an ethylenically unsaturated bond can also be mentioned.

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

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

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

Further, the compound described in Japanese Patent Application Laid-Open No. 10-062986 together with specific examples as formulas (1) and (2) after addition of ethylene oxide or propylene oxide to a polyfunctional alcohol and then (meth) acrylated is also used. It can be used as an ethylenically unsaturated bond-containing cross-linking agent.

Further, the compounds described in paragraphs 0104 to 0131 of JP-A-2015-187211 can also be used as the ethylenically unsaturated bond-containing cross-linking agent, and these contents are incorporated in the present specification.

Examples of the ethylenically unsaturated bond-containing cross-linking agent include dipentaerythritol triacrylate (commercially available KAYARAD D-330; manufactured by Nippon Kayaku Co., Ltd.) and dipentaerythritol tetraacrylate (commercially available KAYARAD D-320; Nippon Kayaku Co., Ltd., A-TMMT: Shin-Nakamura Chemical Industry Co., Ltd.), Dipentaerythritol penta (meth) acrylate (commercially available KAYARAD D-310; Nihon Kayaku Co., Ltd.), Di Pentaerythritol hexa (meth) acrylate (commercially available KAYARAD DPHA; manufactured by Nippon Kayaku Co., Ltd., A-DPH; manufactured by Shin-Nakamura Chemical Industry Co., Ltd.), and these (meth) acryloyl groups are ethylene glycol residues or propylene. A structure that is bound via a glycol residue is preferable. These oligomer types can also be used.

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

Examples of the ethylenically unsaturated bond-containing cross-linking agent are as described in JP-A-48-041708, JP-A-51-0371993, JP-A-02-032293, and JP-B-02-016765. Urethane acrylates and urethane compounds having an ethylene oxide-based skeleton described in Japanese Patent Publication No. 58-049860, Japanese Patent Publication No. 56-017654, Japanese Patent Publication No. 62-039417, and Japanese Patent Publication No. 62-039418 are also suitable. Is. Further, as an ethylenically unsaturated bond-containing cross-linking agent, an amino structure or a sulfide structure in the molecule described in JP-A-63-277653, JP-A-63-260909, and JP-A-01-105238. A compound having the above can also be used.

The ethylenically unsaturated bond-containing cross-linking agent may be an ethylenically unsaturated bond-containing cross-linking agent having an acid group such as a carboxy group or a phosphoric acid group. The ethylenically unsaturated bond-containing cross-linking agent having an acid group is preferably an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid, and a non-aromatic carboxylic acid anhydride is added to the unreacted hydroxy group of the aliphatic polyhydroxy compound. An ethylenically unsaturated bond-containing cross-linking agent which has been reacted to have an acid group is more preferable. Particularly preferably, in an ethylenically unsaturated bond-containing cross-linking agent in which an unreacted hydroxy group of an aliphatic polyhydroxy compound is reacted with a non-aromatic carboxylic acid anhydride to give an acid group, the aliphatic polyhydroxy compound is penta. A compound that is an erythritol or dipentaerythritol. Examples of commercially available products include M-510 and M-520 as polybasic acid-modified acrylic oligomers manufactured by Toagosei Co., Ltd.

The acid value of the ethylenically unsaturated bond-containing cross-linking agent having an acid group is preferably 0.1 to 40 mgKOH / g, and particularly preferably 5 to 30 mgKOH / g. When the acid value of the ethylenically unsaturated bond-containing cross-linking agent is within the above range, it is excellent in manufacturing handleability and further excellent in developability. Moreover, the polymerizability is good. From the viewpoint of the development speed in the case of alkaline development, the acid value of the ethylenically unsaturated bond-containing cross-linking agent having an acid group is preferably 0.1 to 300 mgKOH / g, and particularly preferably 1 to 100 mgKOH / g. The acid value is measured according to the description of JIS K 0070: 1992.

In the negative curable composition of the present invention, a monofunctional ethylenically unsaturated bond-containing cross-linking agent is preferably used as the ethylenically unsaturated bond-containing cross-linking agent from the viewpoint of suppressing warpage associated with controlling the elastic modulus of the cured film. it can. Examples of the monofunctional ethylenically unsaturated bond-containing cross-linking agent include n-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, butoxyethyl (meth) acrylate, and carbitol (meth). Acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, phenoxyethyl (meth) acrylate, N-methylol (meth) acrylamide, glycidyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate (Meta) acrylic acid derivatives such as, N-vinylpyrrolidone, N-vinyl compounds such as N-vinylcaprolactam, and allyl compounds such as allylglycidyl ether, diallyl phthalate, and triallyl trimellitate are preferably used. As the monofunctional ethylenically unsaturated bond-containing cross-linking agent, a compound having a boiling point of 100 ° C. or higher under normal pressure is also preferable in order to suppress volatilization before exposure.

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

The ethylenically unsaturated bond-containing cross-linking agent may be used alone or in combination of two or more. When two or more types are used in combination, the total amount is preferably in the above range.

[Methylol group-containing cross-linking agent, alkoxymethyl group-containing cross-linking agent]
The negative curable composition of the present invention preferably contains at least one cross-linking agent selected from the group consisting of a methylol group-containing cross-linking agent and an alkoxymethyl group-containing cross-linking agent.
As the methylol group-containing cross-linking agent or the alkoxymethyl group-containing cross-linking agent, for example, formaldehyde or formaldehyde and alcohol are reacted with an amino group-containing compound such as melamine, glycoluryl, urea, alkylene urea, and benzoguanamine, and the hydrogen atom of the amino group is described. Examples thereof include compounds having a structure in which the above is substituted with a methylol group or an alkoxymethyl group. The method for producing these compounds is not particularly limited, and any compound having the same structure as the compound produced by the above method may be used. Further, it may be an oligomer formed by self-condensing the methylol groups of these compounds.
As the above amino group-containing compound, the cross-linking agent using melamine is a melamine-based cross-linking agent, the cross-linking agent using glycoluril, urea or alkylene urea is a urea-based cross-linking agent, and the cross-linking agent using alkylene urea is an alkylene urea-based cross-linking agent. A cross-linking agent using an agent or benzoguanamine is called a benzoguanamine-based cross-linking agent.
Among these, the negative curable composition of the present invention preferably contains at least one compound selected from the group consisting of a urea-based cross-linking agent and a melamine-based cross-linking agent, and the glycoluril-based cross-linking agent and the glycol-based cross-linking agent described later are preferably contained. It is more preferable to contain at least one compound selected from the group consisting of melamine-based cross-linking agents.

Specific examples of the melamine-based cross-linking agent include hexamethoxymethylmelamine, hexaethoxymethylmelamine, hexapropoxymethylmelamine, hexabutoxybutyl melamine and the like.

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

Specific examples of the benzoguanamine-based cross-linking agent include monohydroxymethylated benzoguanamine, dihydroxymethylated benzoguanamine, trihydroxymethylated benzoguanamine, tetrahydroxymethylated benzoguanamine, monomethoxymethylated benzoguanamine, dimethoxymethylated benzoguanamine, and trimethoxymethylated benzoguanamine. , Tetramethoxymethylated benzoguanamine, monomethoxymethylated benzoguanamine, dimethoxymethylated benzoguanamine, trimethoxymethylated benzoguanamine, tetraethoxymethylated benzoguanamine, monopropoxymethylated benzoguanamine, dipropoxymethylated benzoguanamine, tripropoxymethylated benzoguanamine, tetrapropoxy Methylated benzoguanamine, monobutoxymethylated benzoguanamine, dibutoxymethylated benzoguanamine, tributoxymethylated benzoguanamine, tetrabutoxymethylated benzoguanamine and the like can be mentioned.

In addition, as the methylol group-containing cross-linking agent or the alkoxymethyl group-containing cross-linking agent, a compound in which at least one group selected from the group consisting of a methylol group and an alkoxymethyl group is directly bonded to an aromatic ring (preferably a benzene ring) is also preferable. Used for.
Specific examples of such compounds include benzenedimethanol, bis (hydroxymethyl) cresol, bis (hydroxymethyl) dimethoxybenzene, bis (hydroxymethyl) diphenyl ether, bis (hydroxymethyl) benzophenone, and hydroxymethylphenyl hydroxymethylbenzoate. , Bis (hydroxymethyl) biphenyl, dimethylbis (hydroxymethyl) biphenyl, bis (methoxymethyl) benzene, bis (methoxymethyl) cresol, bis (methoxymethyl) dimethoxybenzene, bis (methoxymethyl) diphenyl ether, bis (methoxymethyl) Benzenephenone, methoxymethylphenyl methoxymethylbenzoate, bis (methoxymethyl) biphenyl, dimethylbis (methoxymethyl) biphenyl, 4,4', 4''-ethylidentris [2,6-bis (methoxymethyl) phenol], 5 , 5'-[2,2,2-trifluoro-1- (trifluoromethyl) ethylidene] bis [2-hydroxy-1,3-benzenedimethanol], 3,3', 5,5'-tetrakis ( Methoxymethyl) -1,1'-biphenyl-4,4'-diol and the like can be mentioned.

Commercially available products may be used as the methylol group-containing cross-linking agent or the alkoxymethyl group-containing cross-linking agent, and suitable commercially available products include 46DMOC, 46DMOEP (all manufactured by Asahi Organic Materials Industry Co., Ltd.), DML-PC, and DML-. PEP, DML-OC, DML-OEP, DML-34X, DML-PTBP, DML-PCHP, DML-OCHP, DML-PFP, DML-PSBP, DML-POP, DML-MBOC, DML-MBPC, DML-MTrisPC, DML-BisOC-Z, DML-BisOCHP-Z, DML-BPC, DMLBisOC-P, DMOM-PC, DMOM-PTBP, DMOM-MBPC, TriML-P, TriML-35XL, TML-HQ, TML-BP, TML- pp-BPF, TML-BPE, TML-BPA, TML-BPAF, TML-BPAP, TMOM-BP, TMOM-BPE, TMOM-BPA, TMOM-BPAF, TMOM-BPAP, HML-TPPHBA, HML-TPHAP, HMOM- TPPHBA, HMOM-TPHAP (above, manufactured by Honshu Kagaku Kogyo Co., Ltd.), Nicarac (registered trademark, the same applies hereinafter) MX-290, Nicarac MX-280, Nicarac MX-270, Nicarac MX-279, Nicarac MW-100LM, Nicarac MX- 750LM (above, manufactured by Sanwa Chemical Co., Ltd.) and the like can be mentioned.

When the negative curable composition of the present invention contains a methylol group-containing cross-linking agent or an alkoxymethyl group-containing cross-linking agent, the content thereof is 0.1 to 0.1 to the total solid content of the negative curable composition of the present invention. It is preferably 30% by mass, more preferably 0.1 to 20% by mass, further preferably 0.5 to 15% by mass, and particularly preferably 1.0 to 10% by mass. .. Only one type of the methylol group-containing cross-linking agent or the alkoxymethyl group-containing cross-linking agent may be contained, or two or more types may be contained. When two or more kinds of a methylol group-containing cross-linking agent or an alkoxymethyl group-containing cross-linking agent are contained, the total thereof is preferably in the above range.

[Cyclic ether group-containing cross-linking agent]
The negative curable composition of the present invention preferably contains a cyclic ether group-containing cross-linking agent.
As the cyclic ether group-containing cross-linking agent, a cross-linking agent having an epoxy group as a cyclic ether group (epoxide compound) or a cross-linking agent having an oxetanyl group as a cyclic ether group (oxetanyl compound) is preferable.

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

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

Examples of epoxy compounds include bisphenol A type epoxy resin; bisphenol F type epoxy resin; propylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, ethylene glycol diglycidyl ether, butylene glycol diglycidyl ether, hexamethylene glycol diglycidyl ether. , Trimethylol propantriglycidyl ether and other alkylene glycol type epoxy resins or polyhydric alcohol hydrocarbon type epoxy resins; polypropylene glycol diglycidyl ether and other polyalkylene glycol type epoxy resins; polymethyl (glycidyloxypropyl) siloxane and other epoxy groups Examples include, but are not limited to, containing silicones. Specifically, Epicron® 850-S, Epicron® HP-4032, Epicron® HP-7200, Epicron® HP-820, Epicron® HP-4700, Epicron® EXA-4710, Epicron® HP-4770, Epicron® EXA-859CRP, Epicron® EXA-1514, Epicron® EXA-4880, Epicron® EXA-4850-150, Epicron EXA-4850-1000, Epicron (registered trademark) EXA-4816, Epicron (registered trademark) EXA-4822 (trade name, manufactured by DIC Co., Ltd.), Rica Resin (registered trademark) BEO-60E (Product name, Shin Nihon Rika Co., Ltd.), EP-4003S, EP-4000S (trade name, manufactured by ADEKA Co., Ltd.), Serokiside 2021P, 2081, 2000, 3000, EHPE3150, Epolide GT400, Servinus B0134, B0177 ( Product name, manufactured by Daicel Co., Ltd.), NC-3000, NC-3000-L, NC-3000-H, NC-3000-FH-75M, NC-3100, CER-3000-L, NC-2000-L , XD-1000, NC-7000L, NC-7300L, EPPN-501H, EPPN-501HY, EPPN-502H, EOCN-1020, EOCN-102S, EOCN-103S, EOCN-104S, CER-1020, EPPN-201, BREN -S, BREN-10S (trade name, manufactured by Nippon Kayaku Co., Ltd.), Denacol EX-211, EX-212, EX-252, EX-810, EX-811, EX-850, EX-851, EX -821, EX-830, EX-832, EX-841, EX-861, EX-920, EX-931, EX-313, EX-314, EX-321, EX-411, EX-421, EX-512 , EX-521, EX-621, EX-614, EX-614B, EX-201, EX-711, EX-721, EX-121, EX-145, EX-171, EX-192, EX-141, EX -146, EX-147 and the like can be mentioned.

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

When the negative curable composition of the present invention contains a cyclic ether group-containing cross-linking agent, the content thereof shall be 0.1 to 30% by mass with respect to the total solid content of the negative curable composition of the present invention. Is more preferable, 0.1 to 20% by mass is more preferable, 0.5 to 15% by mass is further preferable, and 1.0 to 10% by mass is particularly preferable. Only one type of the cyclic ether group-containing cross-linking agent may be contained, or two or more types may be contained. When two or more kinds of cyclic ether group-containing cross-linking agents are contained, the total is preferably in the above range.

[Benzodiazepine group-containing cross-linking agent]
The negative curable composition of the present invention may contain a benzoxazolyl group-containing cross-linking agent.
The benzoxazolyl group-containing cross-linking agent is preferable because it is a cross-linking reaction derived from a ring-opening addition reaction, so that degassing does not occur during curing, and heat shrinkage is further reduced to suppress warpage.

Preferred examples of the benzoxazolyl group-containing cross-linking agent include BA-type benzoxazine, B-m-type benzoxazine (trade name, manufactured by Shikoku Kasei Kogyo Co., Ltd.), and a benzoxazine adduct of a polyhydroxystyrene resin. Examples thereof include phenol novolac type dihydrobenzoxazine compounds. These may be used alone or in combination of two or more.

When the negative curable composition of the present invention contains a benzoxazolyl group-containing cross-linking agent, the content thereof is 0.1 to 30% by mass based on the total solid content of the negative photosensitive composition of the present invention. It is preferably 0.1 to 20% by mass, further preferably 0.5 to 15% by mass, and particularly preferably 1.0 to 10% by mass. Only one type of benzoxazolyl group-containing cross-linking agent may be contained, or two or more types may be contained. When two or more kinds of benzoxazolyl group-containing cross-linking agents are contained, the total is preferably in the above range.

<Specific silane coupling agent>
In the negative curable composition of the present invention, between an alkoxy group e-1 directly bonded to a silicon atom and a group different from the above e-1 and at least one of the plurality of types of cross-linking agents. Includes a silane coupling agent (specific silane coupling agent) having a group e-2 capable of covalently bonding to.

[Alkoxy group e-1 directly bonded to a silicon atom]
The specific silane coupling agent may have only one alkoxy group e-1 directly bonded to the silicon atom or may have two or more alkoxy groups, but the obtained cured film may have chemical resistance and elongation at break. From the viewpoint of the above, it is preferable to have two or more, more preferably two or three, and further preferably three.
As the alkoxy group in e-1, an alkoxy group having 1 to 10 carbon atoms is preferable, an alkoxy group having 1 to 4 carbon atoms is more preferable, and a methoxy group or an ethoxy group is more preferable.
The specific silane coupling agent preferably contains a monoalkoxysilyl group, a dialkoxysilyl group, or a trialkoxysilyl group as the group containing the above e-1, and preferably contains a dialkoxysilyl group or a trialkoxysilyl group. Is more preferable, and it is further preferable to contain a trialkoxysilyl group.
The alkoxy group contained in the monoalkoxysilyl group, the dialkoxysilyl group, or the trialkoxysilyl group corresponds to the alkoxy group e-1.
Further, the two hydrogen atoms contained in the monoalkoxysilyl group or one hydrogen atom contained in the dialkoxysilyl group may be independently substituted with a group having e-2, which will be described later. , May be substituted with other known substituents.

Further, the specific silane coupling agent may have only one silicon atom or may have two or more silicon atoms, but it is preferable that the specific silane coupling agent has only one silicon atom.
When it has two or more silicon atoms, the above-mentioned alkoxy group e-1 may be bonded to at least one silicon atom, and the above-mentioned alkoxy group e-1 may be bonded to all silicon atoms.

[Group e-2 that can form a covalent bond with a cross-linking agent]
e-2 is not particularly limited as long as it is a group capable of covalently forming a covalent bond with at least one of the above-mentioned plurality of types of cross-linking agents, but is included in at least one of the above-mentioned plurality of types of cross-linking agents. It is preferably a group that can form a covalent bond with the group. That is, it is preferable that the group forms a covalent bond with the crosslinkable group of the crosslinking agent.
Examples of e-2 include a group containing an ethylenically unsaturated bond, a cyclic ether group, an alkoxymethyl group, a carboxy group, an amino group, a hydroxy group, a mercapto group, an acid anhydride group, an isocyanate group, a blocked isocyanate group and the like. , A group containing an ethylenically unsaturated bond, a cyclic ether group, or a carboxy group is preferable.
Examples of the group containing an ethylenically unsaturated bond include a vinyl group, an allyl group, a vinylphenyl group, a (meth) acryloyl group, and the like, a (meth) acryloyl group is preferable, and a (meth) group is preferable from the viewpoint of reactivity. Acryloyl groups are more preferred.
The group containing an ethylenically unsaturated bond is, for example, a group capable of covalently forming a covalent bond with a group containing an ethylenically unsaturated bond contained in an ethylenically unsaturated bond-containing cross-linking agent.
The alkoxymethyl group, carboxy group, amino group, hydroxy group, mercapto group, acid anhydride group, isocyanate group, or blocked isocyanate group is, for example, the cyclic ether group in the cyclic ether group-containing compound and the alkoxymethyl group-containing. It is a group that can form a covalent bond with the alkoxymethyl group contained in the compound or the methylol group contained in the methylol group-containing compound.

The specific silane coupling agent may have 1 or more e-2, and may have 2 or more.
e-2 may be directly bonded to the specific silane coupling agent or may be bonded via a linking group, but it is preferably bonded via a linking group. The linking group is not particularly limited, and an aliphatic hydrocarbon group, an aromatic hydrocarbon group, -O-, -C (= O)-, -S-, -S (= O) _2- , -NR ^N- , Or a group represented by a combination of these, an aliphatic hydrocarbon group, an aromatic hydrocarbon group, or an aliphatic hydrocarbon group, an aromatic hydrocarbon group, -O-, -C (=). A group represented by a combination of O)-,-S-, -S (= O) _2- , -NR ^{N- is preferable.} The ^RN represents a hydrogen atom or a hydrocarbon group, and a hydrogen atom is preferable.

Examples of preferred embodiments of the negative curable composition of the present invention are shown in (1) to (3) below. (1) An ethylenically unsaturated bond-containing cross-linking agent is included as one of the above-mentioned plurality of kinds of cross-linking agents. And, as e-2, a specific silane coupling agent having a group containing an ethylenically unsaturated bond is contained. (2) A cyclic ether group-containing cross-linking agent and an alkoxymethyl group-containing cross-linking agent are contained as one of the above-mentioned plurality of types of cross-linking agents. It contains at least one cross-linking agent selected from the group consisting of a cross-linking agent and a methylol group-containing cross-linking agent, and as e-2, contains a specific silane coupling agent having a group containing a cyclic ether group (3). ) One of the above-mentioned plurality of types of cross-linking agents contains at least one cross-linking agent selected from the group consisting of a cyclic ether group-containing cross-linking agent, an alkoxymethyl group-containing cross-linking agent, and a methylol group-containing cross-linking agent, and , E-2 contains a specific silane coupling agent having a group containing a carboxy group.

[Equation (S-1)]
The specific silane coupling agent of the present invention preferably has a structure represented by the following formula (S-1).

Wherein (S1), E ¹ represents an alkoxy group, L ^S1 represents n + 1 valent linking group, E ² can result in covalent bonds between at least one of the plurality of types of crosslinking agent represents a group, n represents an integer of 1 or more, R ^S1 represents a substituent, a is an integer of 1 or more, b represents an integer of 1 or more, c is an integer of 0 or more, a, The sum of b and c is 4.

In the formula (S-1), E ¹ is a group corresponding to the above-mentioned e-1, preferably an alkoxy group having 1 to 10 carbon atoms, more preferably an alkoxy group having 1 to 4 carbon atoms, and a methoxy group or an ethoxy group. Groups are more preferred.
In the formula (S-1), a is preferably 1, 2 or 3, more preferably 2 or 3, and even more preferably 3.

In the formula (S-1), E ² is a group corresponding to the above-mentioned e-2, and is a group containing an ethylenically unsaturated bond, a cyclic ether group, an alkoxymethyl group, a methylol group, a carboxy group, an amino group, and a hydroxy group. A group, a mercapto group, an acid anhydride group, an isocyanate group, and a blocked isocyanate group are preferable, and a group containing an ethylenically unsaturated bond, a cyclic ether group, or a carboxy group is more preferable.
In the formula (S-1), n is preferably an integer of 1 to 4, more preferably 1 or 2, and even more preferably 1.
In formula (S-1), ^LS1 is an aliphatic hydrocarbon group, an aromatic hydrocarbon group, -O-, -C (= O)-, -S-, -S (= O) _2- , -NR. ^{A group represented by N-} or a combination thereof is preferable, and an aliphatic hydrocarbon group, an aromatic hydrocarbon group, or an aliphatic hydrocarbon group, an aromatic hydrocarbon group, -O-, -C (=) More preferably, a group represented by a combination of O)-, -S-, -S (= O) _2- ^{, -NR N-.} The ^RN represents a hydrogen atom or a hydrocarbon group, and a hydrogen atom is preferable.
In the formula (S-1), b is preferably 1 or 2, and more preferably 1.

Wherein (S1), R ^S1 represents a substituent, may be used without any particular limitation known substituents in the field of the silane coupling agent is preferably an alkyl group or an aromatic hydrocarbon group ..
In the formula (S-1), c is preferably 0, 1 or 2, and more preferably 0.

[Molecular weight]
The molecular weight of the specific silane coupling agent is preferably 100 to 2,000, more preferably 150 to 1,000.

〔Concrete example〕
Specific silane coupling agents include 3-acryloxypropyltrimethoxysilane, 3-acryloxypropyltriethoxysilane, 3-acryloxypropylmethyldimethoxysilane, 3-acryloxypropylmethyldiethoxysilane, and 3-methacryloxypropyl. Trimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, allyltrimethoxysilane, allyltriethoxy Silane, Trimethoxy (4-vinylphenyl) silane, Triethoxy (4-vinylphenyl) silane, 3-acrylamidepropyltrimethoxysilane, 3-acrylamidepropyltriethoxysilane, 3-acrylamidepropylmethyldimethoxysilane, 3-acrylamidepropylmethyldi Ethoxysilane, 3-methacrylamidopropyltrimethoxysilane, 3-methacrylamidepropyltriethoxysilane, 3-methacrylamidopropylmethyldimethoxysilane, 3-methacrylamidepropylmethyldiethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, N- (3- (triethoxysilyl) propyl) maleeamide acid, N- (3- (triethoxysilyl) silyl) ) Propyl) phthalamic acid, benzophenone-3,3'-bis (N- (3-triethoxysilyl) propylamide) -4,4'-dicarboxylic acid, N-2- (aminoethyl) -3-aminopropylmethyl Dimethoxysilane, N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N- (1,3-dimethyl) -Buchilidene) Propylamine, N-phenyl-3-aminopropyltrimethoxysilane, N- (vinylbenzyl) -2-aminoethyl-3-aminopropyltrimethoxysilane hydrochloride, hydroxymethyltrimethoxysilane, hydroxyethyltri Methoxysilane, (3- (N, N-dihydroxyethylamino) propyl) trimethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopro Examples thereof include pyrtrimethoxysilane, 3-trimethoxysilylpropyl succinate anhydride, and 3-isocyanatepropyltriethoxysilane.
As the specific silane coupling agent, a commercially available product may be used, and as the commercially available product, KBM-1003, KBE-1003, KBM-303, KBM-402, KBM-403, KBE-402, KBE-403, KBM-1403, KBM-502, KBM-503, KBE-502, KBE-503, KBM-5103, KBM-602, KBM-603, KBM-903, KBE-903, KBE-9103P, KBM-573, KBM- 575, KBM-9569, KBE-585, KBM-802, KBM-803, KBE-9007N, X-12-967C (manufactured by Shin-Etsu Silicone Co., Ltd.), DOWNSIL® series, XIAMETER series (above, Dow Toray Co., Ltd.), Silane Ace (registered trademark) series (JNC Co., Ltd.) and the like can be mentioned.

〔Content〕
The content of the specific silane coupling agent is preferably 0.1 to 30% by mass, preferably 0.5 to 15% by mass, based on the total solid content of the negative curable composition of the present invention. More preferably, it is more preferably 0.5 to 5% by mass.
The negative curable composition of the present invention may contain only one specific silane coupling agent, or may contain two or more of them. When two or more kinds are contained, the total is preferably in the above range.

<Silane coupling agents other than specific silane coupling agents>
The negative curable composition of the present invention may further contain a silane coupling agent other than the specific silane coupling agent.
As another silane coupling agent, a group e-2 which has an alkoxy group e-1 directly bonded to a silicon atom and can form a covalent bond with at least one of the above-mentioned plurality of types of cross-linking agents. Examples include silane coupling agents that do not have.
Examples of other silane coupling agents include silane coupling agents having a ring structure such as an imidazole structure and an alkoxysilyl group, and silane coupling agents having an alkylamide structure such as N-trimethylsilylacetamide and an alkoxysilyl group. ..

〔Content〕
When the negative curable composition of the present invention contains another silane coupling agent, the content of the other silane coupling agent is 0.1 with respect to the total solid content of the negative curable composition of the present invention. It is preferably about 30% by mass, more preferably 0.5 to 15% by mass, and even more preferably 0.5 to 5% by mass.
The negative curable composition of the present invention may contain only one type of other silane coupling agent, or may contain two or more types of other silane coupling agents. When two or more kinds are contained, the total is preferably in the above range.

<Radical generator>
The negative curable composition of the present invention preferably contains a radical generator.
As the radical generator, a photoradical generator or a thermal radical generator is preferable, and a photoradical generator is more preferable.
Further, as the radical generator, a radical generator having an oxime structure is preferable, and a photoradical generator having an oxime structure is more preferable.

[Photo radical generator]
The photoradical generator is not particularly limited, and for example, a compound known as a photoradical polymerization initiator can be appropriately selected. For example, a photoradical polymerization initiator having photosensitivity to light rays in the ultraviolet region to the visible region is preferable. Further, it may be an activator that produces an active radical by causing some action with the photoexcited sensitizer.

The photoradical generator is at least one compound having a molar extinction coefficient of ^{at least about 50 L · mol -1} · cm ^-1 with respect to light having a wavelength in the range of about 300 to 800 nm (preferably 330 to 500 nm). It is preferably contained. The molar extinction coefficient of a compound can be measured using a known method. For example, it is preferable to measure at a concentration of 0.01 g / L using an ethyl acetate solvent with an ultraviolet-visible spectrophotometer (Cary-5 spectrophotometer manufactured by Varian).

As the photoradical generator, a known compound can be arbitrarily used. For example, halogenated hydrocarbon derivatives (for example, compounds having a triazine skeleton, compounds having an oxadiazole skeleton, compounds having a trihalomethyl group, etc.), acylphosphine compounds such as acylphosphine oxide, hexaarylbiimidazole, oxime derivatives and the like. Oxime compounds, organic peroxides, thio compounds, ketone compounds, aromatic onium salts, ketooxime ethers, aminoacetophenone compounds, hydroxyacetophenones, azo compounds, azide compounds, metallocene compounds, organic boron compounds, iron arene complexes, etc. Can be mentioned. For details thereof, the description of paragraphs 0165 to 0182 of JP2016-027357 and paragraphs 0138 to 0151 of International Publication No. 2015/199219 can be referred to, and the contents thereof are incorporated in the present specification.

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

As the photoradical generator, a hydroxyacetophenone compound, an aminoacetophenone compound, and an acylphosphine compound can also be preferably used. More specifically, for example, the aminoacetophenone-based initiator described in JP-A-10-291969 and the acylphosphine oxide-based initiator described in Japanese Patent No. 4225898 can also be used.

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

As the aminoacetophenone-based initiator, commercially available products IRGACURE 907, IRGACURE 369, and IRGACURE 379 (trade names: all manufactured by BASF), Omnirad 907, Omnirad 369, and Omnirad 379 (all manufactured by IGM Resin). ) Can be used.

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

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

Examples of the metallocene compound include IRGACURE-784 (manufactured by BASF).

Examples of the photoradical generator include a photoradical generator (oxime compound) having an oxime structure. By using the oxime compound, the exposure latitude can be improved more effectively. The oxime compound is particularly preferable because it has a wide exposure latitude (exposure margin) and also acts as a photocuring accelerator.

As specific examples of the oxime compound, the compound described in JP-A-2001-233842, the compound described in JP-A-2000-080068, and the compound described in JP-A-2006-342166 can be used.

Preferred oxime compounds include, for example, compounds having the following structures, 3-benzoyloxyiminobutane-2-one, 3-acetoxyiminobutane-2-one, 3-propionyloxyiminobutane-2-one, 2-acetoxy. Iminopentan-3-one, 2-acetoxyimino-1-phenylpropan-1-one, 2-benzoyloxyimino-1-phenylpropane-1-one, 3- (4-toluenesulfonyloxy) iminobutane-2-one , And 2-ethoxycarbonyloxyimino-1-phenylpropan-1-one and the like. In the negative curable composition of the present invention, it is particularly preferable to use an oxime compound (oxime-based photoradical generator) as the photoradical generator. The oxime compound, which is a photoradical generator, has a linking group represented by> C = NOC (= O)-in the molecule.

As commercially available products, IRGACURE OXE 01, IRGACURE OXE 02 (above, manufactured by BASF), and ADEKA PUTMER N-1919 (manufactured by ADEKA Corporation, Photoradical Polymerization Initiator 2) described in JP2012-014502A are also suitable. Used for. Further, TR-PBG-304 (manufactured by Changzhou Powerful Electronics New Materials Co., Ltd.), Adeka Arkuru's NCI-831 and Adeka Arkuru's NCI-930 (manufactured by ADEKA Corporation) can also be used. Further, DFI-091 (manufactured by Daito Chemix Co., Ltd.) can be used.

The following compounds can also be used.

It is also possible to use an oxime compound having a fluorine atom. Specific examples of such an oxime compound include compounds described in JP-A-2010-262028, compounds 24, 36-40 described in paragraph 0345 of JP-A-2014-500852, and JP-A-2013. Examples thereof include the compound (C-3) described in paragraph 0101 of JP-A-164471.

Examples of the most preferable oxime compound include an oxime compound having a specific substituent shown in JP-A-2007-269779 and an oxime compound having a thioaryl group shown in JP-A-2009-191061.

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

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

The photoradical generator is N, N'-tetraalkyl-4,4'-diaminobenzophenone, 2-benzyl-, such as benzophenone, N, N'-tetramethyl-4,4'-diaminobenzophenone (Michler ketone). 2-Dimethylamino-1- (4-morpholinophenyl) -butanone-1,2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-propanone-1 and other aromatic ketones, alkylanthraquinone and the like Kinones fused with an aromatic ring, benzoin ether compounds such as benzoin alkyl ether, benzoin compounds such as benzoin and alkyl benzoin, and benzyl derivatives such as benzyl dimethyl ketal can also be used. Further, a compound represented by the following formula (I) can also be used.

In formula (I), ^RI00 is an alkyl group having 1 to 20 carbon atoms, an alkyl group having 2 to 20 carbon atoms interrupted by one or more oxygen atoms, an alkoxy group having 1 to 12 carbon atoms, a phenyl group, and the like. Alkyl group with 1 to 20 carbon atoms, alkoxy group with 1 to 12 carbon atoms, halogen atom, cyclopentyl group, cyclohexyl group, alkenyl group with 2 to 12 carbon atoms, carbon number 2 to 2 interrupted by one or more oxygen atoms 18 alkyl group and at least one substituted phenyl group of the alkyl group having 1 to 4 carbon atoms, or biphenyl, R ^I01 is a group represented by formula (II), the same as R ^I00 The groups, R ^I02 to R ^I04, are independently alkyls having 1 to 12 carbon atoms, alkoxy groups having 1 to 12 carbon atoms, or halogens, respectively.

In the formula, R ^I05 to R ^I07 are the same as ^{R I 02} to R I ⁰⁴ of the above formula (I).

Further, as the photoradical generator, the compounds described in paragraphs 0048 to 0055 of International Publication No. 2015/1254669 can also be used.

The content of the photoradical generator is preferably 0.1 to 30% by mass, more preferably 0.1 to 20% by mass, based on the total solid content of the negative curable composition of the present invention. It is more preferably 0.5 to 15% by mass, and even more preferably 1.0 to 10% by mass. Only one type of photoradical generator may be contained, or two or more types may be contained. When two or more kinds of photoradical generators are contained, the total is preferably in the above range.

[Thermal radical generator]
The negative curable composition of the present invention may further contain a thermal radical generator.
A thermal radical generator is a compound that generates radicals by heat energy to initiate or accelerate the polymerization reaction of a polymerizable compound. By adding a thermal radical generator, the radical polymerization reaction further proceeds during heating, so that the crosslink density may be further improved.

Specific examples of the thermal radical generator include the compounds described in paragraphs 0074 to 0118 of JP-A-2008-063554.

When a thermal radical generator is contained, the content thereof is preferably 0.1 to 30% by mass, more preferably 0.1 to 20% by mass, based on the total solid content of the negative curable composition of the present invention. %, More preferably 5 to 15% by mass. Only one type of thermal radical generator may be contained, or two or more types may be contained. When two or more types of thermal radical generators are contained, the total is preferably in the above range.

<Acid generator>
The negative curable composition of the present invention preferably contains an acid generator.
As the acid generator, a thermoacid generator or a photoacid generator is preferable, and a thermoacid generator is more preferable.

[Thermal acid generator]
The thermal acid generator has the effect of generating an acid by heating and accelerating the cross-linking reaction of the above-mentioned cyclic ether group-containing cross-linking agent, alkoxymethyl group-containing cross-linking agent, methylol group-containing cross-linking agent and the like.
In addition, dehydration condensation of the alkoxy group (e-1) in the specific silane coupling agent may be promoted.

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

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

Of these, those that generate alkylsulfonic acid having 1 to 4 carbon atoms or haloalkylsulfonic acid having 1 to 4 carbon atoms are more preferable, and methanesulfonic acid is more preferable, from the viewpoint that there is little residue in the organic film and it is difficult to deteriorate the physical properties of the organic film. (4-Hydroxyphenyl) dimethylsulfonium, methanesulfonic acid (4-((methoxycarbonyl) oxy) phenyl) dimethylsulfonium, benzyl methanesulfonate (4-hydroxyphenyl) methylsulfonium, benzyl methanesulphonate (4-((methoxycarbonyl)) Carbonyl) oxy) phenyl) methylsulfonium, methanesulfonic acid (4-hydroxyphenyl) methyl ((2-methylphenyl) methyl) sulfonium, trifluoromethanesulfonic acid (4-hydroxyphenyl) dimethylsulfonium, trifluoromethanesulfonic acid (4-) ((Methoxycarbonyl) oxy) phenyl) dimethylsulfonium, benzyl (4-hydroxyphenyl) methylsulfonium trifluoromethanesulfonate, benzyl trifluoromethanesulfonate (4-((methoxycarbonyl) oxy) phenyl) methylsulfonium, trifluoromethanesulfonic acid (4-Hydroxyphenyl) methyl ((2-methylphenyl) methyl) sulfonium, 3-(5-(((propylsulfonyl) oxy) imino) thiophen-2 (5H) -iriden) -2- (o-tolyl) Propanenitrile, 2,2-bis (3- (methanesulfonylamino) -4-hydroxyphenyl) hexafluoropropane is preferred as the thermoacid generator.

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

[Neutralized salt type thermoacid generator]
From the viewpoint of the pot life of the negative curable composition, the negative curable composition of the present invention preferably contains a neutralized salt-type thermoacid generator.
As used herein, the pot life of a negative curable composition refers to viscosity stability when the composition is stored in the state of the composition without forming a cured film.
By including a neutralized salt type thermoacid generator as the thermoacid generator, a negative type curable composition having excellent pot life can be obtained.
This is because when a neutralized salt type thermoacid generator is used, for example, even if an acid is generated once during storage, a neutralized salt is formed again and the progress of cross-linking of the cross-linking agent during storage is suppressed. It is presumed that this is because it is done.

The neutralized salt type thermoacid generator may be any thermoacid generator having a neutralized salt structure, and is preferably a thermoacid generator having an organic salt structure.
The neutralized salt structure refers to a structure having an acid-derived anion structure and a base-derived cation structure.
In the neutralized salt type thermoacid generator, the anion structure is not particularly limited, and for example, aryl sulfonic acid such as p-toluene sulfonic acid, benzene sulfonic acid, dodecyl benzene sulfonic acid, methane sulfonic acid, ethane sulfonic acid, The structure is preferably derived from an alkyl sulfonic acid such as butane sulfonic acid, or a haloalkyl sulfonic acid such as trifluoromethane sulfonic acid, and more preferably a structure derived from aryl sulfonic acid or haloalkyl sulfonic acid.
Examples of the cation include a cation derived from an organic compound, a cation derived from a metal, and the like, and a cation derived from an organic compound is preferable, and a cation derived from an amine compound or a quaternary ammonium compound is more preferable.
Among these, the cation is preferably a cation represented by the following formula (C-1) or the following formula (C-2).

In formula (C-1), ^RC11 to ^RC13 independently represent a hydrogen atom or a monovalent substituent.
In formula (C-2), ^RC21 to ^RC24 each independently represent a monovalent substituent.

In the formula (C-1), ^RC11 to ^RC13 each independently preferably represent a hydrocarbon group, and more preferably an alkyl group or an aromatic hydrocarbon group.
In the formula (C-2), ^RC21 to ^RC24 each independently preferably represent a hydrocarbon group, and more preferably an alkyl group or an aromatic hydrocarbon group. Further, ^{at least one of RC21} to ^RC24 preferably represents an aromatic hydrocarbon group.

As the neutralized salt type thermal acid generator, a commercially available product may be used, and examples of the commercially available product include the K-PURE (registered trademark) series. Among these, the K-PURE (registered trademark) TAG -2179, TAG-2172, TAG-2713, TAG-2678, TAG-2679 and the like.

When a thermoacid generator is contained, the content thereof is preferably 0.1 to 30% by mass, more preferably 0.1 to 20% by mass, based on the total solid content of the negative curable composition. It is preferably 2 to 15% by mass, more preferably 2 to 15% by mass. Only one type of thermoacid generator may be contained, or two or more types may be contained. When two or more types of thermoacid generators are contained, the total is preferably in the above range.

[Photoacid generator]
The negative curable composition of the present invention may contain a photoacid generator.
The photoacid generator is not particularly limited as long as it generates an acid by exposure, but is an onium salt compound such as a quinonediazide compound, a diazonium salt, a phosphonium salt, a sulfonium salt, or an iodonium salt, an imide sulfonate, and an oxime. Examples thereof include sulfonate compounds such as sulfonate, diazodisulfone, disulfone, and o-nitrobenzyl sulfonate.

Examples of the quinone diazide compound include the compounds described in paragraphs 0061 to 0063 of International Publication No. 2017/217292.

Examples of the onium salt compound or the sulfonate compound include the compounds described in paragraphs 0064 to 0122 of JP-A-2008-013646.
In addition, a commercially available product may be used as the photoacid generator. Commercially available products include WPAG-145, WPAG-149, WPAG-170, WPAG-199, WPAG-336, WPAG-376, WPAG-370, WPAG-469, WPAG-638, and WPAG-699. (Manufactured by Kojunyaku Co., Ltd.) and the like.

When the photoacid generator is contained, the content thereof is preferably 0.1 to 30% by mass, more preferably 0.1 to 20% by mass, based on the total solid content of the negative type curable. It is more preferably 2 to 15% by mass. Only one type of photoacid generator may be contained, or two or more types may be contained. When two or more photoacid generators are contained, the total is preferably in the above range.

<Solvent>
The negative curable composition of the present invention preferably contains a solvent. As the solvent, a known solvent can be arbitrarily used. The solvent is preferably an organic solvent. Examples of the organic solvent include compounds such as esters, ethers, ketones, aromatic hydrocarbons, sulfoxides, and amides.

Examples of esters include ethyl acetate, -n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, γ-butyrolactone, ε-caprolactone. , Δ-Valerolactone, alkylalkyloxyacetate (eg, methyl alkyloxyacetate, ethyl alkyloxyacetate, butyl alkyloxyacetate (eg, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, etc.) )), 3-alkyloxypropionate alkyl esters (eg, methyl 3-alkyloxypropionate, ethyl 3-alkyloxypropionate, etc. (eg, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, 3-) Methyl ethoxypropionate, ethyl 3-ethoxypropionate, etc.)), 2-alkyloxypropionate alkyl esters (eg, methyl 2-alkyloxypropionate, ethyl 2-alkyloxypropionate, propyl 2-alkyloxypropionate) Etc. (eg, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate), 2-alkyloxy-2-methylpropionate, etc. Methyl acid and ethyl 2-alkyloxy-2-methylpropionate (eg, methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, etc.), methyl pyruvate, ethyl pyruvate, pyruvin Suitable examples include propyl acid acid, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutate, ethyl 2-oxobutate and the like.

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

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

As the aromatic hydrocarbons, for example, toluene, xylene, anisole, limonene and the like are preferable.

As sulfoxides, for example, dimethyl sulfoxide is preferable.

As the amides, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide and the like are preferable.

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

In the present invention, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, methyl 3-methoxypropionate, 2-heptanone, cyclohexanone, cyclopentanone, γ- Consists of one solvent selected from butyrolactone, dimethyl sulfoxide, ethyl carbitol acetate, butyl carbitol acetate, N-methyl-2-pyrrolidone, propylene glycol methyl ether, and propylene glycol methyl ether acetate, or two or more. The mixed solvent to be mixed is preferable. The combined use of dimethyl sulfoxide and γ-butyrolactone is particularly preferred.

From the viewpoint of coatability, the content of the solvent is preferably such that the total solid content concentration of the negative curable composition of the present invention is 5 to 80% by mass, and is preferably 5 to 75% by mass. It is more preferable that the amount is 10 to 70% by mass, and more preferably 40 to 70% by mass. The solvent content may be adjusted according to the desired thickness of the coating film and the coating method.

Only one type of solvent may be contained, or two or more types may be contained. When two or more kinds of solvents are contained, the total is preferably in the above range.

<Compound having at least one structure selected from the group consisting of a sulfonamide structure and a thiourea structure>
From the viewpoint of improving the adhesion of the obtained cured film to the substrate, the negative curable composition of the present invention comprises a compound having at least one structure selected from the group consisting of a sulfonamide structure and a thiourea structure. Further, it is preferable to include it.

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

In the formula (S-1), R represents a hydrogen atom or an organic group, R may be bonded to another structure to form a ring structure, and * may independently form a binding site with another structure. Represent.
The R is preferably the same group as ^{R 2} in the following formula (S-2).
The compound having a sulfonamide structure may be a compound having two or more sulfonamide structures, but a compound having one sulfonamide structure is preferable.

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

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

Among these, ^{compounds in which R 1} is an aryl group and R ² and R ³ are independently hydrogen atoms or alkyl groups are preferable.

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

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

In formula (T-1), R ⁴ and R ⁵ each independently represent a hydrogen atom or a monovalent organic group, and R ⁴ and R ⁵ may be combined to form a ring structure, where R ⁴ is. The ring structure may be formed by ^{combining with other structures to which * is bonded, R 5} may be combined with other structures to which * is bonded to form a ring structure, and * may be independently and others. Represents the site of connection with the structure of.

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

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

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

Wherein (T-2), ^{R 4} and ^{R 5} have the same meanings as ^{R 4} and ^{R 5} in formula (T-1), a preferable embodiment thereof is also the same.
In the formula (T-2), ^{it is preferable that R 6} and R ⁷ are independently monovalent organic groups.
In the formula (T-2), the preferred embodiment of the monovalent organic group in ^{R 6} and R ⁷ is the same as the preferred embodiment of the monovalent organic group in ^{R 4} and R ^{5 in the formula (T-1).} ..

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

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

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

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

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

Examples of other migration inhibitors include rust preventives described in paragraph 0094 of JP2013-015701, compounds described in paragraphs 0073 to 0076 of JP2009-283711, and JP2011-059656. The compounds described in paragraph 0052, the compounds described in paragraphs 0114, 0116 and 0118 of JP2012-194520A, the compounds described in paragraph 0166 of International Publication No. 2015/199219, and the like can be used.

Specific examples of the migration inhibitor include the following compounds.

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

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

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

Examples of the polymerization inhibitor include hydroquinone, p-methoxyphenol, di-tert-butyl-p-cresol, pyrogallol, p-tert-butylcatechol, 1,4-benzoquinone, diphenyl-p-benzoquinone, 4,4'. -Thiobis (3-methyl-6-tert-butylphenol), 2,2'-methylenebis (4-methyl-6-tert-butylphenol), N-nitroso-N-phenylhydroxyamine aluminum salt, phenothiazine, N-nitrosodiphenylamine , N-phenylnaphthylamine, ethylenediamine tetraacetic acid, 1,2-cyclohexanediamine tetraacetic acid, glycol etherdiamine tetraacetic acid, 2,6-di-tert-butyl-4-methylphenol, 5-nitroso-8-hydroxyquinoline, 1 -Nitroso-2-naphthol, 2-nitroso-1-naphthol, 2-nitroso-5- (N-ethyl-N-sulfopropylamino) phenol, N-nitroso-N- (1-naphthyl) hydroxyamine ammonium salt, Bis (4-hydroxy-3,5-tert-butyl) phenylmethane and the like are preferably used. Further, the polymerization inhibitor described in paragraph 0060 of JP-A-2015-127817 and the compound described in paragraphs 0031 to 0046 of International Publication No. 2015/125469 can also be used.

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

When the negative curable composition of the present invention has a polymerization inhibitor, the content of the polymerization inhibitor is 0.01 to 5% by mass with respect to the total solid content of the negative curable composition of the present invention. It is preferably 0.02 to 3% by mass, more preferably 0.05 to 2.5% by mass.

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

<Other additives>
The negative curable composition of the present invention is, if necessary, various additives such as a sensitizer such as N-phenyldiethanolamine, a chain transfer agent, and a surfactant, as long as the effects of the present invention can be obtained. , Higher fatty acid derivatives, inorganic particles, curing agents, curing catalysts, fillers, antioxidants, ultraviolet absorbers, anti-aggregation agents and the like can be blended. When these additives are blended, the total blending amount is preferably 3% by mass or less of the solid content of the negative curable composition.

[Sensitizer]
The negative curable composition of the present invention may contain a sensitizer. The sensitizer absorbs specific active radiation and becomes an electron-excited state. The sensitizer in the electron-excited state comes into contact with the thermal radical polymerization initiator, the photoradical polymerization initiator, and the like, and acts such as electron transfer, energy transfer, and heat generation occur. As a result, the thermal radical polymerization initiator and the photoradical polymerization initiator undergo a chemical change and decompose to generate radicals, acids or bases.
Examples of the sensitizer include sensitizers such as N-phenyldiethanolamine.
Moreover, you may use a sensitizing dye as a sensitizer.
For details of the sensitizing dye, the description in paragraphs 0161 to 0163 of JP-A-2016-0273557 can be referred to, and this content is incorporated in the present specification.

When the negative curable composition of the present invention contains a sensitizer, the content of the sensitizer is 0.01 to 20% by mass with respect to the total solid content of the negative curable composition of the present invention. It is preferably 0.1 to 15% by mass, more preferably 0.5 to 10% by mass. The sensitizer may be used alone or in combination of two or more.

[Chain transfer agent]
The negative curable 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, 2005), pp. 683-684. As the chain transfer agent, for example, a group of compounds having SH, PH, SiH, and GeH in the molecule is used. They can donate hydrogen to low-activity radicals to generate radicals, or they can be oxidized and then deprotonated to generate radicals. In particular, a thiol compound can be preferably used.

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

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

[Surfactant]
Each type of surfactant may be added to the negative curable composition of the present invention from the viewpoint of further improving the coatability. As the surfactant, various types of surfactants such as fluorine-based surfactants, nonionic surfactants, cationic surfactants, anionic surfactants, and silicone-based surfactants can be used. The following surfactants are also preferable. In the following formula, the parentheses indicating the repeating unit of the main chain represent the content (mol%) of each repeating unit, and the parentheses indicating the repeating unit of the side chain represent the number of repetitions of each repeating unit.

Further, as the surfactant, the compound described in paragraphs 0159 to 0165 of International Publication No. 2015/199219 can also be used.

When the negative curable composition of the present invention has a surfactant, the content of the surfactant is 0.001 to 2.0 mass by mass with respect to the total solid content of the negative curable composition of the present invention. %, More preferably 0.005 to 1.0% by mass. The surfactant may be only one kind or two or more kinds. When there are two or more types of surfactant, the total is preferably in the above range.

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

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

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

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

The metal content of the negative curable composition of the present invention is preferably less than 5 mass ppm (parts per million), more preferably less than 1 mass ppm, still more preferably less than 0.5 mass ppm, from the viewpoint of insulating properties. .. Examples of the metal include sodium, potassium, magnesium, calcium, iron, chromium, nickel and the like. When a plurality of metals are contained, the total of these metals is preferably in the above range.

Further, as a method for reducing metal impurities unintentionally contained in the negative curable composition of the present invention, a raw material having a low metal content is selected as the raw material constituting the negative curable composition of the present invention. , Filter filtration is performed on the raw materials constituting the negative curable composition of the present invention, the inside of the apparatus is lined with polytetrafluoroethylene or the like, and distillation is performed under conditions in which contamination is suppressed as much as possible. The method can be mentioned.

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

A conventionally known storage container can be used as the storage container for the negative curable composition of the present invention. In addition, as the storage container, a multi-layer bottle composed of 6 types and 6 layers of resin and 6 types of resin are used for the purpose of suppressing impurities from being mixed into the raw materials and the negative curable composition. It is also preferable to use a bottle having a 7-layer structure. Examples of such a container include the container described in Japanese Patent Application Laid-Open No. 2015-123351.

<Use of negative curable composition>
The negative curable composition of the present invention is preferably used for forming an interlayer insulating film for a rewiring layer.
In addition, it can also be used for forming an insulating film of a semiconductor device, forming a stress buffer film, and the like.

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

Further, it is preferable to perform filtration using a filter for the purpose of removing foreign substances such as dust and fine particles in the negative curable composition. The filter pore diameter is preferably 1 μm or less, more preferably 0.5 μm or less, and even more preferably 0.1 μm or less. The filter material is preferably polytetrafluoroethylene, polyethylene or nylon. The filter may be one that has been pre-cleaned with an organic solvent. In the filter filtration step, a plurality of types of filters may be connected in series or in parallel. When using a plurality of types of filters, filters having different pore diameters or materials may be used in combination. Moreover, you may filter various materials a plurality of times. When filtering a plurality of times, circulation filtration may be used. Moreover, you may pressurize and perform filtration. When pressurizing and filtering, the pressurizing pressure is preferably 0.05 MPa or more and 0.3 MPa or less.
In addition to filtration using a filter, impurities may be removed using an adsorbent. Filter filtration and impurity removal treatment using an adsorbent may be combined. As the adsorbent, a known adsorbent can be used. Examples thereof include inorganic adsorbents such as silica gel and zeolite, and organic adsorbents such as activated carbon.

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

The cured film of the present invention is obtained by curing the negative curable composition of the present invention. The film thickness of the cured film of the present invention can be, for example, 0.5 μm or more, and can be 1 μm or more. Further, the upper limit value can be 100 μm or less, and can be 30 μm or less.

The cured film of the present invention may be laminated in two or more layers, and further in three to seven layers to form a laminated body. It is preferable that the laminate of the present invention contains two or more cured films and includes a metal layer between any of the cured films. For example, a laminate containing at least a layer structure in which three layers of a first cured film, a metal layer, and a second cured film are laminated in this order is preferable. The first cured film and the second cured film are both cured films of the present invention. For example, both the first cured film and the second cured film are the negative type of the present invention. A preferred embodiment is a film obtained by curing the curable composition. The negative curable composition of the present invention used for forming the first cured film and the negative curable composition of the present invention used for forming the second cured film have the same composition. It may be a product or a composition having a different composition. The metal layer in the laminate of the present invention is preferably used as metal wiring such as a rewiring layer.

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

The cured film in the present invention can also be used for manufacturing plate surfaces such as offset plate surfaces or screen plate surfaces, for etching molded parts, and for manufacturing protective lacquers and dielectric layers in electronics, especially in microelectronics.

The method for producing a cured film of the present invention (hereinafter, also simply referred to as “the method for producing the present invention”) includes a film forming step of applying the negative curable composition of the present invention to a substrate to form a film. Is preferable.
The method for producing a cured film of the present invention preferably includes the film forming step, an exposure step of exposing the film, and a developing step of developing the exposed film.
Further, the method for producing a cured film of the present invention more preferably includes a heating step of heating the film.
Specifically, it is also preferable to include the following steps (a) to (d).
(A) Film forming step of applying a negative curable composition to a substrate to form a film (negative curable composition layer) (b) Exposure step of exposing the film after the film forming step (b) Development step of developing the exposed film (d) Heating step of heating the developed film By heating in the heating step, the resin layer cured by exposure can be further cured. In this heating step, for example, the above-mentioned thermal acid generator is decomposed, and the generated acid promotes the cross-linking of the thermal cross-linking agent, so that sufficient curability can be obtained.

The method for producing a laminate according to a preferred embodiment of the present invention includes the method for producing a cured film of the present invention. The method for producing the laminated body of the present embodiment is the step (a), the steps (a) to (c), or (a) after forming the cured film according to the above-mentioned method for producing the cured film. )-(D). In particular, it is preferable to carry out each of the above steps a plurality of times, for example, 2 to 5 times (that is, 3 to 6 times in total) in order. By laminating the cured film in this way, a laminated body can be obtained. In the present invention, it is particularly preferable to provide a metal layer on the portion provided with the cured film, between the cured films, or both. In the production of the laminate, it is not necessary to repeat all the steps (a) to (d), and as described above, at least (a), preferably (a) to (c) or (a) to (d). ) Can be performed a plurality of times to obtain a laminated body of the cured film.

<Film formation process (layer formation process)>
The production method according to a preferred embodiment of the present invention includes a film forming step (layer forming step) in which a negative curable composition is applied to a substrate to form a film (layered).

The type of base material can be appropriately determined depending on the application, but semiconductor-made base materials such as silicon, silicon nitride, polysilicon, silicon oxide, and amorphous silicon, quartz, glass, optical film, ceramic material, and thin-film deposition film, There are no particular restrictions on magnetic film, reflective film, metal substrate such as Ni, Cu, Cr, Fe, paper, SOG (Spin On Glass), TFT (thin film transistor) array substrate, plasma display panel (PDP) electrode plate, and the like.
In the present invention, a semiconductor-made base material is particularly preferable, and a silicon base material is more preferable.
Further, these base materials may be provided with a layer such as an adhesion layer or an oxide layer on the surface thereof.
Further, the shape of the base material is not particularly limited, and may be circular or rectangular.
The size of the base material is, for example, 100 to 450 mm in diameter, preferably 200 to 450 mm in a circular shape. If it is rectangular, for example, the length of the short side is 100 to 1000 mm, preferably 200 to 700 mm.
Further, as the base material, for example, a plate-shaped base material (board) is used.

Further, when a negative curable composition layer is formed on the surface of the resin layer or the surface of the metal layer, the resin layer or the metal layer serves as a base material.

Coating is preferable as a means for applying the negative curable composition to the substrate.

Specifically, the means to be applied include a dip coating method, an air knife coating method, a curtain coating method, a wire bar coating method, a gravure coating method, an extrusion coating method, a spray coating method, a spin coating method, and a slit coating method. And the inkjet method and the like are exemplified. From the viewpoint of the uniformity of the thickness of the negative curable composition layer, a spin coating method, a slit coating method, a spray coating method, and an inkjet method are more preferable. A resin layer having a desired thickness can be obtained by adjusting an appropriate solid content concentration and coating conditions according to the method. Further, the coating method can be appropriately selected depending on the shape of the base material. For a circular base material such as a wafer, a spin coating method, a spray coating method, an inkjet method, etc. are preferable, and for a rectangular base material, a slit coating method or a spray coating method is used. The method, the inkjet method and the like are preferable. In the case of the spin coating method, for example, it can be applied at a rotation speed of 500 to 2,000 rpm for about 10 seconds to 1 minute.
Further, it is also possible to apply a method of transferring a coating film previously formed on a temporary support by the above-mentioned application method onto a substrate.
Regarding the transfer method, the production method described in paragraphs 0023, 0036 to 0051 of JP-A-2006-023696 and paragraphs 096 to 0108 of JP-A-2006-047592 can be preferably used in the present invention.
Further, a step of removing the excess film at the edge of the base material may be performed. Examples of such a process include edge bead conditioner (EBR), air knife and the like.

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

<Exposure process>
The production method of the present invention may include an exposure step of exposing the film (negative curable composition layer). The exposure amount is not particularly determined as long as the negative curable composition can be cured, but for example, ^{it is preferable to irradiate 100 to 10,000 mJ / cm 2 in} terms of exposure energy at a wavelength of 365 nm, and 200 to 8,000 mJ. It is more preferable to irradiate with / cm ^2.

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

In relation to the light source, the exposure wavelengths are (1) semiconductor laser (wavelength 830 nm, 532 nm, 488 nm, 405 nm, etc.), (2) metal halide lamp, (3) high-pressure mercury lamp, g-ray (wavelength 436 nm), h. Line (wavelength 405 nm), i-line (wavelength 365 nm), broad (3 wavelengths of g, h, i-line), (4) excimer laser, KrF excimer laser (wavelength 248 nm), ArF excimer laser (wavelength 193 nm), F2 excimer Examples thereof include a laser (wavelength 157 nm), (5) extreme ultraviolet rays; EUV (wavelength 13.6 nm), and (6) electron beam. For the negative curable composition of the present invention, exposure with a high-pressure mercury lamp is particularly preferable, and exposure with an i-line is particularly preferable. As a result, particularly high exposure sensitivity can be obtained.

<Development process>
The production method of the present invention may include a developing step of developing the exposed film (negative curable composition layer) (developing the film). By developing, the unexposed portion (non-exposed portion) is removed. The developing method is not particularly limited as long as a desired pattern can be formed, and examples thereof include ejection from a nozzle, spray spraying, immersion of a developing solution in a base material, and the like, and ejection from a nozzle is preferably used. The developing process includes a process in which the developer is continuously supplied to the substrate, a process in which the developer is kept in a substantially stationary state on the substrate, a process in which the developer is vibrated by ultrasonic waves, and a process in which they are combined. It can be adopted.

Development is performed using a developer. The developer can be used without particular limitation as long as the unexposed portion (non-exposed portion) is removed.

The developer preferably has an organic solvent content of 10% by mass or less based on the total mass of the developer, more preferably 5% by mass or less, and 1% by mass or less. Is more preferable, and a developing solution containing no organic solvent is particularly preferable.
In addition, the developer may contain a known surfactant.
The developing solution in alkaline development is more preferably an aqueous solution having a pH of 10 to 15.
Examples of the alkaline compound contained in the developing solution in alkaline development include sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, sodium silicate, potassium silicate, sodium metasilicate, and metasilicate. Examples include potassium silicate, ammonia or amine. Examples of amines include ethylamine, n-propylamine, diethylamine, di-n-propylamine, triethylamine, methyldiethylamine, alkanolamine, dimethylethanolamine, triethanolamine, quaternary ammonium hydroxide, and tetramethylammonium hydroxide. (TMAH), tetraethylammonium hydroxide, tetrabutylammonium hydroxide and the like can be mentioned. Of these, an alkaline compound containing no metal is preferable, and an ammonium compound is more preferable.
When, for example, TMAH is used as the alkaline compound, the content of TMAH is preferably 0.01 to 10% by mass, more preferably 0.1 to 5% by mass, and 0.3 to 3 to the total mass of the developing solution. Mass% is more preferred.
The alkaline compound may be only one kind or two or more kinds. When there are two or more alkaline compounds, the total is preferably in the above range.

The development time is preferably 10 seconds to 5 minutes. The temperature of the developing solution at the time of development is not particularly specified, but is usually 20 to 40 ° C.

After the treatment with the developing solution, further rinsing may be performed. The rinsing is preferably performed with a solvent different from that of the developing solution. For example, it can be rinsed with water. The rinsing time is preferably 5 seconds to 1 minute.

<Heating process>
The production method of the present invention preferably includes a step (heating step) of heating the developed film.
The heating step is preferably included after the film forming step (layer forming step), the drying step, and the developing step. In the heating step, for example, cross-linking of an unreacted cross-linking agent can proceed. The heating temperature (maximum heating temperature) of the layer in the heating step is preferably 50 ° C. or higher, more preferably 80 ° C. or higher, further preferably 140 ° C. or higher, and 150 ° C. or higher. Is even more preferable, 160 ° C. or higher is even more preferable, and 170 ° C. or higher is even more preferable. The upper limit is preferably 500 ° C. or lower, more preferably 450 ° C. or lower, further preferably 350 ° C. or lower, further preferably 250 ° C. or lower, and preferably 220 ° C. or lower. Even more preferable.

The heating is preferably performed at a heating rate of 1 to 12 ° C./min from the temperature at the start of heating to the maximum heating temperature, more preferably 2 to 10 ° C./min, and even more preferably 3 to 10 ° C./min. By setting the temperature rise rate to 1 ° C./min or more, it is possible to prevent excessive volatilization of the acid or solvent while ensuring productivity, and by setting the temperature rise rate to 12 ° C./min or less, curing is possible. The residual stress of the film can be relaxed.

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

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

Particularly when forming a multi-layered laminate, the heating temperature is preferably 180 ° C. to 320 ° C., more preferably 180 ° C. to 260 ° C. from the viewpoint of adhesion between layers of the cured film. The reason is not clear, but it is considered that the ethynyl groups of the specific resin between the layers are undergoing a cross-linking reaction at this temperature.

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

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

The heating step is preferably performed in an atmosphere having a low oxygen concentration by flowing an inert gas such as nitrogen, helium, or argon from the viewpoint of preventing decomposition of the specific resin. The oxygen concentration is preferably 50 ppm (volume ratio) or less, and more preferably 20 ppm (volume ratio) or less.
The heating means in the heating step is not particularly limited, and examples thereof include a hot plate, an infrared furnace, an electric heating oven, and a hot air oven.

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

As the metal layer, existing metal types can be used without particular limitation, and copper, aluminum, nickel, vanadium, titanium, chromium, cobalt, gold, tungsten, alloys containing these metals and the like are exemplified, and copper is used. And aluminum are more preferred, and copper is even more preferred.

The method for forming the metal layer is not particularly limited, and an existing method can be applied. For example, the methods described in JP-A-2007-157879, JP-A-2001-521288, JP-A-2004-214501, and JP-A-2004-101850 can be used. For example, photolithography, lift-off, electrolytic plating, electroless plating, etching, printing, and a method combining these can be considered. More specifically, a patterning method combining sputtering, photolithography and etching, and a patterning method combining photolithography and electroplating can be mentioned.

The thickness of the metal layer is preferably 0.1 to 50 μm, more preferably 1 to 10 μm in the thickest portion.

<Laminating process>
The production method of the present invention preferably further includes a laminating step.

The laminating step means that (a) a film forming step (layer forming step), (b) an exposure step, (c) a developing step, and (d) a heating step are performed again on the surface of the cured film (resin layer) or the metal layer. , A series of steps including performing in this order. However, the mode may be such that only the film forming step (a) is repeated.
Further, (d) the heating step may be performed collectively at the end or the middle of the lamination. That is, the steps (a) to (c) may be repeated a predetermined number of times, and then the heating of (d) may be performed to cure the laminated negative curable composition layers all at once. Further, the (c) developing step may be followed by the (e) metal layer forming step, and even if the heating is performed each time (d), the steps of (d) are collectively performed after laminating a predetermined number of times. Heating may be performed. Needless to say, the laminating step may further include the above-mentioned drying step, heating step, and the like as appropriate.

When the laminating step is further performed after the laminating step, the surface activation treatment step may be further performed after the heating step, the exposure step, or the metal layer forming step. An example of the surface activation treatment is plasma treatment.

The laminating step is preferably performed 2 to 5 times, more preferably 3 to 5 times.
Further, each layer in the laminating step may be a layer having the same composition, shape, film thickness, etc., or may be a different layer.

For example, a structure such as a resin layer / metal layer / resin layer / metal layer / resin layer / metal layer is preferable, and the resin layer is preferably 3 layers or more and 7 layers or less, and more preferably 3 layers or more and 5 layers or less.

In the present invention, it is particularly preferable to form a cured film (resin layer) of the negative curable composition so as to cover the metal layer after the metal layer is provided. Specifically, a mode in which (a) a film forming step, (b) an exposure step, (c) a developing step, (e) a metal layer forming step, and (d) a heating step are repeated in this order, or (a) film forming. Examples thereof include an embodiment in which the steps, (b) exposure steps, (c) development steps, and (e) metal layer forming steps are repeated in this order, and (d) heating steps are collectively provided at the end or in the middle. By alternately performing the laminating step of laminating the negative type curable composition layer (resin layer) and the metal layer forming step, the negative type curable composition layer (resin layer) and the metal layer can be alternately laminated. it can.

The present invention also discloses a semiconductor device containing the cured film or laminate of the present invention. Specific examples of the semiconductor device in which the negative curable composition of the present invention is used to form the interlayer insulating film for the rewiring layer are described in paragraphs 0213 to 0218 and FIG. It can be taken into consideration and these contents are incorporated in the present specification.

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

<Synthesis example 1>
[Alkali-soluble polyimide A-1: oxydiphthalic acid dianhydride, 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane, 1,3-bis (3-aminopropyl) tetramethyldisiloxane and 2 -Synthesis using isocyanatoethyl methacrylate]
65.56 g (179 mmol) of 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane while removing water in a drying reactor equipped with a flat bottom joint equipped with a stirrer, condenser and internal thermometer. ) And 2.48 g (10 mmol) of 1,3-bis (3-aminopropyl) tetramethyldisiloxane were dissolved in 300 g of N-methylpyrrolidone (NMP). Subsequently, 62.04 g (200 mmol) of oxydiphthalic dianhydride was added, and the mixture was stirred at a temperature of 40 ° C. for 2 hours. Then, 50 mL of toluene and 2.18 g (10 mmol) of 3-aminophenol were added, and the mixture was stirred at 40 ° C. for 2 hours. After stirring, the temperature was raised to 180 ° C. while flowing nitrogen at a flow rate of 200 ml / min, and the mixture was stirred for 6 hours.
After cooling the above reaction solution to 25 ° C., 0.005 g of p-methoxyphenol was added and dissolved. To this solution, 24.82 g (160 mmol) of 2-isocyanatoethyl methacrylate was added dropwise, and the mixture was stirred at 25 ° C. for 2 hours and then at 60 ° C. for 3 hours. This was cooled to 25 ° C., 10 g of acetic acid was added, and the mixture was stirred at 25 ° C. for 1 hour. After stirring, the mixture was precipitated in 2 liters of water / methanol = 75/25 (volume ratio) and stirred at a rate of 2,000 rpm for 30 minutes. The precipitated polyimide resin was obtained by filtration, washed with 1.5 liters of water, mixed with 2 liters of methanol, stirred again for 30 minutes, and filtered again. The obtained polyimide was dried under reduced pressure at 40 ° C. for 1 day to obtain A-1.

<Synthesis example 2>
[Alkali-soluble polyimide A-2: oxydiphthalic acid dianhydride, 2,2-bis (3-amino-4-hydroxyphenyl) propane, 1,3-bis (3-aminopropyl) tetramethyldisiloxane and 2-isocyanate Synthesis using natoethylmethacrylate]
In the synthesis of A-1, the same molar amount of 2,2-bis (3-amino-4-hydroxyphenyl) propane is used instead of 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane. Alkali-soluble polyimide A-2 was synthesized by the same method as that of A-1 except for the above.

<Synthesis example 3>
[Alkali-soluble polyimide A-3: Synthesis using oxydiphthalic dianhydride, 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane and 2-isocyanatoethyl methacrylate]
In the synthesis of A-1, the amount of 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane used was 69. without using 1,3-bis (3-aminopropyl) tetramethyldisiloxane. Alkali-soluble polyimide A-3 was synthesized by the same method as in the synthesis of A-1, except that the amount was 22 g (189 mmol).

<Synthesis example 4>
[Alkali-soluble polyimide A-4: oxydiphthalic dianhydride, 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane, and 1,3-bis (3-aminopropyl) tetramethyldisiloxane. Synthesis using]
In the synthesis of A-1, the alkali-soluble polyimide A-4 was synthesized by the same method as in the synthesis of A-1, except that 2-isocyanatoethyl methacrylate was not added.

<Synthesis example 5>
[Alkali-soluble polyimide A-5: oxydiphthalic dianhydride, 2,5-dimercapto-p-phenylenediamine, 1,3-bis (3-aminopropyl) tetramethyldisiloxane and 2-isocyanatoethyl methacrylate were used. Synthetic]
In the synthesis of A-1, except that the same molar amount of 2,5-dimercapto-p-phenylenediamine was used instead of 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane, A- Alkali-soluble polyimide A-5 was synthesized by the same method as in the synthesis of 1.

<Examples and Comparative Examples>
In each example, the components shown in Tables 1 to 3 below were mixed to obtain each negative curable composition. Further, in each comparative example, the components shown in Table 3 below were mixed to obtain each comparative composition.
Specifically, the content of the components shown in Tables 1 to 3 was the amount shown in "Mass parts" in Tables 1 to 3. Further, in each composition, the solvent content was adjusted so that the solid content concentration of the composition was the value shown in Tables 1 to 3.
In the table, for example, the description of "E-1 / E-4" and "0.5 / 0.5" refers to 0.5 parts by mass of E-1 and 0.5 parts by mass of E-4. It means that it was used.
The description in the column of "metal concentration" in Tables 1 to 3 represents the metal content (mass ppm) with respect to the total mass of the composition.
The obtained negative curable composition and the comparative composition were pressure-filtered through a filter made of polytetrafluoroethylene having a pore width of 0.8 μm.
Further, in Tables 1 to 3, the description of "-" indicates that the composition does not contain the corresponding component.

Details of each component listed in Tables 1 to 3 are as follows.

[Alkali-soluble polyimide]
-A-1 to A-5: A-1 to A-5 synthesized above

[Crosslinking agent]
-B-1: Dipentaerythritol hexaacrylate-B-2: Light ester BP-6EM (manufactured by Kyoeisha Chemical Co., Ltd.)
・ B-3: Nicarac MX-270 (manufactured by Sanwa Chemical Co., Ltd.)
・ B-4: Nicarac MW-100LM (manufactured by Sanwa Chemical Co., Ltd.)
・ B-5: Denacol EX-421 (manufactured by Nagase ChemteX Corporation)
・ B-6: Denacol EX-212 (manufactured by Nagase ChemteX Corporation)
B-1 and B-2 are ethylenically unsaturated bond-containing cross-linking agents, B-3 and B-4 are alkoxymethyl group-containing cross-linking agents, and B-5 and B-6 are cyclic ether group-containing cross-linking agents. Is.

[Radical generator]
-C-1: ADEKA NCI-930 (manufactured by ADEKA Corporation)
-C-2: Omnirad 819 (manufactured by IGM Resins)
-C-3: Irgacure 784 (manufactured by BASF)

[Thermal acid generator]
・ D-1: K-PURE TAG-2179
-D-2: Isopropyl p-toluenesulfonic acid-D-3: K-PURE TAG-2172
・ D-4: K-PURE TAG-2713
・ D-5: K-PURE TAG-2678
・ D-6: K-PURE TAG-2679

〔Silane coupling agent〕
E-1: KBM-5103 (manufactured by Shin-Etsu Silicone Co., Ltd.)
-E-2: N- (3- (triethoxysilyl) propyl) phthalamic acid-E-3: KBE-403 (manufactured by Shin-Etsu Silicone Co., Ltd.)
・ E-4: IM-1000 (manufactured by JX Nippon Mining & Metals Co., Ltd.)
E-1 to E-3 are compounds corresponding to the specific silane coupling agent.
Since E-4 does not have the group e-2, it is a compound that does not correspond to the specific silane coupling agent.

[Polymerization inhibitor]
・ F-1: 4-Methoxy-1-naphthol

〔Additive〕
-G-1: 1,3-dibutylthiourea-G-2: N-butylbenzenesulfonamide

〔solvent〕
・ H-1: γ-butyrolactone ・ H-2: ε-caprolactone ・ H-3: N-methyl-2-pyrrolidone ・ H-4: dimethyl sulfoxide ・ H-5: ethyl lactate In Tables 1 to 3, " The description in the column of "ratio in solvent" indicates the content (mass%) of each solvent with respect to the total mass of the solvent.

<Evaluation>
[Breaking elongation]
In each of Examples and Comparative Examples other than Example 15, each negative curable composition or comparative composition is applied (coated) in layers on a silicon wafer by a spin coating method to form a curable resin composition. A layer was formed. In Example 15, the negative curable composition was applied (coated) in layers on a silicon wafer by the slit coating method to form a composition layer.
In each Example and Comparative Example, the silicon wafer to which the obtained composition layer was applied was dried on a hot plate at 80 ° C. for 5 minutes, and the curability of the thickness shown in Tables 1 to 3 was obtained on the silicon wafer. A resin composition layer was formed. The curable resin composition layer on the silicon wafer was entirely exposed to an exposure energy of ^{500 mJ / cm 2 using a stepper (Nikon NSR 2005 i9C).} After exposure, it was heated at 100 ° C. for 5 minutes. The curable resin composition layer (resin layer) after heating is heated at a heating rate of 10 ° C./min under a nitrogen atmosphere to the temperature of "cure temperature (° C.)" in Tables 1 to 3. After reaching, this temperature was maintained for the time listed in "Cure Time (min)" in Tables 1-3. The cured resin layer was immersed in a 4.9 mass% hydrofluoric acid aqueous solution, and the resin layer was peeled off from the silicon wafer to obtain a resin film 1.

The elongation at break of the resin film 1 was set to a crosshead speed of 300 mm / min, a sample width of 10 mm, and a sample length of 50 mm using a tensile tester (Tensilon) at 25 ° C. and 65% relative humidity (RH) in the longitudinal direction of the film. The measurement was performed in accordance with JIS-K6251: 2017 in an environment. The elongation at break is E _b (%) = (L _{b −} L ₀ ) / L ₀ × 100 (E _b : elongation at cutting, L ₀ : length of test piece before test, L _b : test piece is cut. It was calculated by the length of the test piece at that time). The elongation at break in the longitudinal direction was measured 5 times, and the arithmetic average value was used as an index value. The evaluation was performed according to the following evaluation criteria. The evaluation results are described in the column of "evaluation of elongation at break" in Tables 1 to 3. It can be said that the larger the index value is, the more excellent the obtained cured film is in elongation at break.
-Evaluation criteria-
A: The above index value exceeded 60%.
B: The index value was more than 40% and 60% or less.
C: The above index value was 40% or less.

〔chemical resistance〕
In each of Examples and Comparative Examples other than Example 15, each of the prepared curable resin compositions or comparative compositions was applied onto a silicon wafer by a spin coating method to form a composition layer. In Example 15, the negative curable composition was applied (coated) in layers on a silicon wafer by the slit coating method to form a composition layer.
The silicon wafer to which the obtained composition layer was applied was dried on a hot plate at 100 ° C. for 5 minutes to form a composition layer having a uniform thickness of 15 μm on the silicon wafer. ^{The composition layer on the silicon wafer was exposed to an exposure energy of 500 mJ / cm 2} using a stepper (Nikon NSR 2005 i9C), and the exposed composition layer (resin layer) was exposed at 10 ° C./ After the temperature is raised at a heating rate of 1 minute and reaches the temperature of "cure temperature (° C.)" in Tables 1 to 3, this temperature is set to the time shown in "cure time (min)" in Tables 1 to 3. It was maintained for a while to obtain a cured film.
The obtained cured film was immersed in the following chemical solution under the following conditions, and the dissolution rate was calculated.
Chemical solution: Mixture of dimethyl sulfoxide (DMSO) and 25 mass% tetramethylammonium hydroxide (TMAH) aqueous solution at 90:10 (mass ratio) Evaluation conditions: Immerse the cured membrane in the chemical solution at 75 ° C. for 15 minutes before and after. The film thickness was compared and the dissolution rate (nm / min) was calculated.
The evaluation was performed according to the following evaluation criteria, and the evaluation results are described in the "Chemical resistance evaluation" column of Tables 1 to 3.

-Evaluation criteria-
A The dissolution rate was less than 200 nm / min.
B The dissolution rate was 200 nm / min or more and less than 300 nm / min.
C The dissolution rate was 300 nm / min or more.

[Adhesion]
In each of Examples and Comparative Examples other than Example 15, each negative curable composition or comparative composition is applied (coated) in layers on a copper substrate by a spin coating method to form a curable resin composition. A layer was formed. In Example 15, the negative curable composition was applied (coated) in layers on a copper substrate by the slit coating method to form a composition layer.
In each Example and Comparative Example, the copper substrate to which the obtained composition layer was applied was dried on a hot plate at 80 ° C. for 5 minutes, and the curability of the thickness shown in Tables 1 to 3 was obtained on the copper substrate. A resin composition layer was formed.
The curable resin composition layer on the copper substrate is exposed using a stepper (Nikon NSR 2005 i9C) with ^{an exposure energy of 500 mJ / cm 2} using a photomask having a 100 μm square unmasked portion. After the exposure, the mixture was heated at 100 ° C. for 5 minutes. After the above heating, the mixture was developed with a 2.38 mass% tetramethylammonium hydroxide aqueous solution for 5 minutes and rinsed with pure water for 20 seconds to obtain a 100 μm square resin layer. Further, in a nitrogen atmosphere, the temperature is raised at a heating rate of 10 ° C./min, and after reaching the temperature of "cure temperature (° C.)" in Tables 1 to 3, the "cure time (cure time) in Tables 1 to 3 is reached. It was maintained for the time described in "min)".

The shear force of a 100 μm rectangular resin layer on a copper substrate was measured using a bond tester (CondorSigma, manufactured by XYZTEC) in an environment of 25 ° C. and 65% relative humidity (RH). It can be said that the larger the shearing force, the larger the adhesion force and the better the adhesion. The evaluation was performed according to the following evaluation criteria. The evaluation results are described in the "Adhesion evaluation" column of Tables 1 to 3.
-Evaluation criteria-
A: The shearing force exceeded 40 gf.
B: The shearing force was more than 25 gf and 40 gf or less.
C: The shearing force was 25 gf or less.
However, 1 gf is 9.80665 × 10 ^-3 N (Newton).

[Pot life]
In each Example and Comparative Example, the viscosity (mPa · s) of each negative curable composition or comparative composition was measured by "RE-85L" manufactured by Toki Sangyo Co., Ltd. After the above measurement, the composition was allowed to stand under the conditions of 45 ° C., light shielding, and 3 days, and the viscosity (mPa · s) was measured again. The pot life was evaluated according to the following evaluation criteria from the viscosity difference (ΔVis) before and after the standing. The evaluation results are listed in the "Pot Life" column of Tables 1 to 3. It can be said that the smaller the value of the viscosity difference (ΔVis), the better the pot life of the composition. In each of the above viscosity measurements, the temperature and humidity were controlled to 22 ± 5 ° C. and 60 ± 20% in a laboratory, and the temperature of the composition was adjusted to 25 ° C.

-Evaluation criteria-
A: ΔVis was 1.0 mPa · s or less.
B: ΔVis exceeded 1.0 mPa · s.

From the above results, the negative curable composition containing the alkali-soluble polyimide, a plurality of types of cross-linking agents having different cross-linking groups, and a specific silane coupling agent according to the present invention has excellent chemical resistance. It can be seen that a cured film can be obtained.
The comparative composition according to Comparative Example 1 does not contain a specific silane coupling agent. It can be seen that the comparative composition according to Comparative Example 1 is inferior in chemical resistance in the obtained cured film.

<Example 101>
The negative curable composition used in Example 1 was applied in layers to the surface of the copper thin layer of the resin base material having the copper thin layer formed on the surface by a spin coating method, and dried at 80 ° C. for 5 minutes. After forming a negative curable composition layer having a film thickness of 20 μm, exposure was performed using a stepper (NSR1505 i6, manufactured by Nikon Corporation). The exposure was performed through a mask (a binary mask having a pattern of 1: 1 line and space and a line width of 10 μm) at a wavelength of 365 nm. After exposure, it was heated at 100 ° C. for 5 minutes. After the above heating, the mixture was developed with a 2.38 mass% tetramethylammonium hydroxide aqueous solution for 5 minutes and rinsed with pure water for 20 seconds to obtain a layer pattern.
Next, the temperature was raised at a heating rate of 10 ° C./min under a nitrogen atmosphere, and after reaching 200 ° C., the temperature was maintained at 200 ° C. for 120 minutes to form an interlayer insulating film for the rewiring layer. The interlayer insulating film for the rewiring layer was excellent in insulating property.
Moreover, when a semiconductor device was manufactured using these interlayer insulating films for the rewiring layer, it was confirmed that the semiconductor device operated without any problem.

Claims

Alkali-soluble polyimide,
Multiple types of cross-linking agents with different cross-linking groups, and
Contains silane coupling agent,
The silane coupling agent has a covalent bond between an alkoxy group e-1 directly bonded to a silicon atom and a group different from the e-1 and at least one of the plurality of types of cross-linking agents. A negative curable composition having a possible group e-2.
The plurality of types of cross-linking agents have a cross-linking agent having a radical polymerizable group in which the cross-linking reaction proceeds by the action of a radical as a cross-linking group, and an acid-cross-linking group in which the cross-linking reaction proceeds by the action of an acid as a cross-linking group. The negative curable composition according to claim 1, which comprises a cross-linking agent.
The negative curable composition according to claim 1 or 2, wherein the alkali-soluble polyimide has a fluorine atom.
The negative curable composition according to any one of claims 1 to 3, wherein the alkali-soluble polyimide has a silicon atom.
The negative curable composition according to any one of claims 1 to 4, wherein the alkali-soluble polyimide has an ethylenically unsaturated bond.
The negative curable composition according to any one of claims 1 to 5, wherein the alkali-soluble polyimide has a phenolic hydroxy group.
The negative curable composition according to any one of claims 1 to 6, which comprises a compound having at least one structure selected from the group consisting of a sulfonamide structure and a thiourea structure.
The negative curable composition according to any one of claims 1 to 7, which contains a radical generator having an oxime structure.
The negative curable composition according to any one of claims 1 to 8, which contains a compound having 3 to 6 ethylenically unsaturated bonds as at least one of the plurality of types of cross-linking agents.
The negative curable composition according to any one of claims 1 to 9, which contains a neutralized salt-type thermoacid generator.
The negative curable composition according to any one of claims 1 to 10, which is used for forming an interlayer insulating film for a rewiring layer.
A cured film obtained by curing the negative curable composition according to any one of claims 1 to 11.
A laminate containing two or more layers of the cured film according to claim 12 and containing a metal layer between any of the cured films.
A method for producing a cured film, which comprises a film forming step of applying the negative curable composition according to any one of claims 1 to 11 to a substrate to form a film.
The method for producing a cured film according to claim 14, further comprising an exposure step of exposing the film and a developing step of developing the exposed film.
The method for producing a cured film according to claim 14 or 15, which comprises a heating step of heating the film at 50 to 450 ° C.
A semiconductor device comprising the cured film according to claim 12 or the laminate according to claim 13.