JP2021167396A - Method for producing laminate, method for producing micro-lens, method for producing cmos image sensor, and curable composition - Google Patents

Abstract

To provide: a method for producing a laminate which, when curing a layer comprising a curable composition in a state where the curable composition is in contact with a layer comprising a nitrogen-containing compound with a nitrogen atom having a lone electron pair, suppresses cure inhibition of the layer comprising a curable composition; a method for producing a micro-lens, comprising the production method of a laminate; a method for producing a CMOS image sensor, comprising the method for producing a micro-lens; and a curable composition used suitably in the method for producing a laminate.SOLUTION: Provided is a method for producing a laminate by curing a layer formed of a curable composition comprising a cationically curable composition (A) and a cationic curing agent (B) in a state where the curable composition is in contact with a layer comprising a nitrogen-containing compound with a nitrogen atom having a lone electron pair, where a sulfonium salt having a sulfonium cation of a specific structure is used as the cationic curing agent (B).SELECTED DRAWING: None

Description

The present invention is suitable for a method for manufacturing a laminate, a method for manufacturing a microlens including a method for manufacturing the laminate, a method for manufacturing a CMOS image sensor including a method for manufacturing the microlens, and a method for manufacturing the laminate described above. With respect to the curable composition used in.

Conventionally, cationically polymerizable curable compositions containing a cationically polymerizable compound such as an epoxy compound as a curable component have been used for various purposes.

Such a curable composition includes, for example, a cationically polymerizable compound containing an aromatic ring-containing alicyclic epoxy compound, a cationically polymerizable compound other than the aromatic ring-containing alicyclic epoxy compound, and a thermocationic polymerization initiator. Thermosetting compositions are known (see Patent Document 1). By using such a curable composition, it is possible to form a cured product having a high glass transition temperature, transparency (heat-resistant yellowing and less coloring), and excellent substrate adhesion.

Japanese Unexamined Patent Publication No. 2014-156522

However, as a result of studies by the present inventors, when a cured product is formed using a curable composition as described in Patent Document 1, a layer containing a nitrogen-containing compound containing a nitrogen atom having a lone electron pair. It has been found that curing the curable composition in contact with the curable composition often significantly inhibits the curing of the curable composition.

The present invention has been made in view of the above problems, and a layer made of a curable composition in a state where the curable composition is in contact with a layer containing a nitrogen-containing compound containing a nitrogen atom having a lone electron pair. A method for producing a laminate in which curing inhibition of a layer made of a curable composition is suppressed when cured, a method for producing a microlens including a method for producing the laminate, and a CMOS including a method for producing the microlens. It is an object of the present invention to provide a method for producing an image sensor and a curable composition preferably used in the above-mentioned method for producing a laminate.

The present inventors have formed a layer composed of a curable composition containing a cationic curing compound (A) and a cationic curing agent (B) into a layer containing a nitrogen-containing compound containing a nitrogen atom having a lone electron pair. We have found that the above problems can be solved by using a sulfonium salt having a sulfonium cation having a specific structure as the cation curing agent (B) in the method of producing a laminate by curing in contact with each other, and completed the present invention. I came to do it. Specifically, the present invention provides the following.

The first aspect of the present invention is
A curable composition containing a cationic curable compound (A) and a cationic curing agent (B) is applied to at least a part of the main surface of the nitrogen-containing compound-containing layer.
A method for producing a laminate, which comprises curing a curable composition to form a cured product layer.
The nitrogen-containing compound-containing layer contains a nitrogen-containing compound containing a nitrogen atom having a lone electron pair.
A method for producing a laminate, wherein the cation curing agent (B) contains a sulfonium salt having a cation portion represented by the following formula (B1).
Ar-CH _2- S ⁺ -R ^B1 R ^B2 ... (B1)
(In the formula (B1), Ar is substituted is also an aromatic hydrocarbon group, R ^B1, and R ^B2 are each independently may be substituted hydrocarbon group. )

A second aspect of the present invention is
By the method according to the first aspect, the cured product layer is formed on a green color filter, a blue color filter, or a red color filter as a nitrogen-containing compound-containing layer.
Forming a mask with a shape corresponding to the shape of the lens to be formed on the cured product layer,
Including forming a lens to which the shape of the mask is transferred by etching the cured product layer together with the mask.
This is a method for manufacturing a microlens in which the cured product layer is transparent.

A third aspect of the present invention is a method for manufacturing a CMOS image sensor, which comprises manufacturing a microlens on a green color filter, a blue color filter, or a red color filter by the method according to the second aspect.

A fourth aspect of the present invention is a curable composition used in the method for producing a laminate according to the first aspect.
Containing a cationic curing compound (A) and a cationic curing agent (B),
The cationic curing agent (B) is a curable composition containing a sulfonium salt having a cation portion represented by the following formula (B1).
Ar-CH _2- S ⁺ -R ^B1 R ^B2 ... (B1)
(In the formula (B1), Ar is substituted is also an aromatic hydrocarbon group, R ^B1, and R ^B2 are each independently may be substituted hydrocarbon group. )

According to the present invention, when the layer composed of the curable composition is cured in a state where the curable composition is in contact with the layer containing the nitrogen-containing compound containing a nitrogen atom having a lone electron pair, the composition comprises the curable composition. A method for manufacturing a laminate in which inhibition of layer curing is suppressed, a method for manufacturing a microlens including a method for manufacturing the laminate, a method for manufacturing a CMOS image sensor including a method for manufacturing the microlens, and the above-mentioned laminate. It is possible to provide a curable composition preferably used in the production method of the above.

≪Manufacturing method of laminated body≫
The method of manufacturing the laminate is
A curable composition containing a cationic curable compound (A) and a cationic curing agent (B) is applied to at least a part of the main surface of the nitrogen-containing compound-containing layer.
Curing the curable composition to form a cured product layer,
including.

In the above method, the nitrogen-containing compound-containing layer contains a nitrogen-containing compound containing a nitrogen atom having a lone electron pair. The cation curing agent (B) contains a sulfonium salt having a cation portion represented by the following formula (B1).
Ar-CH _2- S ⁺ -R ^B1 R ^B2 ... (B1)
(In the formula (B1), Ar is substituted is also an aromatic hydrocarbon group, R ^B1, and R ^B2 are each independently may be substituted hydrocarbon group. )

When the curable composition is cured in a state where the curable composition containing the cationically curable compound is in contact with such a nitrogen-containing compound-containing layer, the effect is often hindered and the curable composition is not cured well. ..

However, by incorporating the cation-curable compound (A) and a sulfonium salt having a cation portion represented by the above formula (B1) as the cation-curing agent (B) in the curable composition, the curable composition can be obtained. The curable composition can be satisfactorily cured even when it is in contact with the above-mentioned nitrogen-containing compound-containing layer.

Hereinafter, the application of the curable composition containing the cationic curable compound (A) and the cationic curing agent (B) to at least a part of the main surface of the nitrogen-containing compound-containing layer is also referred to as a “coating step”.
Curing the curable composition to form a cured product layer is also referred to as a "curing step".

Hereinafter, the coating process and the curing process will be described.

<Applying process>
A curable composition containing the cationic curable compound (A) and the cationic curing agent (B) is applied to at least a part of the main surface of the nitrogen-containing compound-containing layer.
Hereinafter, the nitrogen-containing compound-containing layer, the curable composition, and the method for applying the curable composition will be described in order.

[Nitrogen-containing compound-containing layer]
The nitrogen-containing compound-containing layer is a layer containing a nitrogen-containing compound containing a nitrogen atom having a lone electron pair. In the nitrogen-containing compound layer, the base material component which is a matrix for dispersing the nitrogen-containing compound is not particularly limited as long as the object of the present invention is not impaired.
Examples of the base material component include cured products of various resins and various curable compounds.

Specific examples of the resin that can be used as the base material component include polyacetal resin, polyamide resin, polycarbonate resin, polyester resin (polybutylene terephthalate, polyethylene terephthalate, polyarylate, etc.), FR-AS resin, FR-ABS resin, AS resin. , ABS resin, polyphenylene oxide resin, polyphenylene sulfide resin, polysulfone resin, polyethersulfone resin, polyether ether ketone resin, fluororesin, polyimide resin, polyamideimide resin, polyamidebismaleimide resin, polyetherimide resin, polybenzoxazole Resin, polybenzothiazole resin, polybenzoimidazole resin, silicone resin, BT resin, polymethylpentene, ultrahigh molecular weight polyethylene, FR-polypropylene, (meth) acrylic resin (polymethylmethacrylate, etc.), cardo resin, polystyrene, etc. Can be mentioned. These resins may be used in combination of two or more.

Examples of the curable compound that gives a cured product as a base material component include a bifunctional or higher functional epoxy compound and a bifunctional or higher functional oxetane compound. The polyfunctional epoxy compound and the polyfunctional oxetane compound are cured by exposure and / or heating after using a curing agent or a curing accelerator as necessary to give a cured product having excellent heat resistance and mechanical properties.

Further, as will be described later, etching may be performed on the laminate containing the nitrogen-containing compound-containing layer and the cured product layer. In this case, for example, a sacrificial film may be further formed on the upper layer of the cured product layer. When forming the sacrificial film, the etching rate of each layer of the sacrificial film and the cured product layer with respect to the etchant may be appropriately adjusted according to the shape of the cured product layer after etching or the film thickness and shape of the sacrificial film. When the cured product layer has a protruding or hemispherical shape for microlens applications, for example, the etching rates of the sacrificial film and the cured product layer may be the same, and the matrix of the cured product layer is a cation. The curable compound (A) preferably contains an aromatic ring, and more preferably contains a compound represented by the formula (a1). The matrix of the nitrogen-containing compound-containing layer on the lower side of the cured product layer may be appropriately selected depending on the necessity of patterning or removal of the nitrogen-containing compound-containing layer. A (meth) acrylic resin, a (meth) acrylic resin containing an aromatic ring, or a cardo-based resin is preferable.

The thickness of the nitrogen-containing compound-containing layer is not particularly limited. Typically, the thickness of the nitrogen-containing compound-containing layer is, for example, 0.1 μm or more and 10 μm or less, preferably 0.2 μm or more and 5 μm or less, and more preferably 0.3 μm or more and 2 μm or less.

[Nitrogen-containing compound]
The nitrogen-containing compound is not particularly limited as long as it is a nitrogen-containing compound containing a nitrogen atom having a lone electron pair. The nitrogen-containing compound containing a nitrogen atom having a lone electron pair may be a salt or a complex.
Hereinafter, a nitrogen-containing compound containing a nitrogen atom having a lone electron pair may be simply referred to as a "nitrogen-containing compound". In the specification and claims of the present application, "nitrogen-containing compound" means a nitrogen-containing compound containing a nitrogen atom having a lone electron pair, unless otherwise specified.

The above method for producing a laminate is particularly effective when the lone electron pair of the nitrogen atom in the nitrogen-containing compound is not delocalized in the molecule of the nitrogen-containing compound by conjugation. This is because when the nitrogen-containing compound-containing layer contains such a nitrogen-containing compound, the problem of poor curing of the curable composition is remarkable.

Examples of nitrogen-containing compounds that are likely to cause curing defects in curable compositions include amines that do not have an aromatic group that binds to a nitrogen atom, imines that do not have an aromatic group that binds to a nitrogen atom, and imines that do not have an aromatic group that binds to a nitrogen atom. Examples thereof include aromatic nitrogen-containing heterocyclic compounds in which a lone electron pair is not incorporated in the aromatic ring system.

In nitrogen-containing compounds as described above, nitrogen atoms having lone electron pairs often form so-called chromophores or axochromes. In various laminates, a colored layer containing a dye compound containing a nitrogen atom having a lone electron pair is often formed.
Typical examples of the case where the nitrogen-containing compound is a dye compound include a phthalocyanine pigment, a dioxazine pigment and the like. The phthalocyanine pigment may be, for example, a metal phthalocyanine complex such as copper phthalocyanine.

When the nitrogen-containing compound is a dye compound, the nitrogen-containing compound-containing layer is colored. The colored nitrogen-containing compound-containing layer is preferably a color filter used in various types of image display panels, CMOS image sensors, and the like.
The hue of the color filter is not particularly limited. When the nitrogen-containing compound-containing layer is a color filter, the color filter may typically be a green color filter, a blue color filter, or a red color filter.

The content of the nitrogen-containing compound in the nitrogen-containing compound-containing layer is not particularly limited. The content of the nitrogen-containing compound in the nitrogen-containing compound-containing layer is typically 1% by mass or more and 80% by mass or less, preferably 5% by mass or more and 75% by mass or less, based on the mass of the nitrogen-containing compound-containing layer. , 40% by mass or more and 70% by mass or less is more preferable.

[Curable composition]
The curable composition contains a cationic curable compound (A) and a cationic curing agent (B).
The curable composition preferably gives a transparent cured product. Here, in the specification of the present application and the scope of claims, "transparency" means that the value when the transmittance at a wavelength of 400 nm is measured using a spectroscopic measuring instrument is 95% or more. The transmittance is measured using a cured film of a curable composition having a film thickness of 3 μm. As the spectroscopic measuring instrument, MCPD-3000 manufactured by Otsuka Electronics Co., Ltd. can be used.
Further, the curable composition preferably gives a cured product having a high refractive index at a wavelength of 589 nm. Specifically, the refractive index of the cured product is preferably 1.60 or more, more preferably 1.63 or more, further preferably 1.65 or more, and particularly preferably 1.68 or more. The upper limit of the refractive index of the cured product is not particularly limited, but usually 2.3 or less, 2.0 or less, or when only organic materials are used (when fine particles such as inorganic or metal oxides are not used) 1. It is 8 or less.
A cured product layer made of a cured product exhibiting such a high refractive index can be suitably used as an optical functional layer or a precursor layer for forming a microlens in a laminated body.

Hereinafter, essential or arbitrary components contained in the curable composition will be described.

[Cation-curable compound (A)]
As the cationically curable compound (A), various compounds conventionally known as cationically curable compounds can be used. By curing the cationically curable compound (A) with a cationic curing agent (B) described later, the curable composition is satisfactorily cured even if the curable composition is in contact with the nitrogen-containing compound-containing layer.

（式（ａ１）中、Ｗ^１及びＷ^２は、それぞれ独立に、下記式（ａ２）：

で表される基であり、
式（ａ２）中、環Ｚは芳香族炭化水素環を示し、Ｘは単結合又は−Ｓ−で示される基を示し、Ｒ^１は単結合、炭素原子数が１以上４以下であるアルキレン基、又は炭素原子数が１以上４以下であるアルキレンオキシ基を示し、Ｒ^１がアルキレンオキシ基である場合、アルキレンオキシ基中の酸素原子が環Ｚと結合し、Ｒ^２は１価炭化水素基、水酸基、−ＯＲ^４ａで示される基、−ＳＲ^４ｂで示される基、アシル基、アルコキシカルボニル基、ハロゲン原子、ニトロ基、シアノ基、メルカプト基、カルボキシ基、アミノ基、カルバモイル基、−ＮＨＲ^４ｃで示される基、−Ｎ（Ｒ^４ｄ）_２で示される基、スルホ基、又は１価炭化水素基、−ＯＲ^４ａで示される基、−ＳＲ^４ｂで示される基、アシル基、アルコキシカルボニル基、−ＮＨＲ^４ｃで示される基、もしくは−Ｎ（Ｒ^４ｄ）_２で示される基に含まれる炭素原子に結合した水素原子の少なくとも一部が１価炭化水素基、水酸基、−ＯＲ^４ａで示される基、−ＳＲ^４ｂで示される基、アシル基、アルコキシカルボニル基、ハロゲン原子、ニトロ基、シアノ基、メルカプト基、カルボキシル基、アミノ基、カルバモイル基、−ＮＨＲ^４ｃで示される基、−Ｎ（Ｒ^４ｄ）_２で示される基、メシルオキシ基、もしくはスルホ基で置換された基を示し、Ｒ^４ａ〜Ｒ^４ｄは独立に１価炭化水素基を示し、ｍは０以上の整数を示し、Ｒ^３は、水素原子、ビニル基、チイラン−２−イルメチル基、又はグリシジル基であり、
Ｗ^１とＷ^２との双方がＲ^３として水素原子を有することはなく、
環Ｙ^１及び環Ｙ^２は同一の又は異なる芳香族炭化水素環を示し、Ｒは単結合、置換基を有してもよいメチレン基、置換基を有してもよく、２個の炭素原子間にヘテロ原子を含んでもよいエチレン基、−Ｏ−で示される基、−ＮＨ−で示される基、又は−Ｓ−で示される基を示し、Ｒ^３ａ及びＲ^３ｂは独立にシアノ基、ハロゲン原子、又は１価炭化水素基を示し、ｎ１及びｎ２は独立に０以上４以下の整数を示す。） As the cationically curable compound (A), a compound represented by the following formula (a1) is preferable in that it has good transparency, has a high refractive index, and easily forms a cured product that can be etched well.

(In the formula (a1), ^{W 1} and ^{W 2} are each independently represented by the following formula (a2):

It is a group represented by
In the formula (a2), ring Z represents an aromatic hydrocarbon ring, X represents a single bond or a group represented by −S−, R ¹ is a single bond, and an alkylene group having 1 or more and 4 or less carbon atoms. , Or an alkyleneoxy group having 1 or more and 4 or less carbon atoms, and when R ¹ is an alkyleneoxy group, the oxygen atom in the alkyleneoxy group is bonded to the ring Z, and R ² is a monovalent hydrocarbon group. , Hydrocarbon, group represented by -OR ^4a , group represented by -SR ^4b , acyl group, alkoxycarbonyl group, halogen atom, nitro group, cyano group, mercapto group, carboxy group, amino group, carbamoyl group, -NHR ^4c , -N (R ^4d ) ₂ , sulfo group, or monovalent hydrocarbon group, -OR ^4a , -SR ^4b , acyl group, alkoxycarbonyl group, At least a part of the hydrogen atoms bonded to the carbon atom contained in the group represented by ^{−NHR 4c} or the group represented by −N (R ^4d ) ₂ ^{is a monovalent hydrocarbon group, a hydroxyl group, or a group represented by −OR 4a.} , -SR ^4b group, acyl group, alkoxycarbonyl group, halogen atom, nitro group, cyano group, mercapto group, carboxyl group, amino group, carbamoyl group, -NHR ^4c group, -N (R ^4d) ) _{Indicates a group represented by 2} , a mesyloxy group, or a group substituted with a sulfo group, R ^{4a to} R ^4d independently indicate a monovalent hydrocarbon group, m indicates an integer of 0 or more, and R ³ indicates an integer of 0 or more. A hydrogen atom, a vinyl group, a thiran-2-ylmethyl group, or a glycidyl group,
Both W ¹ and W ² do not have a hydrogen atom as R ^3,
Ring Y ¹ and ring Y ² denote the same or different aromatic hydrocarbon ring, R represents a single bond, methylene group which may have a substituent, may have a substituent, 2 carbon atoms An ethylene group which may contain a hetero atom in between, a group represented by -O-, a group represented by -NH-, or a group represented by -S- is shown, and R ^3a and R ^3b are independently cyano groups and halogens. It represents an atom or a monovalent hydrocarbon group, and n1 and n2 independently represent an integer of 0 or more and 4 or less. )

In the above formula (a2), the ring Z is, for example, a benzene ring, a fused polycyclic aromatic hydrocarbon ring [for example, a fused bicyclic hydrocarbon ring (for example, a _C8-20 fused binary ring such as a naphthalene ring). _{Condensed 2-4 ring aromatic hydrocarbons such as formal} hydrocarbon rings, preferably C 10-16 fused bicyclic hydrocarbon rings), fused tricyclic aromatic hydrocarbon rings (eg, anthracene rings, phenanthrene rings, etc.) Hydrogen ring] and the like. Ring Z is preferably a benzene ring or a naphthalene ring, and more preferably a naphthalene ring. ^{Since W 1} and W ² in the formula (a 1) are independently represented by the following formula (a 2), W ¹ and W ² each include a ring Z. The ^{ring Z contained in W 1} and the ring Z contained in W ² may be the same or different. For example, one ring may be a benzene ring, the other ring may be a naphthalene ring, or the like. It is particularly preferable that the ring of is also a naphthalene ring.

Further, the substitution position of the ring Z bonded to the carbon atom to which both ^{W 1} and W ^{2 are directly connected via X is not particularly limited.} For example, when the ring Z is a naphthalene ring, the group corresponding to the ring Z bonded to the carbon atom may be a 1-naphthyl group, a 2-naphthyl group, or the like.

In the above formula (a2), X independently represents a single bond or a group represented by −S−, and is typically a single bond.

In the above formula (a2), R ¹ is, for example, a single bond; an alkylene having a carbon atom number of 1 or more and 4 or less, such as a methylene group, an ethylene group, a trimethylene group, a propylene group, and a butane-1,2-diyl group. Group: An alkyleneoxy group having 1 or more and 4 or less carbon atoms such as a methyleneoxy group, an ethyleneoxy group and a propyleneoxy group can be mentioned, and a single bond; a C _2-4 alkylene group (particularly, an ethylene group, a propylene group and the like) can be mentioned. C _2-3 alkylene group); C _2-3 alkyleneoxy group (particularly, C _2-3 alkylene group such as ethyleneoxy group and propyleneoxy group) is preferable, and a single bond is more preferable. When R ¹ is an alkyleneoxy group, the oxygen atom in the alkyleneoxy group is bonded to the ring Z. ^{Further, since W 1} and W ² in the formula (a 1) are independently represented by the following formula (a 2), W ¹ and W ² each have a divalent group R ¹ . include. The R ¹ contained in R ¹ and W ² included in W ^1, it may be the same or may be different.

In the above formula (a2), R ² _{is, for example, a C 1-12} alkyl group such as an alkyl group (for example, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, etc., preferably a C _1-8 alkyl group. , More preferably a C _1-6 alkyl group, etc.), a cycloalkyl group (a C _5-10 cycloalkyl group such as a cyclohexyl group, preferably a C _5-8 cycloalkyl group, more preferably a C _5-6 cycloalkyl group, etc.) _{), Aryl group (for example, C 6-14} aryl group such as phenyl group, trill group, xsilyl group, naphthyl group, preferably C _6-10 aryl group, more preferably C _6-8 aryl group, etc.), Alkoxy group. Monovalent hydrocarbon groups such as (C _6-10 aryl-C _{1-4 alkyl groups such as benzyl group and phenethyl group); hydroxyl groups; C 1} such as alkoxy groups (methoxy group, ethoxy group, propoxy group, butoxy group, etc.) _-12 Alkoxy groups, preferably C _1-8 alkoxy groups, more preferably C _1-6 alkoxy groups, etc.), cycloalkoxy groups (C _5-10 cycloalkoxy groups such as cyclohexyloxy groups), aryloxy groups (phenoxy). _{C 6-10} aryloxy groups such as groups), an aralkyl group (e.g., group [wherein represented by ^{-OR 4a} of _{C 6-10} aryl _{-C 1-4} alkyl group) such as a benzyloxy group, R ^4a represents a monovalent hydrocarbon group (such as the above-exemplified monovalent hydrocarbon group). _{]; Alkylthio group (C 1-12} alkyl thio group such as methyl thio group, ethyl thio group, propyl thio group, butyl thio group, preferably C _1-8 alkyl thio group, more preferably C _1-6 alkyl thio group, etc.), cycloalkyl thio group ( _{C 5-10} cycloalkylthio group such as cyclohexylthio group), arylthio group (C _6-10 arylthio group such as phenylthio group), aralkylthio group (for example, C _6-10aryl- C _{1-4 such as benzylthio group)} Alkylthio group) and other groups represented by −SR ^4b [In the formula, R ^4b represents a monovalent hydrocarbon group (such as the above-exemplified monovalent hydrocarbon group). ]; Acyl group (C _1-6 acyl group such as acetyl group); alkoxycarbonyl group (C _1-4 alkoxy-carbonyl group such as methoxycarbonyl group); halogen atom (fluorine atom, chlorine atom, bromine atom, etc.) Iodine atom, etc.); Nitro group; Cyan group; Mercapto group; carboxyl group; Amino group; Carbamoyl group; Alkylamino group (methylamino group, ethylamino group, propylamino group, butylamino group, etc. C _1-12 alkylamino Group, preferably C _1-8 alkylamino group, more preferably C _1-6 alkylamino group, etc.), cycloalkylamino group (C _5-10 cycloalkylamino group such as cyclohexylamino group), arylamino group (preferably C 5-10 cycloalkylamino group such as cyclohexylamino group), arylamino group ( A group represented by −NHR ^4c such as a C _6-10 arylamino group such as a phenylamino group) and an aralkylamino group (for example, a C _6-10aryl- C _1-4 alkylamino group such as a benzylamino group) [formula]. Among them, R ^4c represents a monovalent hydrocarbon group (such as the above-exemplified monovalent hydrocarbon group). ]; Dialkylamino groups (dimethylamino group, diethylamino group, dipropylamino group, dibutylamino group and other di (C _1-12 alkyl) amino groups, preferably di (C _1-8 alkyl) amino groups, more preferably. Di (C _1-6 alkyl) amino group, etc.), Dicycloalkylamino group (di (C _5-10 cycloalkyl) amino group such as dicyclohexylamino group, etc.), Diarylamino group (di (C) such as diphenylamino group) _6-10 aryl) amino group), dialalkylamino group (for example, di (C _6-10aryl- C _1-4 alkyl) amino group such as dibenzylamino group), etc. indicated by ^{-N (R 4d} ) _2. [In the formula, R ^4d independently represents a monovalent hydrocarbon group (such as the above-exemplified monovalent hydrocarbon group). ]; (Meta) acryloyloxy group; sulfo group; the above monovalent hydrocarbon group, the group represented by -OR ^4a , the group represented by -SR ^4b , the acyl group, the alkoxycarbonyl group, the group represented by -NHR ^4c. Or, at least a part of the hydrogen atom bonded to the carbon atom contained in the group represented by -N (R ^4d ) ₂ ^{is the above monovalent hydrocarbon group, hydroxyl group, group represented by -OR 4a} , -SR ^4b . Represented group, acyl group, alkoxycarbonyl group, halogen atom, nitro group, cyano group, mercapto group, carboxyl group, amino group, carbamoyl group, group represented by -NHR ^4c , represented by -N (R ^4d ) _2. Group, (meth) acryloyloxy group, mesyloxy group, or sulfo group-substituted group [eg, alkoxyaryl group (eg, C _1-4 alkoxy C _6-10 aryl group such as methoxyphenyl group), alkoxycarbonylaryl Groups (for example, C _1-4 alkoxy-carbonyl C _6-10 aryl groups such as methoxycarbonylphenyl group and ethoxycarbonylphenyl group)] and the like can be mentioned.

Of these, typically R ² is a monovalent hydrocarbon group, a group represented by -OR ^4a , a group represented by -SR ^4b , an acyl group, an alkoxycarbonyl group, a halogen atom, a nitro group, and a cyano group. , The ^{group represented by -NHR 4c} , the group represented by -N (R ^4d ) ₂ , and the like may be used.

Preferred R ^2s include monovalent hydrocarbon groups [eg, alkyl groups (eg, C _1-6 alkyl groups), cycloalkyl groups (eg, C _5-8 cycloalkyl groups), aryl groups (eg, C _{6-). 10} aryl group), aralkyl group (for example, C _6-8 aryl-C _1-2 alkyl group), etc.], alkoxy group (C _1-4 alkoxy group, etc.) and the like. In particular, R ^2a and R ^2b are monovalent hydrocarbons such as alkyl groups [C _1-4 alkyl groups (particularly methyl groups)] and aryl groups [for example, C _6-10 aryl groups (particularly phenyl groups)]. It is preferably a group (particularly an alkyl group).

When m is an integer of 2 or more, the plurality of R ^2s may be different from each other or may be the same. Further, the R ² contained in R ² and W ² included in W ^1, it may be the same or may be different.

In the above formula (a2), ^{the number m of R 2} can be selected according to the type of ring Z, and may be, for example, 0 or more and 4 or less, preferably 0 or more and 3 or less, and more preferably 0 or more and 2 or less. .. Note that ^{m in W 1} and m in W ² may be the same or different.

In the above formula (a3), ^{R 3} is a hydrogen atom, a vinyl group, thiirane-2-ylmethyl group, or a glycidyl group. Both W ¹ and W ² do not have a hydrogen atom as ^{R 3.}

The vinyloxy group, the thiran-2-ylmethyl group, and the glycidyl group are all cationically polymerizable functional groups. Therefore, the compound represented by the formula (a1) is a cationically polymerizable compound having 1 or 2 cationically polymerizable functional groups.

The R ³ contained in R ³ and W ² included in W ^1, as long as both are not hydrogen atoms, may be the same or may be different. The ^{R 3} contained in ^{R 3} and ^{W 2} included in W ^1, both a vinyl group, thiirane-2-ylmethyl group, or is preferably Ku glycidyl group, both a vinyl group, thiirane -2 -It is more preferable that it is the same group selected from the group consisting of an ylmethyl group and a glycidyl group.

The R ^3, since the synthesis and availability of the compound represented by the formula (a1) is easy, vinyl group, or glycidyl group is preferable.

In the above formula (a1), the ring Y ¹ and the ring Y ² include, for example, a benzene ring, a fused polycyclic aromatic hydrocarbon ring [for example, a fused bicyclic hydrocarbon ring (for example, C _{8 such as a naphthalene ring). Condensation 2-4 of -20} fused bicyclic hydrocarbon rings, preferably C _10-16 fused bicyclic hydrocarbon rings), fused tricyclic aromatic hydrocarbon rings (eg, anthracene rings, phenanthrene rings, etc.) Cyclic aromatic hydrocarbon ring] and the like. Ring Y ¹ and ring Y ² are preferably a benzene ring or a naphthalene ring, and more preferably a benzene ring. Ring Y ¹ and ring Y ² may be the same or different. For example, one ring may be a benzene ring, the other ring may be a naphthalene ring, or the like.

In the above formula (a1), R is a single bond, a methylene group which may have a substituent, an ethylene group which may have a substituent and may contain a heteroatom between two carbon atoms, −O. It represents a group represented by −, a group represented by −NH−, or a group represented by −S−, and is typically a single bond. Here, as the substituent, for example, a cyano group, a halogen atom (fluorine atom, chlorine atom, bromine atom, etc.), a monovalent hydrocarbon group [for example, an alkyl group (methyl group, ethyl group, propyl group, isopropyl group, etc., _{C 1-6} alkyl group such as butyl group and t-butyl group), aryl group (C _6-10 aryl group such as phenyl group), etc.] and the like, and examples of the hetero atom include an oxygen atom and a nitrogen atom. , Sulfur atom, silicon atom and the like.

In the above formula (a1), R ^3a and R ^3b are usually non-reactive substituents such as a cyano group, a halogen atom (fluorine atom, chlorine atom, bromine atom, etc.) and a monovalent hydrocarbon group [for example. Alkyl group, aryl group (C _6-10 aryl group such as phenyl group), etc.] and the like, preferably a cyano group or an alkyl group, and particularly preferably an alkyl group. _{Examples of the alkyl group include C 1-6} alkyl groups such as methyl group, ethyl group, propyl group, isopropyl group, butyl group and t-butyl group (for example, C _1-4 alkyl group, particularly methyl group) and the like. .. When n1 is an integer of 2 or more, R ^3a may be different from each other or may be the same. Further, when n2 is an integer of 2 or more, R ^3b may be different from each other or may be the same. Further, R ^3a and R ^3b may be the same or different. Further, the bonding position (replacement position) of R ^3a and R ^{3b with} respect to the ring Y ¹ and the ring Y ^{2 is not particularly limited.} The preferred substitution numbers n1 and n2 are 0 or 1, especially 0. Note that n1 and n2 may be the same or different from each other.

The compound represented by the above formula (a1) has high reactivity because it has a cationically polymerizable functional group while maintaining excellent optical and thermal properties. In particular, when rings Y ¹ and Y ² are benzene rings and R is a single bond, the compound represented by the above formula (a1) has a fluorene skeleton, and further has optical and thermal properties. Excellent.

Further, the compound represented by the above formula (a1) gives a cured product having high hardness and is preferable as a base material component in the composition.

Among the compounds represented by the above formula (a1), particularly preferable specific examples are 9,9-bis [4- [2- (glycidyloxy) ethoxy] phenyl] -9H-fluorene, 9,9-bis [ 4- [2- (glycidyloxy) ethyl] phenyl] -9H-fluorene, 9,9-bis [4- (glycidyloxy) -3-methylphenyl] -9H-fluorene, 9,9-bis [4-( Glycidyloxy) -3,5-dimethylphenyl] -9H-fluorene, 9,9-bis (6-glycidyloxynaphthalene-1-yl) -9H-fluorene and 9,9-bis (5-glycidyloxynaphthalene-2) -Il) -9H-Epoxy group-containing fluorene compounds such as fluorene; and compounds represented by the following formulas can be mentioned.

Among the compounds represented by the formula (a1) described above, the following compounds are particularly preferable.

The cationically curable compound (A) may contain a cationically curable compound other than the compound represented by the above formula (a1). When the cationically curable compound (A) contains a cationically curable compound other than the compound represented by the above formula (a1), the amount of the compound represented by the above formula (a1) in the cationically curable compound (A) is , 50% by mass or more, more preferably 70% by mass or more, even more preferably 80% by mass or more, particularly preferably 90% by mass or more, and most preferably 100% by mass.

Preferred examples of the cationically curable compound other than the compound represented by the formula (a1) include a vinyl ether compound containing a vinyloxy group, an epoxy compound containing an epoxy group, and an episulfide compound containing an episulfide group. Hereinafter, vinyl ether compounds, epoxy compounds, and episulfide compounds will be described.

(Vinyl ether compound)
The vinyl ether compound as the cationically curable compound (A) other than the compound represented by the formula (a1) is not particularly limited as long as it has a vinyloxy group and is cationically polymerizable.

The vinyl ether compound used in combination with the compound represented by the formula (a1) may or may not contain an aromatic group.
From the viewpoint of good thermal decomposition resistance of the cured product, the vinyl ether compound used in combination with the compound represented by the formula (a1) is preferably a compound having a vinyloxy group bonded to an aromatic group.

Suitable specific examples of the vinyl ether compound that can be used together with the compound represented by the formula (a1) include vinylphenyl ether, 4-vinyloxytoluene, 3-vinyloxytoluene, 2-vinyloxytoluene, and 1-vinyloxy-. 4-Chlorobenzene, 1-vinyloxy-3-chlorobenzene, 1-vinyloxy-2-chlorobenzene, 1-vinyloxy-2,3-dimethylbenzene, 1-vinyloxy-2,4-dimethylbenzene, 1-vinyloxy-2,5- Dimethylbenzene, 1-vinyloxy-2,6-dimethylbenzene, 1-vinyloxy-3,4-dimethylbenzene, 1-vinyloxy-3,5-dimethylbenzene, 1-vinyloxynaphthalene, 2-vinyloxynaphthalene, 2- Vinyloxyfluorene, 3-vinyloxyfluorene, 4-vinyloxy-1,1'-biphenyl, 3-vinyloxy-1,1'-biphenyl, 2-vinyloxy-1,1'-biphenyl, 6-vinyloxytetraline, and Aromatic monovinyl ether compounds such as 5-vinyloxytetraline; 1,4-divinyloxybenzene, 1,3-divinyloxybenzene, 1,2-divinyloxybenzene, 1,4-divinyloxynaphthalene, 1 , 3-Divinyloxynaphthalene, 1,2-dibinyloxynaphthalene, 1,5-dibinyloxynaphthalene, 1,6-dibinyloxynaphthalene, 1,7-dibinyloxynaphthalene, 1,8-dibini Loxynaphthalene, 2,3-dibinyloxynaphthalene, 2,6-dibinyloxynaphthalene, 2,7-dibinyloxynaphthalene, 1,2-dibinyloxyfluorene, 3,4-dibinyloxyfluorene, 2, 7-Diviniroxyfluorene, 4,4'-dibiniroxybiphenyl, 3,3'-dibiniroxybiphenyl, 2,2'-dibiniroxybiphenyl, 3,4'-dibiniroxybiphenyl, 2,3 Examples include aromatic divinyl ether compounds such as'-dibinyloxybiphenyl, 2,4'-dibinyloxybiphenyl, and bisphenol A divinyl ether.
These vinyl ether compounds may be used in combination of two or more.

(Epoxy compound)
Examples of the epoxy compound as the cationic curable compound (A) other than the compound represented by the formula (a1) include a bisphenol A type epoxy resin, a bisphenol F type epoxy resin, a bisphenol S type epoxy resin, and a bisphenol AD type epoxy resin. , Naphthalene type epoxy resin, biphenyl type epoxy resin and other bifunctional epoxy resins; phenol novolac type epoxy resin, brominated phenol novolac type epoxy resin, orthocresol novolac type epoxy resin, bisphenol A novolac type epoxy resin, and bisphenol AD novolac. Novolak epoxy resin such as type epoxy resin; ring-type aliphatic epoxy resin such as epoxidized product of dicyclopentadiene type phenol resin; aromatic epoxy resin such as epoxidized product of naphthalene type phenol resin; glycidyl ester of dimer acid, and triglycidyl ester Glycidyl ester type epoxy resin such as tetraglycidylaminodiphenylmethane, triglycidyl-p-aminophenol, tetraglycidylmethoxylylylene diamine, and glycidylamine type epoxy resin such as tetraglycidylbisaminomethylcyclohexane; complex such as triglycidyl isocyanurate. Cyclic epoxy resin; fluoroglycinol triglycidyl ether, trihydroxybiphenyl triglycidyl ether, trihydroxyphenylmethane triglycidyl ether, glycerin triglycidyl ether, 2- [4- (2,3-epoxypropoxy) phenyl] -2- [4- [1,1-bis [4- (2,3-epoxypropoxy) phenyl] ethyl] phenyl] propane, and 1,3-bis [4- [1- [4- (2,3-epoxypropoxy) phenyl] ethyl] propane ) Phenyl] -1- [4- [1- [4- (2,3-epoxypropoxy) phenyl] -1-methylethyl] phenyl] ethyl] phenoxy] -2-propanol and other trifunctional epoxy resins; tetra Tetrafunctional epoxy resins such as hydroxyphenyl ethane tetraglycidyl ether, tetraglycidyl benzophenone, bisresorcinol tetraglycidyl ether, and tetraglycidoxybiphenyl; 1,2-epoxy of 2,2-bis (hydroxymethyl) -1-butanol; -4- (2-oxylanyl) cyclohexane adducts can be mentioned. The 1,2-epoxy-4- (2-oxylanyl) cyclohexane adduct of 2,2-bis (hydroxymethyl) -1-butanol is commercially available as EHPE-3150 (manufactured by Daicel).

Further, an oligomer-type or polymer-type polyfunctional epoxy compound can also be preferably used as the cationically curable compound (A).
Typical examples are phenol novolac type epoxy compound, brominated phenol novolac type epoxy compound, orthocresol novolac type epoxy compound, xylenol novolac type epoxy compound, naphthol novolac type epoxy compound, bisphenol A novolac type epoxy compound, bisphenol AD novolac. Examples thereof include a type epoxy compound, an epoxidized product of a dicyclopentadiene type phenol resin, and an epoxidized product of a naphthalene type phenol resin.

Another example of a suitable epoxy compound is a polyfunctional alicyclic epoxy compound having an alicyclic epoxy group. When the cationically curable compound (A) contains an alicyclic epoxy compound, it is easy to form a cured product having excellent transparency by using the curable composition.

Specific examples of the alicyclic epoxy compound include 2- (3,4-epoxycyclohexyl-5,5-spiro-3,4-epoxy) cyclohexane-meth-dioxane and bis (3,4-epoxycyclohexylmethyl) adipate. , Bis (3,4-epoxy-6-methylcyclohexylmethyl) adipate, 3,4-epoxy-6-methylcyclohexyl-3', 4'-epoxy-6'-methylcyclohexanecarboxylate, ε-caprolactone modified 3, 4-Epoxycyclohexylmethyl-3', 4'-epoxycyclohexanecarboxylate, trimethylcaprolactone modified 3,4-epoxycyclohexylmethyl-3', 4'-epoxycyclohexanecarboxylate, β-methyl-δ-valerolactone modified 3, 4-epoxycyclohexylmethyl-3', 4'-epoxycyclohexanecarboxylate, methylenebis (3,4-epoxycyclohexane), ethylene glycol di (3,4-epoxycyclohexylmethyl) ether, ethylenebis (3,4-epoxy) Cyclohexanecarboxylate), dioctyl epoxycyclohexahydrophthalate, and di-2-ethylhexyl epoxycyclohexahydrophthalate, epoxy resins having a tricyclodeceneoxide group, and the following formulas (a01-1) to (a01-5). Examples thereof include compounds represented by.

Among the specific examples of these alicyclic epoxy compounds, the alicyclic epoxy compounds represented by the following formulas (a01-1) to (a01-5) are preferable because they give a cured product having a high hardness.

（式（ａ０１−１）中、Ｚ^０１は単結合又は連結基（１以上の原子を有する２価の基）を示す。Ｒ^ａ０１〜Ｒ^ａ０１８は、それぞれ独立に、水素原子、ハロゲン原子、及び有機基からなる群より選択される基である。）

(In formula (a01-1), Z ⁰¹ represents a single bond or a linking group (a divalent group having one or more atoms). R ^{a01 to} R ^a018 are independent hydrogen atoms, halogen atoms, and halogen atoms, respectively. It is a group selected from the group consisting of organic groups.)

Examples of the linking group Z ⁰¹ include divalent hydrocarbon groups, -O-, -O-CO-, -S-, -SO-, _{-SO 2- , -CBr 2-} , and -C (CBr ₃ ). _{2 -, - C (CF 3} ) 2 -, and ^{-R a019} -O-CO- 2 divalent group and which are selected from the group consisting of these can be exemplified a plurality bonded group.

Examples of the divalent hydrocarbon group as the linking group Z ⁰¹ include a linear or branched alkylene group having 1 to 18 carbon atoms and a divalent alicyclic hydrocarbon group. Can be done. Examples of the linear or branched alkylene group having 1 or more and 18 or less carbon atoms include a methylene group, a methylmethylene group, a dimethylmethylene group, a dimethylene group, a trimethylene group and the like. Examples of the divalent alicyclic hydrocarbon group include 1,2-cyclopentylene group, 1,3-cyclopentylene group, cyclopentylidene group, 1,2-cyclohexylene group and 1,3-. Examples thereof include a cycloalkylene group (including a cycloalkylidene group) such as a cyclohexylene group, a 1,4-cyclohexylene group and a cyclohexylidene group.

R ^a019 is an alkylene group having 1 or more carbon atoms and 8 or less carbon atoms, and is preferably a methylene group or an ethylene group.

（式（ａ０１−２）中、Ｒ^ａ０１〜Ｒ^ａ０１８は、水素原子、ハロゲン原子、及び有機基からなる群より選択される基である。Ｒ^ａ０２及びＲ^ａ０１０は、互いに結合してもよい。Ｒ^ａ０１３及びＲ^ａ０１６は互いに結合して環を形成してもよい。ｍ^ａ１は、０又は１である。）

(In the formula (a01-2), R ^{a01 to} R ^a018 are groups selected from the group consisting of a hydrogen atom, a halogen atom, and an organic group. R ^a02 and R ^a010 may be bonded to each other. R ^A013 and ^{R A016} good ^{.m a1} be bonded to each other to form a ring is 0 or 1.)

（式（ａ０１−２−１）中、Ｒ^ａ０１〜Ｒ^ａ０１２は、水素原子、ハロゲン原子、及び有機基からなる群より選択される基である。Ｒ^ａ０２及びＲ^ａ０１０は互いに結合して環を形成してもよい。） Examples of the alicyclic epoxy compound represented by the above formula (a01-2), corresponds to the compound ^{m a1} is 0 in the formula (a01-2), represented by the following formula (a01-2-1) Compounds are preferred.

(In the formula (a01-2-1), R ^{a01 to} R ^a012 are groups selected from the group consisting of a hydrogen atom, a halogen atom, and an organic group. R ^a02 and R ^a010 are bonded to each other to form a ring. May be formed.)

（式（ａ０１−３）中、Ｒ^ａ０１〜Ｒ^ａ０１０は、水素原子、ハロゲン原子、及び有機基からなる群より選択される基である。Ｒ^ａ０２及びＲ^ａ０８は、互いに結合してもよい。）

(In the formula (a01-3), R ^{a01 to} R ^a010 are groups selected from the group consisting of a hydrogen atom, a halogen atom, and an organic group. R ^a02 and R ^a08 may be bonded to each other. )

（式（ａ０１−４）中、Ｒ^ａ０１〜Ｒ^ａ０１２は、水素原子、ハロゲン原子、及び有機基からなる群より選択される基である。Ｒ^ａ０２及びＲ^ａ０１０は、互いに結合してもよい。）

(In the formula (a01-4), R ^{a01 to} R ^a012 are groups selected from the group consisting of a hydrogen atom, a halogen atom, and an organic group. R ^a02 and R ^a010 may be bonded to each other. )

（式（ａ０１−５）中、Ｒ^ａ０１〜Ｒ^ａ０１２は、水素原子、ハロゲン原子、及び有機基からなる群より選択される基である。）

(In the formula (a01-5), R ^{a01 to} R ^a012 are groups selected from the group consisting of a hydrogen atom, a halogen atom, and an organic group.)

In the formulas (a01-1) to (a01-5), when R ^{a01 to} R ^a018 are organic groups, the organic group is not particularly limited as long as it does not impair the object of the present invention, and even if it is a hydrocarbon group. , A group consisting of a carbon atom and a halogen atom, or a group containing a hetero atom such as a halogen atom, an oxygen atom, a sulfur atom, a nitrogen atom and a silicon atom together with a carbon atom and a hydrogen atom. .. Examples of halogen atoms include chlorine atom, bromine atom, iodine atom, fluorine atom and the like.

The organic group includes a hydrocarbon group, a group consisting of a carbon atom, a hydrogen atom, and an oxygen atom, a halogenated hydrocarbon group, a group consisting of a carbon atom, an oxygen atom, and a halogen atom, and a carbon atom and a hydrogen atom. , An oxygen atom, and a group consisting of a halogen atom are preferable. When the organic group is a hydrocarbon group, the hydrocarbon group may be an aromatic hydrocarbon group, an aliphatic hydrocarbon group, or a group containing an aromatic skeleton and an aliphatic skeleton. The number of carbon atoms of the organic group is preferably 1 or more and 20 or less, more preferably 1 or more and 10 or less, and particularly preferably 1 or more and 5 or less.

Specific examples of the hydrocarbon group include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group and n-hexyl group. , N-Heptyl group, n-octyl group, 2-ethylhexyl group, n-nonyl group, n-decyl group, n-undecyl group, n-tridecyl group, n-tetradecyl group, n-pentadecyl group, n-hexadecyl group , N-Heptadecyl group, n-octadecyl group, n-nonadecil group, n-icosyl group and other chain alkyl groups; vinyl group, 1-propenyl group, 2-n-propenyl group (allyl group), 1-n Chain alkenyl groups such as -butenyl group, 2-n-butenyl group, and 3-n-butenyl group; cycloalkyl groups such as cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, and cycloheptyl group; phenyl group , O-tolyl group, m-tolyl group, p-tolyl group, α-naphthyl group, β-naphthyl group, biphenyl-4-yl group, biphenyl-3-yl group, biphenyl-2-yl group, anthryl group, And aryl groups such as phenanthryl groups; aralkyl groups such as benzyl group, phenethyl group, α-naphthylmethyl group, β-naphthylmethyl group, α-naphthylethyl group and β-naphthylethyl group can be mentioned.

Specific examples of halogenated hydrocarbon groups include chloromethyl group, dichloromethyl group, trichloromethyl group, bromomethyl group, dibromomethyl group, tribromomethyl group, fluoromethyl group, difluoromethyl group, trifluoromethyl group, 2,2. , 2-Trifluoroethyl group, pentafluoroethyl group, heptafluoropropyl group, perfluorobutyl group, and perfluoropentyl group, perfluorohexyl group, perfluoroheptyl group, perfluorooctyl group, perfluorononyl group, and Halogen chain alkyl group such as perfluorodecyl group; 2-chlorocyclohexyl group, 3-chlorocyclohexyl group, 4-chlorocyclohexyl group, 2,4-dichlorocyclohexyl group, 2-bromocyclohexyl group, 3-bromocyclohexyl group , And cycloalkyl halides such as 4-bromocyclohexyl group; 2-chlorophenyl group, 3-chlorophenyl group, 4-chlorophenyl group, 2,3-dichlorophenyl group, 2,4-dichlorophenyl group, 2,5-dichlorophenyl group. , 2,6-dichlorophenyl group, 3,4-dichlorophenyl group, 3,5-dichlorophenyl group, 2-bromophenyl group, 3-bromophenyl group, 4-bromophenyl group, 2-fluorophenyl group, 3-fluorophenyl Aryl halide groups such as groups and 4-fluorophenyl groups; 2-chlorophenylmethyl group, 3-chlorophenylmethyl group, 4-chlorophenylmethyl group, 2-bromophenylmethyl group, 3-bromophenylmethyl group, 4-bromophenyl It is a halogenated aralkyl group such as a methyl group, a 2-fluorophenylmethyl group, a 3-fluorophenylmethyl group, and a 4-fluorophenylmethyl group.

Specific examples of the group consisting of a carbon atom, a hydrogen atom, and an oxygen atom are hydroxy chains such as a hydroxymethyl group, a 2-hydroxyethyl group, a 3-hydroxy-n-propyl group, and a 4-hydroxy-n-butyl group. Alkyl group; Cycloalkyl halide group such as 2-hydroxycyclohexyl group, 3-hydroxycyclohexyl group, and 4-hydroxycyclohexyl group; 2-hydroxyphenyl group, 3-hydroxyphenyl group, 4-hydroxyphenyl group, 2,3 Hydroxyaryl groups such as −dihydroxyphenyl group, 2,4-dihydroxyphenyl group, 2,5-dihydroxyphenyl group, 2,6-dihydroxyphenyl group, 3,4-dihydroxyphenyl group, and 3,5-dihydroxyphenyl group. Hydroxyaralkyl groups such as 2-hydroxyphenylmethyl group, 3-hydroxyphenylmethyl group, and 4-hydroxyphenylmethyl group; methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butyloxy group, isobutyloxy Group, sec-butyloxy group, tert-butyloxy group, n-pentyloxy group, n-hexyloxy group, n-heptyloxy group, n-octyloxy group, 2-ethylhexyloxy group, n-nonyloxy group, n-decyloxy Group, n-undecyloxy group, n-tridecyloxy group, n-tetradecyloxy group, n-pentadecyloxy group, n-hexadecyloxy group, n-heptadecyloxy group, n-octadecyloxy group, Chain alkoxy groups such as n-nonadesyloxy group and n-icosyloxy group; vinyloxy group, 1-propenyloxy group, 2-n-propenyloxy group (allyloxy group), 1-n-butenyloxy group, 2-n-butenyloxy Group and chain alkenyloxy group such as 3-n-butenyloxy group; phenoxy group, o-tolyloxy group, m-tolyloxy group, p-tolyloxy group, α-naphthyloxy group, β-naphthyloxy group, biphenyl-4 Aryloxy groups such as −yloxy group, biphenyl-3-yloxy group, biphenyl-2-yloxy group, anthryloxy group, and phenanthryloxy group; benzyloxy group, phenethyloxy group, α-naphthylmethyloxy group, Aralkyloxy groups such as β-naphthylmethyloxy group, α-naphthylethyloxy group, and β-naphthylethyloxy group; methoxymethyl group, ethoxymethyl group, n-propoxymethi Lu group, 2-methoxyethyl group, 2-ethoxyethyl group, 2-n-propoxyethyl group, 3-methoxy-n-propyl group, 3-ethoxy-n-propyl group, 3-n-propoxy-n-propyl Ekalkalkyl groups such as groups, 4-methoxy-n-butyl groups, 4-ethoxy-n-butyl groups, and 4-n-propoxy-n-butyl groups; methoxymethoxy groups, ethoxymethoxy groups, n-propoxymethoxy groups. , 2-Methoxyethoxy group, 2-ethoxyethoxy group, 2-n-propoxyethoxy group, 3-methoxy-n-propoxy group, 3-ethoxy-n-propoxy group, 3-n-propoxy-n-propoxy group, Alkoxyalkoxy groups such as 4-methoxy-n-butyloxy group, 4-ethoxy-n-butyloxy group, and 4-n-propoxy-n-butyloxy group; 2-methoxyphenyl group, 3-methoxyphenyl group, and 4- An alkoxyaryl group such as a methoxyphenyl group; an alkoxyaryloxy group such as a 2-methoxyphenoxy group, a 3-methoxyphenoxy group, and a 4-methoxyphenoxy group; a formyl group, an acetyl group, a propionyl group, a butanoyl group, a pentanoyl group, and a hexanoyl group. An aliphatic acyl group such as a group, a heptanoid group, an octanoyl group, a nonanoyl group, and a decanoyyl group; an aromatic acyl group such as a benzoyl group, an α-naphthoyl group, and a β-naphthoyl group; a methoxycarbonyl group, an ethoxycarbonyl group, n -Propoxycarbonyl group, n-butyloxycarbonyl group, n-pentyloxycarbonyl group, n-hexylcarbonyl group, n-heptyloxycarbonyl group, n-octyloxycarbonyl group, n-nonyloxycarbonyl group, and n-decyl Chain alkyloxycarbonyl groups such as oxycarbonyl groups; aryloxycarbonyl groups such as phenoxycarbonyl groups, α-naphthoxycarbonyl groups, and β-naphthoxycarbonyl groups; formyloxy groups, acetyloxy groups, propionyloxy groups, pigs An aliphatic acyloxy group such as a noyloxy group, a pentanoyloxy group, a hexanoyloxy group, a heptanoiloxy group, an octanoyloxy group, a nonanoyloxy group, and a decanoyloxy group; a benzoyloxy group, an α-naphthoyloxy group, And aromatic acyloxy groups such as β-naphthoyloxy group.

R ^{a01 to} R ^a018 are preferably groups independently selected from the group consisting of a hydrogen atom, a halogen atom, an alkyl group having 1 or more and 5 or less carbon atoms, and an alkoxy group having 1 or more and 5 or less carbon atoms. In particular, it is more preferable that all of ^{R a01 to} R ^a018 are hydrogen atoms because it is easy to form a cured film having excellent mechanical properties.

Wherein ^{(a01-2) ~ (a01-5),} R a01 ~R a018 is the same as ^R a01 ^{to R A018} in formula (a01-1). In the formula (a01-2) and the formula (a01-4), when R ^a02 and R ^a010 are combined with each other, in the formula (a01-2), when R ^a013 and R ^a016 are combined with each other, and in the formula (a01-2). In a01-3), ^{examples of the divalent group formed when R a02} and R a08 are bonded to each other include −CH ₂ − and −C (CH ₃ ) ₂ −.

Among the alicyclic epoxy compounds represented by the formula (a01-1), specific examples of suitable compounds are the following formulas (a01-1a), (a01-1b), and (a01-1c). Examples include the alicyclic epoxy compound represented, 2,2-bis (3,4-epoxycyclohexane-1-yl) propane [= 2,2-bis (3,4-epoxycyclohexyl) propane], and the like. can.

Among the alicyclic epoxy compounds represented by the formula (a01-2), specific examples of suitable compounds are the alicyclic epoxy represented by the following formula (a01-2a) and the following formula (a01-2b). Examples include compounds.

Among the alicyclic epoxy compounds represented by the formula (a01-3), specific examples of suitable compounds include S spiro [3-oxatricyclo [3.2.1.0 ^2,4 ] octane-6. , 2'-Oxylan] and the like.

Among the alicyclic epoxy compounds represented by the formula (a01-4), specific examples of suitable compounds include 4-vinylcyclohexenedioxide, dipentenedioxide, limonene dioxide, and 1-methyl-4- (3). -Methyloxylan-2-yl) -7-oxabicyclo [4.1.0] heptane and the like can be mentioned.

Among the alicyclic epoxy compounds represented by the formula (a01-5), specific examples of suitable compounds include 1,2,5,6-diepoxycyclooctane and the like.

（式（ａ１−Ｉ）中、Ｘ^ａ１、Ｘ^ａ２、及びＸ^ａ３は、それぞれ独立に、水素原子、又はエポキシ基を含んでいてもよい有機基であり、Ｘ^ａ１、Ｘ^ａ２、及びＸ^ａ３が有するエポキシ基の総数が２以上である。） Further, the compound represented by the following formula (a1-I) can be suitably used as the cationically curable compound (A).

(In the formula (a1-I), X ^a1 , X ^a2 , and X ^a3 are organic groups that may independently contain a hydrogen atom or an epoxy group, respectively, and are X ^a1 , X ^a2 , and X ^a3. The total number of epoxy groups contained in is 2 or more.)

（式（ａ１−ＩＩ）中、Ｒ^ａ２０〜Ｒ^ａ２２は、直鎖状、分岐鎖状又は環状のアルキレン基、アリーレン基、−Ｏ−、−Ｃ（＝Ｏ）−、−ＮＨ−及びこれらの組み合わせからなる基であり、それぞれ同一であってもよいし、異なっていてもよい。Ｅ^１〜Ｅ^３は、エポキシ基、オキセタニル基、エチレン性不飽和基、アルコキシシリル基、イソシアネート基、ブロックイソシアネート基、チオール基、カルボキシ基、水酸基及びコハク酸無水物基からなる群より選択される少なくとも１種の置換基又は水素原子である。ただし、Ｅ^１〜Ｅ^３のうち少なくとも２つは、エポキシ基及びオキセタニル基からなる群より選択される少なくとも１種である。） As the compound represented by the above formula (a1-I), a compound represented by the following formula (a1-II) is preferable.

(In the formula (a1-II), R ^{a20 to} R ^a22 are linear, branched or cyclic alkylene groups, arylene groups, -O-, -C (= O)-, -NH- and these. It is a group composed of a combination, and may be the same or different from each other. E ^{1 to} E ³ are an epoxy group, an oxetanyl group, an ethylenically unsaturated group, an alkoxysilyl group, an isocyanate group, and a blocked isocyanate. At least one substituent or hydrogen atom selected from the group consisting of a group, a thiol group, a carboxy group, a hydroxyl group and a succinic anhydride group. However, at least two of ^{E 1 to} E ^{3 are epoxy groups.} And at least one selected from the group consisting of oxetanyl groups.)

In the formula (a1-II) ^{, for example, at least two groups represented by R a20} and E ¹ , R ^a21 and E ² , and R ^a22 and E ³ are represented by the following formula (a1-IIa), respectively. It is preferable that each group is a group represented by the following formula (a1-IIa). The groups represented by the plurality of formulas (a1-IIa) bonded to one compound are preferably the same group.
-LC ^a (a1-IIa)
(In the formula (a1-IIa), L is a group consisting of a linear, branched or cyclic alkylene group, an arylene group, -O-, -C (= O)-, -NH- and a combination thereof. There, ^{C a} is an epoxy group in. the formula (a1-IIa), may form a ring structure by bonding with L and ^{C a.)}

In the formula (a1-IIa), the linear, branched or cyclic alkylene group as L is preferably an alkylene group having 1 or more and 10 or less carbon atoms, and the arylene group as L is preferably an arylene group. An arylene group having 5 or more and 10 or less carbon atoms is preferable. In the formula (a1-IIa), L is a linear alkylene group having 1 or more and 3 or less carbon atoms, a phenylene group, -O-, -C (= O)-, -NH- and a combination thereof. It is preferably a group consisting of, at least one of an alkylene group and a phenylene group having a linear carbon atom number of 1 or more and 3 or less, such as a methylene group, or these, and −O−, −C (=). A group consisting of a combination of at least one of O)-and NH- is preferable.

（式（ａ１−ＩＩｂ）中、Ｒ^ａ２３は、水素原子又はメチル基である。） Wherein (a1-IIa), as if the L and the C ^a is other to form a ring structure bonds, for example, branched alkylene groups and epoxy groups are bonded to a cyclic structure (alicyclic structure (Structure having an epoxy group of) is formed, examples of the organic group represented by the following formulas (a1-IIb) to (a1-IId) can be mentioned.

(In formula (a1-IIb), ^Ra23 is a hydrogen atom or a methyl group.)

Hereinafter, examples of the compound represented by the formula (a1-II) include, but are not limited to, an epoxy compound having an oxylanyl group or an alicyclic epoxy group.

Further, a siloxane compound having two or more glycidyl groups in the molecule (hereinafter, also simply referred to as “siloxane compound”) can be suitably used as the cationically curable compound (A).

The siloxane compound is a compound having a siloxane skeleton composed of a siloxane bond (Si—O—Si) and two or more glycidyl groups in the molecule.

Examples of the siloxane skeleton in the siloxane compound include a cyclic siloxane skeleton and a cage-type or ladder-type polysilsesquioxane skeleton.

As the siloxane compound, a compound having a cyclic siloxane skeleton represented by the following formula (a1-III) (hereinafter, may be referred to as “cyclic siloxane”) is preferable.

In formula (a1-III), ^Ra24 and ^Ra25 represent a monovalent group or an alkyl group containing an epoxy group. ^{However, of the x1 R a24} and the x1 R ^{a25 in} the compound represented by the formula (a1-III), at least two are monovalent groups containing an epoxy group. Further, x1 in the formula (a1-III) indicates an integer of 3 or more. ^{In addition, Ra24} and ^Ra25 in the compound represented by the formula (a1-III) may be the same or different. Further, the plurality of Ra ^24s may be the same or different. The plurality of Ra ^25s may be the same or different.
The alkyl group has, for example, a methyl group, an ethyl group, a propyl group, an isopropyl group, or the like having 1 or more and 18 or less carbon atoms (preferably 1 or more and 6 or less carbon atoms, and particularly preferably 1 or more carbon atoms. 3 or less) Linear or branched alkyl groups can be mentioned.

X1 in the formula (a1-III) represents an integer of 3 or more, and among them, an integer of 3 or more and 6 or less is preferable in terms of excellent cross-linking reactivity when forming a cured film.
The number of epoxy groups contained in the molecule of the siloxane compound is 2 or more, and from the viewpoint of excellent cross-linking reactivity when forming a cured film, 2 or more and 6 or less are preferable, and 2 or more and 4 or less are particularly preferable. Is.

（上記式（ａ１−ＩＩＩａ）及び式（ａ１−ＩＩＩｂ）中、Ｄ^１及びＤ^２は、それぞれ独立にアルキレン基を表し、ｍｓは０以上２以下の整数を表す。） Examples of the monovalent group containing an epoxy group, alicyclic epoxy group, and ^-D A ^{-O-R a26} glycidyl ether group ^{[D A} represented by represents an alkylene ^{group, R a26} is a glycidyl group ] Is preferable, the alicyclic epoxy group is more preferable, and the alicyclic epoxy group represented by the following formula (a1-IIIa) or the following formula (a1-IIIb) is further preferable. As the D ^{A (alkylene),} for example, methylene group, methylmethylene group, dimethylmethylene group, a dimethylene group, a linear or branched alkylene group having carbon atoms is 1 to 18, such as trimethylene group And so on.

(In the above formulas (a1-IIIa) and (a1-IIIb), D ¹ and D ² each independently represent an alkylene group, and ms represents an integer of 0 or more and 2 or less.)

The curable composition is described in JP-A-2008-248169 as a cationic curable compound (A), in addition to the siloxane compound represented by the formula (a1-III), an alicyclic epoxy group-containing cyclic siloxane. Contains an alicyclic epoxy group-containing silicone resin and a compound having a siloxane skeleton such as an organopolysilsesquioxane resin having at least two epoxy functional groups in one molecule described in JP-A-2008-19422. You may be doing it.

More specific examples of the siloxane compound include cyclic siloxanes having two or more glycidyl groups in the molecule, which are represented by the following formulas. Examples of the siloxane compound include trade names "X-40-2670", "X-40-2701", "X-40-2728", "X-40-2738", and "X-40-2740". Commercially available products such as (above, manufactured by Shin-Etsu Chemical Co., Ltd.) can be used.

(Episulfide compound)
The type of episulfide compound is not particularly limited as long as the object of the present invention is not impaired. Preferred episulfide compounds include compounds in which the oxygen atom in the epoxy group is replaced with a sulfur atom in the above-mentioned epoxy compound.

The content of the (A) curable compound in the curable composition is not particularly limited as long as it does not impair the object of the present invention. The content of the (A) curable compound in the curable composition is 60 parts by mass or more and 99.9 parts by mass when the mass of the curable composition excluding the mass of the solvent (S) described later is 100 parts by mass. It is preferably 75 parts by mass or more, more preferably 99.5 parts by mass or less, and particularly preferably 90 parts by mass or more and 99 parts by mass or less.

[Cation hardener (B)]
The curable composition contains a cationic curing agent (B) as a component for curing the above-mentioned cationic curing compound (A). The cation curing agent (B) contains a sulfonium salt having a cation portion represented by the following formula (B1).
Ar-CH _2- S ⁺ -R ^B1 R ^B2 ... (B1)
(In the formula (B1), Ar is substituted is also an aromatic hydrocarbon group, R ^B1, and R ^B2 are each independently may be substituted hydrocarbon group. )

Such a cation curing agent (B) is decomposed by energy given by heating or exposure to generate an arylmethyl cation represented by ^{Ar—C +} H _2. Since the arylmethyl cation is less susceptible to the inhibition of curing by the nitrogen-containing compound-containing layer, the above-mentioned cation-curable compound (A) can be produced even if the curable composition is in contact with the nitrogen-containing compound-containing layer. It is considered to cure well.

In formula (B1), ^RB1 and ^RB2 are organic groups attached to S ^+. R ^B1 and R ^B2 may be the same or different from each other. ^{Organic groups as RB1} and ^RB2 include aromatic hydrocarbon groups having 6 to 14 carbon atoms, alkyl groups having 1 to 18 carbon atoms, alkenyl groups having 2 to 18 carbon atoms, and carbon. Examples thereof include an alkynyl group having 2 or more and 18 or less atoms.

^{Preferable examples of the aromatic hydrocarbon groups as RB1} and ^RB2 are phenyl group, naphthalene-1-yl group, naphthalene-2-yl group, 2-phenylphenyl group, 3-phenylphenyl group, and 4 -Phenylphenyl group is mentioned.
^{Preferable examples of alkyl groups as RB1} and ^RB2 are methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, n-pentyl group, n-hexyl group and n-heptyl group. , N-octyl group, 2-ethylhexyl group, n-nonyl group, n-decyl group, n-undecyl group, n-dodecyl group, n-tridecyl group, n-tetradecyl group, n-pentadecyl group, n-hexadecyl group. , N-Heptadecyl group, and n-octadecyl group.
^{Preferable examples of the alkenyl group as RB1} and ^RB2 include a vinyl group, a 1-propenyl group, a 2-propenyl group (allyl group), a 3-butenyl group, a 4-pentenyl group, and a 5-hexenyl group. Be done.
Preferred examples of the alkynyl group as R ^B1 and ^{R B2} are ethynyl, 1-propynyl, 2-propynyl group (propargyl group), 3-butynyl group, 4-pentynyl group, and 5-hexynyl groups mentioned Be done.

The above aromatic hydrocarbon group, alkyl group, alkenylki group, and alkynyl group may have a substituent. Examples of the substituent include a hydroxyl group, an alkoxy group, an alkylcarbonyl group, an arylcarbonyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an arylthiocarbonyl group, an acyloxy group, an alkoxycarbonyloxy group, an arylthio group, an alkylthio group and an aryl group. Heterocyclic hydrocarbon group, aryloxy group, alkylsulfinyl group, arylsulfinyl group, alkylsulfonyl group, arylsulfonyl group, hydroxy (poly) alkyleneoxy group, optionally substituted silyl group, optionally substituted Examples include an amino group and a halogen atom.

In the formula (B1), R ^B1 and R ^B2 may form a ring together with the sulfur atom in the formula (B1). The ^{ring formed by R B1} and R ^B2 together with the sulfur atom has -O-, -S-, -SO-, -SO _2- , -NH-, -CO-, -COO- in its ring structure. , And more bonds selected from the group consisting of -CONH- may be included.

Ar in the formula (B1) is an aromatic hydrocarbon group which may have a substituent. Examples of the aromatic hydrocarbon group as Ar include a phenyl group, a naphthalene-1-yl group, a naphthalene-2-yl group, a 2-phenylphenyl group, a 3-phenylphenyl group, and a 4-phenylphenyl group. Be done. The substituents that these aromatic hydrocarbon groups may have are the same as the substituents that the above-mentioned aromatic hydrocarbon groups, alkyl groups, alkenyl groups, and alkynyl groups may have.

Specific examples of the cation portion represented by the formula (B1) include the following sulfonium cations.

Examples of the counter anion to the cation represented by the formula (B1) include AsF ₆ ⁻ , SbF ₆ ⁻ , PF ₆ ⁻ , and (C ₆ F ₅ ) ₄ B ⁻ . Of these, (C ₆ F ₅ ) ₄ B ⁻ is preferred. In addition, "C ₆ F ₅ " represents a pentafluorophenyl group.

（式（Ｂ２）中、Ｒ^ｂ３、Ｒ^ｂ４、Ｒ^ｂ５、及びＲ^ｂ６は、それぞれ独立に、置換基を有していてもよい炭化水素基、又は置換基を有していてもよい複素環基であり、Ｒ^ｂ３、Ｒ^ｂ４、Ｒ^ｂ５、及びＲ^ｂ６のうちの少なくとも１つが置換基を有していてもよい芳香族炭化水素基である。）

（式（Ｂ３）中、Ｒ^ｂ７、Ｒ^ｂ８、Ｒ^ｂ９、及びＲ^￥ｂ１０は、それぞれ独立に、置換基を有していてもよい炭化水素基、又は置換基を有していてもよい複素環基であり、Ｒ^ｂ７、Ｒ^ｂ８、Ｒ^ｂ９、及びＲ^ｂ１０のうちの少なくとも１つが置換基を有していてもよい芳香族炭化水素基である。） The counter anion to the cation represented by the formula (B1) is an anion represented by the following formula (B2) or an anion represented by the following formula (B3) because it is easy to form a cured product having excellent curability and transparency. The anion represented by is preferable.

(In the formula (B2), R ^b3 , R ^b4 , R ^b5 , and R ^b6 each independently have a hydrocarbon group which may have a substituent or a heterocycle which may have a substituent. It is a group, and ^{at least one of R b3} , R ^b4 , R ^b5 , and R ^{b6 is} an aromatic hydrocarbon group which may have a substituent.)

(In the formula (B3), R ^b7 , R ^b8 , R ^b9 , and R ^{\ b10} each independently have a hydrocarbon group which may have a substituent or a complex which may have a substituent. It is a ring group, and ^{at least one of R b7} , R ^b8 , R ^b9 , and R ^{b10 is} an aromatic hydrocarbon group which may have a substituent.)

^{The number of carbon atoms of the hydrocarbon group or heterocyclic group as R b3 to} R ^b6 in the formula (B2) is not particularly limited, but is preferably 1 or more and 50 or less, more preferably 1 or more and 30 or less, and 1 or more and 20 or less. Especially preferable.

Specific examples of the hydrocarbon groups as R ^{b3 to} R ^b6 include linear or branched alkyl groups, linear or branched alkenyl groups, linear or branched alkynyl groups, and aromatics. Examples thereof include group hydrocarbon groups, alicyclic hydrocarbon groups, and aralkyl groups.
As described ^above, R b3 at least one aromatic group which may have a substituent of a ^{to R b6,} aromatic also have three or more substituents of R b3 ^{to R b6} It is more preferably a group, and it is particularly preferable that all of ^{R b3 to} R ^{b6 are aromatic groups which may have a substituent.}

As the ^{substituents that the hydrocarbon group as R b3 to} R ^b6 or the heterocyclic group may have, an alkyl halide group having 1 to 18 carbon atoms and a halogenated group having 3 to 18 carbon atoms An aliphatic cyclic group, a nitro group, a hydroxyl group, a cyano group, an alkoxy group having 1 to 18 carbon atoms, an aryloxy group having 6 to 14 carbon atoms, an aliphatic acyl group having 2 to 19 carbon atoms, Aromatic acyl groups with 7 to 15 carbon atoms, aliphatic acyloxy groups with 2 to 19 carbon atoms, aromatic acyloxy groups with 7 to 15 carbon atoms, alkylthio groups with 1 to 18 carbon atoms, Examples thereof include an arylthio group having 6 to 14 carbon atoms, an amino group in which 1 or 2 hydrogen atoms bonded to a nitrogen atom may be substituted with a hydrocarbon group having 1 to 18 carbon atoms, and a halogen atom. ..
When ^{the hydrocarbon group as R b3 to} R ^b6 is an aromatic hydrocarbon group, the aromatic hydrocarbon group is an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, and an alkenyl group having 2 to 18 carbon atoms. And it may be substituted with one or more substituents selected from the group consisting of alkynyl groups having 2 or more and 18 or less carbon atoms.

When ^{the hydrocarbon groups as R b3 to} R ^b6 have substituents, the number of substituents is not particularly limited, and may be 1 or 2 or more. When the number of substituents is plural, the plurality of substituents may be the same or different.

Suitable specific examples when R ^{b3 to} R ^b6 are alkyl groups include methyl group, ethyl group, n-propyl group, n-butyl group, n-pentyl group, n-hexyl group and n-octyl group. n-nonyl group, n-decyl group, n-undecyl group, n-dodecyl group, n-tridecyl group, n-tetradecyl group, n-pentadecyl group, n-hexadecyl group, n-heptadecyl group, n-octadecyl group, Linear alkyl groups such as n-nonadesyl group and n-icosyl group; isopropyl group, isobutyl group, sec-butyl group, tert-butyl group, isopentyl group, neopentyl group, tert-pentyl group, isohexyl group, 2-ethylhexyl Examples include a group and a branched alkyl group such as a 1,1,3,3-tetramethylbutyl group.

Preferable examples when R ^{b3 to} R ^b6 are an alkenyl group or an alkynyl group include an alkenyl group corresponding to the above-mentioned group suitable as an alkyl group and an alkynyl group.

Preferable examples when R ^{b3 to} R ^b6 are aromatic hydrocarbon groups are a phenyl group, an α-naphthyl group, a β-naphthyl group, a biphenyl-4-yl group, a biphenyl-3-yl group, and a biphenyl-2. -Il group, anthryl group, phenyl group and the like can be mentioned.

Preferable examples when R ^{b3 to} R ^b6 are alicyclic hydrocarbon groups include cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cyclopentyl group, cyclooctyl group, cyclononyl group, cyclodecyl group and the like. Cycloalkyl groups; examples include crosslinked aliphatic cyclic hydrocarbon groups such as norbornyl group, adamantyl group, tricyclodecyl group, and pinanyl group.

Preferable examples when R ^{b3 to} R ^b6 are aralkyl groups include a benzyl group, a phenethyl group, an α-naphthylmethyl group, a β-naphthylmethyl group, an α-naphthylethyl group, a β-naphthylethyl group and the like. Can be mentioned.

Preferable examples of cases where R ^{b3 to} R ^b6 are heterocyclic groups include thienyl group, furanyl group, selenophenyl group, pyranyl group, pyrrolyl group, oxazolyl group, thiazolyl group, pyridyl group, pyrimidyl group and pyrazinyl group. Indrill group, benzofuranyl group, benzothienyl group, quinolyl group, isoquinolyl group, quinoxalinyl group, quinazolinyl group, carbazolyl group, acridinyl group, phenothiazine group, phenazinyl group, xanthenyl group, thianthrenyl group, phenoxadinyl group, phenoxatinyl group, Examples thereof include a chromanyl group, an isochromanyl group, a dibenzothienyl group, a xanthonyl group, a thioxanthonyl group, and a dibenzofuranyl group.

^{Examples of R b7 to} R b10 in the formula (B3) include groups similar to those described above for ^{R b3 to} R ^b6 in the formula (B2).

As a preferable specific example of the anion portion represented by the formula (b2) described above,
Tetrakis (4-nonafluorobiphenyl) gallium anion,
Tetrakis (1-heptafluoronaphthyl) gallium anion,
Tetrakis (pentafluorophenyl) gallium anion,
Tetrakis (3,4,5-trifluorophenyl) gallate anion,
Tetrakis (2-nonaphenylbiphenyl) gallium anion,
Tetrakis (2-heptafluoronaphthyl) gallium anion,
Tetrakis (7-nonafluoroanthril) gallium anion,
Tetrakis (4'-(methoxy) octafluorobiphenyl) gallium anion,
Tetrakis (2,4,6-tris (trifluoromethyl) phenyl) gallium anion,
Tetrakis (3,5-bis (trifluoromethyl) phenyl) gallium anion,
Tetrakis (2,3-bis (pentafluoroethyl) naphthyl) gallium anion,
Tetrakis (2-isopropoxy-hexafluoronaphthyl) gallium anion,
Tetrakis (9,10-bis (heptafluoropropyl) heptafluoroanthril) gallium anion,
Tetrakis (9-nonafluorophenanthril) gallate anion,
Tetrakis (4- [tri (isopropyl) silyl] -tetrafluorophenyl) gallium anion,
Tetrakis (9,10-bis (p-tolyl) -heptafluorophenanthril) gallium anion,
Tetrakis (4- [dimethyl (t-butyl) silyl] -tetrafluorophenyl) gallium anion,
Examples thereof include monophenyltris (pentafluorophenyl) gallium anion and monoperfluorobutyltris (pentafluorophenyl) gallium anion, and more preferably, the following anions are mentioned.

Further, as a preferable specific example of the anion portion represented by the formula (b3),
Tetrakis (4-nonafluorobiphenyl) boron anion,
Tetrakis (1-heptafluoronaphthyl) boron anion,
Tetrakis (pentafluorophenyl) boron anion,
Tetrakis (3,4,5-trifluorophenyl) boron anion,
Tetrakis (2-nonaphenylbiphenyl) boron anion,
Tetrakis (2-heptafluoronaphthyl) boron anion,
Tetrakis (7-nonafluoroanthril) boron anion,
Tetrakis (4'-(methoxy) octafluorobiphenyl) boron anion,
Tetrakis (2,4,6-tris (trifluoromethyl) phenyl) boron anion,
Tetrakis (3,5-bis (trifluoromethyl) phenyl) boron anion,
Tetrakis (2,3-bis (pentafluoroethyl) naphthyl) boron anion,
Tetrakis (2-isopropoxy-hexafluoronaphthyl) boron anion,
Tetrakis (9,10-bis (heptafluoropropyl) heptafluoroanthril) boron anion,
Tetrakis (9-nonafluorophenanthryl) boron anion,
Tetrakis (4- [tri (isopropyl) silyl] -tetrafluorophenyl) boron anion,
Tetrakis (9,10-bis (p-tolyl) -heptafluorophenanthril) boron anion,
Tetrakis (4- [dimethyl (t-butyl) silyl] -tetrafluorophenyl) boron anion,
Examples thereof include monophenyltris (pentafluorophenyl) boron anion and monoperfluorobutyltris (pentafluorophenyl) boron anion, and more preferably, the following anions are mentioned.

The content of the sulfonium salt having a cation portion represented by the above formula (B1) in the cation curing agent (B) is preferably 50% by mass or more, more preferably 70% by mass or more, and further more preferably 80% by mass or more. It is preferable, 90% by mass or more is particularly preferable, and 100% by mass is most preferable.

The cation curing agent that can be used as the cation curing agent (B) together with the sulfonium salt having a cation portion represented by the above formula (B1) is not particularly limited, and various types conventionally used for curing a cation curing compound. A cationic curing agent can be used.

The content of the cationic curing agent (B) in the curable composition is not particularly limited as long as it does not impair the object of the present invention. The content of the cationic curing agent (B) in the curable composition is preferably 0.1 part by mass or more and 15 parts by mass or less, and 0.3 parts by mass or more and 10 parts by mass with respect to 100 parts by mass of the cationically curable compound (A). It is more preferably parts by mass or less, and particularly preferably 0.4 parts by mass or more and 5 parts by mass or less from the viewpoint of transparency.

By using an amount of the cationic curing agent (B) within such a range, a cured product having good heat resistance (heat-decomposability) and good adhesion to the substrate can be formed, and the curing property is good. Easy to obtain sex composition.

[Curing accelerator (C)]
The curable composition may contain a curing accelerator (C). When the curable composition contains a curing accelerator (C), the curability of the curable composition is particularly good, and it has heat resistance (heat decomposition resistance), solvent resistance, and adhesion to a nitrogen-containing compound-containing layer. A cured product having particularly good properties can be formed.

Examples of the curing accelerator (C) include urea compounds, tertiary amines and salts thereof, imidazoles and salts thereof, phosphine compounds and derivatives thereof, metal carboxylates and Lewis acids, blended acids and salts thereof, and the like. Examples thereof include tetraphenylboron salts.

Preferred specific examples of the curing accelerator (C) include 1,8-diazabicyclo (5,4,0) undecene-7, triethylenediamine, benzyldimethylamine, triethanolamine, dimethylaminoethanol, and tris (dimethylaminomethyl). ) Tertiary amines such as phenol; imidazoles such as 2-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, and 2-heptadecylimidazole; tributylphosphine, methyldiphenylphosphine, triphenylphosphine, Phenyl-based compounds such as diphenylphosphine and phenylphosphine; tetraphenylphosphonium tetraphenylborate, triphenylphosphine tetraphenylborate, 2-ethyl-4-methylimidazole tetraphenylborate, and tetraphenylborone of N-methylmorpholine tetraphenylborate. Examples include salt.

Among the curing accelerators (C) described above, a phosphine compound, a derivative thereof, and a tetraphenylboron salt are preferable. Among the above specific examples, triphenylphosphine and triphenylphosphine triphenylborane are preferable.

The amount of the curing accelerator (C) used is not particularly limited as long as it does not impair the object of the present invention. The amount of the curing accelerator (C) used is preferably 0.5 parts by mass or more and 8 parts by mass or less, more preferably 1.5 parts by mass or more and 6 parts by mass or less, when the cationic curing agent (B) is 1 part by mass. It is preferable, and 2 parts by mass or more and 4.5 parts by mass or less are particularly preferable.

[Sensitizer (D)]
The curable composition may contain a sensitizer (D). As the sensitizer (D), a known sensitizer that has been conventionally used in combination with various cationic curing agents can be used without particular limitation.

Specific examples of the sensitizer include anthracene, 9,10-dibutoxyanthracene, 9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, and 9,10-. Anthracene compounds such as dipropoxyanthracene; pyrene; 1,2-benzanthracene; perylene; tetracene; coronen; thioxanthone, 2-methylthioxanthone, 2-ethylthioxanthone, 2-chlorothioxanthone, 2-isopropylthioxanthone and 2,4-diethyl Thioxanthone compounds such as thioxanthone; phenothiazine compounds such as phenothracene, N-methylphenothracene, N-ethylphenothracene, and N-phenylphenothracene; xanthone; 1-naphthol, 2-naphthol, 1-methoxynaphthalene, 2-methoxynaphthalene, 1, Naphthalene compounds such as 4-dihydroxynaphthalene and 4-methoxy-1-naphthol; dimethoxyacetophenone, diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 4'-isopropyl-2-hydroxy Ketones such as -2-methylpropiophenone and 4-benzoyl-4'-methyldiphenylsulfide; carbazole compounds such as N-phenylcarbazole, N-ethylcarbazole, poly-N-vinylcarbazole, and N-glycidylcarbazole; Crescent compounds such as 1,4-dimethoxycrisen and 1,4-di-α-methylbenzyloxythracene; 9-hydroxyphenanthrene, 9-methoxyphenanthrene, 9-hydroxy-10-methoxyphenanthrene, and 9-hydroxy-10- Examples thereof include phenanthren compounds such as ethoxyphenanthrene.
These sensitizers (D) may be used in combination of two or more.

The amount of the sensitizer (D) used is not particularly limited, but is preferably 1% by mass or more and 300% by mass or less, and more preferably 5% by mass or more and 200% by mass or less, based on the mass of the cationic curing agent (B). By using an amount of the sensitizer (D) within such a range, it is easy to obtain a desired sensitizing effect.

[Other ingredients]
Curable compositions include surfactants, thermal polymerization inhibitors, defoamers, silane coupling agents, colorants (pigments, dyes), resins (thermoplastic resins, alkali-soluble resins, etc.), as required. Additives such as inorganic fillers and organic fillers can be contained. As any of the additives, conventionally known ones can be used. Examples of the surfactant include anionic, cationic and nonionic compounds, examples of the thermal polymerization inhibitor include hydroquinone and hydroquinone monoethyl ether, and examples of the antifoaming agent include silicone and fluorine. Examples include compounds.

The curable composition containing the essential or arbitrary components described above can form a cured product having good heat resistance (heat-decomposability), solvent resistance, and adhesion to a substrate, and has good curability. Since it is good, it can be suitably used in various applications.

In particular, when the curable composition contains the compound represented by the above formula (a1) as the cationic curable compound (B), a cured product having a high refractive index can be formed. Such a cured product having a high refractive index is preferably used for forming a microlens.

[Solvent (S)]

The curable composition preferably contains a solvent (S) for the purpose of adjusting the coatability and viscosity. As the solvent (S), an organic solvent is typically used. The type of organic solvent is not particularly limited as long as the components contained in the curable composition can be uniformly dissolved or dispersed.

Preferable examples of the organic solvent that can be used as the solvent (S) are ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol-n-propyl ether, ethylene glycol mono-n-butyl ether, diethylene glycol monomethyl ether, and diethylene glycol mono. Ethyl ether, diethylene glycol mono-n-propyl ether, diethylene glycol mono-n-butyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether , Propropylene glycol mono-n-butyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol mono-n-propyl ether, dipropylene glycol mono-n-butyl ether, tripropylene glycol monomethyl ether, tripropylene glycol (Poly) alkylene glycol monoalkyl ethers such as monoethyl ether; ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether (Poly) alkylene glycol monoalkyl ether acetates such as acetate; other ethers such as diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, tetrahydrofuran; ketones such as methyl ethyl ketone, cyclohexanone, 2-heptanone, 3-heptanone; Lactic acid alkyl esters such as methyl 2-hydroxypropionate and ethyl 2-hydroxypropionate; ethyl 2-hydroxy-2-methylpropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, 3-ethoxypropionic acid Methyl, ethyl 3-ethoxypropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, methyl 2-hydroxy-3-methyl part, 3-methyl-3-methoxybutyl acetate, 3-methyl-3-methoxybutyl propio Nate, ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, n-pentyl formate, isopentyl acetate, n-butyl propionate, ethyl butyrate, n-propyl butyrate, isopropyl butyrate, n-butyl butyrate. , Methyl pyruvate, ethyl pyruvate, n-propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, ethyl 2-oxobutanoate and other esters; aromatic hydrocarbons such as toluene and xylene; N-methylpyrrolidone , N, N-dimethylformamide, N, N-dimethylacetamide and other amides and the like. These organic solvents can be used alone or in combination of two or more.

The amount of the solvent (S) used in the curable composition is not particularly limited. From the viewpoint of coatability of the curable composition, the amount of the solvent (S) used is, for example, 30% by mass or more and 99.9% by mass or less, preferably 50% by mass or more, based on the entire curable composition. It is 98% by mass or less.

A curable composition can be produced by uniformly mixing each of the components described above in a predetermined ratio. If desired, the curable composition may be filtered using a filter with openings of the desired size to remove insoluble foreign matter.

[Applying method of curable composition]
The above-mentioned curable composition is applied to at least a part of the main surface of the nitrogen-containing organic compound-containing layer described above.

The coating method is not particularly limited. For example, a contact transfer type coating device such as a roll coater, a reverse coater, a bar coater, or a slit coater, or a non-contact type coating device such as a spinner (rotary coating device) or a curtain flow coater is used to obtain the above curable composition. Is applied onto the nitrogen-containing organic compound-containing layer so as to have a desired film thickness.

The film made of the curable composition formed by coating is appropriately heat-treated (pre-baked (post-applied (PAB)) treatment) to remove the organic solvent, thereby forming a coating film.

The prebaking method is not particularly limited, and for example, (i) drying using a hot plate at a temperature of 80 ° C. to 120 ° C. (preferably 85 to 100 ° C., more preferably 85 to 95 ° C.) for 60 seconds to 120 seconds. It may be either (ii) a method of leaving it at room temperature for several hours to several days, or (iii) a method of putting it in a warm air heater or an infrared heater for several tens of minutes to several hours to remove the solvent.

The film thickness of the coating film after drying is, for example, preferably 0.1 μm or more and 10 μm or less, preferably 0.2 μm or more and 5 μm or less, and more preferably 0.3 μm or more and 2 μm or less.

<Curing process>
In the curing step, the curable composition is cured to form a cured product layer. The curable composition is typically in the form of a dried coating film.
The curing method is not particularly limited. The curing method may be heating, exposure, or a combination of both, and heating is preferable.
The temperature at the time of heating is not particularly limited, and is preferably 180 ° C. or higher and 280 ° C. or lower, more preferably 180 ° C. or higher and 250 ° C. or lower, and particularly preferably 180 ° C. or higher and 230 ° C. or lower. The heating time is typically preferably 1 minute or more and 60 minutes or less, more preferably 10 minutes or more and 50 minutes or less, and particularly preferably 20 minutes or more and 40 minutes or less.

The cured product formed as described above is applied to various uses. In particular, according to the above method, a cured product can be satisfactorily formed on a green color filter, a blue color filter, or a red color filter containing a nitrogen-containing organic compound such as a phthalocyanine pigment. A green color filter, a blue color filter, or a cured product formed on the red color filter is particularly preferably used for forming a microlens in a CMOS image sensor.

≪Manufacturing method of microlens≫
The manufacturing method of microlenses is
By forming a cured product layer on a green color filter, a blue color filter, or a red color filter by the method described above,
Forming a mask with a shape corresponding to the shape of the lens to be formed on the cured product layer,
This includes forming a lens to which the shape of the mask is transferred by etching the cured product layer together with the mask.
The cured product layer used to form the microlens is transparent.

The method for forming the cured product layer is as described above. The method of forming a mask having a shape corresponding to the shape of the lens to be formed on the cured product layer is not particularly limited. Typically, a dot pattern considering the size of the lens is formed by a photolithography method using a resist composition, and then the formed dot pattern is allowed to flow by heating to be similar to the shape of the formed lens. A mask of shape is formed.
The temperature at which the dot pattern is allowed to flow by heating is appropriately set according to the type of resist composition.

Then, by etching the cured product layer together with the mask, a lens to which the shape of the mask is transferred can be formed. The etching method is not particularly limited, but dry etching is preferable. The dry etching is not particularly limited, and examples _{thereof include dry etching by plasma (oxygen, argon, CF 4,} etc.), corona discharge, and the like.

The microlens produced on the green color filter, the blue color filter, or the red color filter by the above method is made of a cured product obtained by successfully curing the above-mentioned curable composition, and is excellent in heat resistance and solvent resistance. ..

≪Manufacturing method of CMOS image sensor≫
According to the above method for manufacturing a microlens, a CMOS image sensor can be satisfactorily manufactured by forming a microlens on a green color filter, a blue color filter, or a red color filter.
In this case, various members usually possessed by a CMOS image sensor such as a light-shielding layer, a photodiode, and a silicon transistor are provided on the surface of the color fielder opposite to the surface on which the microlens is provided.

Hereinafter, the present invention will be described in more detail with reference to Examples, but the scope of the present invention is not limited to these Examples.

[Example 1 and Comparative Example 1]
In Example 1 and Comparative Example 1, a compound having the following structure was used as the cationic curable compound.

In Example 1, as the cation curing agent, a cation portion composed of a sulfonium cation in which Ar of the formula (B1) is a phenyl group, ^RB1 is a 4-hydroxyphenyl group, and ^RB2 _{is a methyl group and (C 6).} F ₅ ) A sulfonium salt B1 consisting of an anion portion represented by ₄ Ga ^{− was used.} In Comparative Example 1, the following compound B2 was used as the cationic curing agent.

The curable composition (solid content concentration) of Example 1 and Comparative Example 1 was uniformly mixed with 100 parts by mass of the above-mentioned cation-curable compound, 3 parts by mass of the above-mentioned cation-curing agent, and propylene glycol monomethyl ether acetate. : 25% by mass) was obtained.

The obtained curable composition was applied onto a cured product with a green resist having a film thickness of 7,000 Å, and then dried at 100 ° C. for 120 seconds to obtain a coating film. The obtained coating film was heated at 230 ° C. for 20 minutes to be cured to obtain a cured film having a film thickness of 3 μm.
The formed cured film was immersed in propylene glycol monomethyl ether acetate at 25 ° C. for 5 minutes. After the cured film after immersion was dried, the residual film ratio was calculated from the film thickness T1 of the cured film before immersion and the film thickness T2 of the cured film after immersion according to the following formula.
Residual film ratio (%) = T2 / T1 × 100

The green resist is a propylene glycol monomethyl ether acetate solution of 10 parts by mass of a phthalocyanine compound and 12 parts by mass of a resin solution (Mw: 30,000 benzyl methacrylate / methacrylate (70/30 [molar ratio]) copolymer. (Solid content 50%)) 129 parts by mass of propylene glycol monoethyl ether acetate, 0.5 parts by mass of fluorine-based surfactant (trade name: Megafuck F475 manufactured by Dainippon Ink, Ltd.), 12 parts by mass of dipentaerythritol Hexaacrylate, 3 parts by mass of photopolymerization initiator (2- (o-chlorophenyl) -4,5-diphenylimidazolyl dimer), 2 parts by mass of 2-mercaptobenzothiazole, 0.001 part by mass of p-methoxy Phenol and propylene of 30 parts by mass of yellow pigment dispersion composition (130 parts by mass Pigment Yellow 138, 15 parts by mass resin solution (Mw: 5000 benzyl methacrylate / methacrylate (70/30 [molar ratio]) copolymer) Glycol monomethyl ether acetate solution (solid content 50% by mass)), 60 parts by mass of dispersant (Disperbyk-161, manufactured by Big Chemie Japan Co., Ltd.), and 795 parts by mass of propylene glycol monomethyl ether acetate are dispersed. The treated product) was mixed and prepared.

As a result, the residual film ratio of the cured film formed by using the curable composition of Example 1 was 99.9%, whereas it was formed by using the curable composition of Comparative Example 1. The residual film ratio of the cured film was 69.5%.
An FT-IR analysis was performed on the coating film before curing by heating and the cured film before immersion using the measurement of the residual film ratio, and the epoxy group residual ratio after curing was calculated. The epoxy group residual rate of the cured film was 15%, and the epoxy group residual rate of the cured film of Comparative Example 1 was 51%.
That is, when the curable composition of Example 1 containing a sulfonium salt having a cation portion represented by the formula (B1) as a cation curing agent is used, phthalocyanine corresponding to a nitrogen-containing compound containing a nitrogen atom having a lone electron pair. It can be seen that even if the cured film is formed on the green resist containing the pigment, the curing of the curable composition is hardly inhibited.
On the other hand, when the curable composition of Comparative Example 1 containing an ammonium salt having a cation portion other than the cation portion represented by the formula (B1) as a cation curing agent is used, when forming a cured film on a green resist, , It can be seen that the curing of the curable composition is greatly inhibited.

By using the curable composition described above, a microlens can be formed by the following method. Hereinafter, a method for forming a microlens using the photosensitive composition of Example 1 will be described.
First, a cured product having a thickness of 1 μm is obtained on the green resist layer in the same manner as in the evaluation of the residual film ratio. Then, a coating film is formed using the positive photosensitive resin composition described in Example 1 of JP-A-2016-133733, and the above coating is performed on a hot plate at 100 ° C. for 90 seconds. By drying the film, a positive photosensitive resin composition layer having a film thickness of 800 nm is formed.
Next, using a KrF exposure apparatus NSR-S203B (manufactured by Nikon, NA = 0.68, S = 0.75), a KrF excimer laser (248 nm) was applied to the positive photosensitive resin composition layer via a mask. Irradiate selectively. Then, the positive photosensitive resin composition layer is subjected to PEB treatment at 110 ° C. for 90 seconds, and then developed at 23 ° C. with a 2.38 mass% tetramethylammonium hydroxide aqueous solution for 60 seconds. Then, the developed resist pattern is rinsed with pure water for 30 seconds. Pure water was shaken off and dried to obtain a dot pattern consisting of dots having a size of 250 nm in length and 250 nm in width. The obtained dot pattern is flowed at 140 ° C. to obtain a hemispherical pattern.
Using the hemispherical pattern after the flow as a mask, _{etching treatment is performed using a fluorocarbon gas containing CF 4} in a dry etching apparatus to obtain a hemispherical cured product.

Claims (11)

A curable composition containing a cationic curable compound (A) and a cationic curing agent (B) is applied to at least a part of the main surface of the nitrogen-containing compound-containing layer.
A method for producing a laminate, which comprises curing the curable composition to form a cured product layer.
The nitrogen-containing compound-containing layer contains a nitrogen-containing compound containing a nitrogen atom having a lone electron pair.
A method for producing a laminate, wherein the cation curing agent (B) contains a sulfonium salt having a cation portion represented by the following formula (B1).
Ar-CH _2- S ⁺ -R ^B1 R ^B2 ... (B1)
(In the formula (B1), Ar is substituted is also an aromatic hydrocarbon group, R ^B1, and R ^B2 are each independently may be substituted hydrocarbon group. ) The method for producing a laminate according to claim 1, wherein the curable composition gives a transparent cured product. The method for producing a laminate according to claim 2, wherein the curable composition gives a cured product having a refractive index of 1.60 or more at a wavelength of 589 nm. The method for producing a laminate according to any one of claims 1 to 3, wherein the cationically curable compound (A) is a compound represented by the following formula (a1).

(In the formula (a1), ^{W 1} and ^{W 2} are each independently represented by the following formula (a2):

It is a group represented by
In the formula (a2), ring Z represents an aromatic hydrocarbon ring, X represents a single bond or a group represented by −S−, R ¹ is a single bond, and an alkylene group having 1 or more and 4 or less carbon atoms. , Or an alkyleneoxy group having 1 or more and 4 or less carbon atoms, and when R ¹ is an alkyleneoxy group, the oxygen atom in the alkyleneoxy group is bonded to the ring Z, and R ² is a monovalent hydrocarbon group. , Hydrocarbon, group represented by -OR ^4a , group represented by -SR ^4b , acyl group, alkoxycarbonyl group, halogen atom, nitro group, cyano group, mercapto group, carboxy group, amino group, carbamoyl group, -NHR ^4c , -N (R ^4d ) ₂ , sulfo group, or monovalent hydrocarbon group, -OR ^4a , -SR ^4b , acyl group, alkoxycarbonyl group, At least a part of the hydrogen atoms bonded to the carbon atom contained in the group represented by ^{−NHR 4c} or the group represented by −N (R ^4d ) ₂ ^{is a monovalent hydrocarbon group, a hydroxyl group, or a group represented by −OR 4a.} , -SR ^4b group, acyl group, alkoxycarbonyl group, halogen atom, nitro group, cyano group, mercapto group, carboxyl group, amino group, carbamoyl group, -NHR ^4c group, -N (R ^4d) ) _{Indicates a group represented by 2} , a mesyloxy group, or a group substituted with a sulfo group, R ^{4a to} R ^4d independently indicate a monovalent hydrocarbon group, m indicates an integer of 0 or more, and R ³ indicates an integer of 0 or more. A hydrogen atom, a vinyl group, a thiran-2-ylmethyl group, or a glycidyl group,
Both W ¹ and W ² do not have a hydrogen atom as R ^3,
Ring Y ¹ and ring Y ² denote the same or different aromatic hydrocarbon ring, R represents a single bond, methylene group which may have a substituent, may have a substituent, 2 carbon atoms An ethylene group which may contain a hetero atom in between, a group represented by -O-, a group represented by -NH-, or a group represented by -S- is shown, and R ^3a and R ^3b are independently cyano groups and halogens. It represents an atom or a monovalent hydrocarbon group, and n1 and n2 independently represent an integer of 0 or more and 4 or less. ) The method for producing a laminate according to claim 4, wherein W ¹ and W ^{2 each contain a naphthalene ring as the ring Z.} The method for producing a laminate according to any one of claims 1 to 5, wherein the nitrogen-containing compound is a dye compound. The method for producing a laminate according to claim 6, wherein the nitrogen-containing compound is a phthalocyanine pigment. The method for producing a laminate according to claim 7, wherein the nitrogen-containing compound-containing layer is a green color filter, a blue color filter, or a red color filter. To form the cured product layer on the green color filter, the blue color filter, or the red color filter by the method according to claim 8.
By forming a mask having a shape corresponding to the shape of the lens to be formed on the cured product layer,
Including forming a lens to which the shape of the mask is transferred by etching the cured product layer together with the mask.
A method for manufacturing a microlens, wherein the cured product layer is transparent. A method for manufacturing a CMOS image sensor, which comprises manufacturing a microlens on the green color filter, the blue color filter, or the red color filter by the method according to claim 9. A curable composition used in the method for producing a laminate according to any one of claims 1 to 8.
Containing a cationic curing compound (A) and a cationic curing agent (B),
A curable composition in which the cation curing agent (B) contains a sulfonium salt having a cation portion represented by the following formula (B1).
Ar-CH _2- S ⁺ -R ^B1 R ^B2 ... (B1)
(In the formula (B1), Ar is substituted is also an aromatic hydrocarbon group, R ^B1, and R ^B2 are each independently may be substituted hydrocarbon group. )