JP2015151408A - Curable composition containing vinyl group-containing compound - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a curable composition excellent in storage stability even containing a compound containing a vinyl group as a form such as a vinyloxy group, and providing a cured film excellent in pencil hardness, transparency, refraction index and heat resistance by curing, the cured article and a manufacturing method of the cured film using the curable composition.SOLUTION: The curable composition contains a vinyl group-containing compound represented by the formula (1) and an aliphatic ether group-containing compound having an aliphatic ether group having 2 to 6 carbon atoms. In the formula (1), a Wand Ware groups of the formula (2), hydroxyl groups or (meth)acryloyloxy groups, ring Yand Yare aromatic hydrocarbon rings, R is a single bond or a specific bivalent group, Rand Rare cyano groups, halogen atoms or monovalent hydrocarbon groups, and n1 and n2 are integer of 0 to 4. In the formula (2), a ring Z is an aromatic hydrocarbon ring, X is a single bond or a group represented by -S-, Ris a single bond or an alkylene group having 1 to 4 carbon atoms, Ris a specific substituent such as a monovalent hydrocarbon group and m is an integer of 0 or more.

Description

  The present invention relates to a curable composition containing a vinyl group-containing compound, a cured product thereof, and a method for producing a cured film using the curable composition.

  Conventionally, a compound containing a vinyl group in the form of a vinyloxy group or the like is used as a component of a curable composition together with an alicyclic ether group-containing compound. For example, Patent Document 1 describes a curable composition containing a cationically polymerizable unsaturated vinyl compound such as a divinyl ether compound and an epoxy compound.

JP-A-6-298912

  However, a curable composition containing a conventional vinyl group-containing compound as described in Patent Document 1 is inferior in storage stability, and a cured film obtained from this curable composition has a pencil hardness and transparency. There is a problem that the refractive index and heat resistance are poor.

  The present invention has been made in view of the situation as described above, and contains a compound containing a vinyl group in the form of a vinyloxy group or the like, and has excellent storage stability, and by curing, pencil hardness, transparency, It aims at providing the manufacturing method of the curable composition which gives the cured film which is excellent in refractive index and heat resistance, its cured material, and the said curable composition.

  The inventors of the present invention have made extensive studies to solve the above problems. As a result, it has been found that the above problems can be solved by using a novel vinyl group-containing condensed polycyclic compound, and the present invention has been completed. Specifically, the present invention provides the following.

  The 1st aspect of this invention is hardening containing the vinyl group containing compound represented by following General formula (1), and the alicyclic ether group containing compound which has a C2-C6 alicyclic ether group. Composition.

（式中、Ｗ^１及びＷ^２は独立に下記一般式（２）で表される基、水酸基、又は（メタ）アクリロイルオキシ基を示し、ただし、Ｗ^１及びＷ^２は同時に水酸基ではなく、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０〜４の整数を示す。）

(W ¹ and W ² independently represent a group represented by the following general formula (2), a hydroxyl group, or a (meth) acryloyloxy group, provided that W ¹ and W ² are not a hydroxyl group but a ring. Y ¹ and ring Y ² represent the same or different aromatic hydrocarbon rings, and R represents a single bond, a methylene group which may have a substituent, or a substituent, which may have two substituents. Represents an ethylene group that may contain a hetero atom, a group represented by -O-, a group represented by -NH-, or a group represented by -S-, wherein R ^3a and R ^3b independently represent a cyano group, a halogen atom Or a monovalent hydrocarbon group, and n1 and n2 independently represent an integer of 0 to 4.)

（式中、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は単結合又は炭素数１〜４のアルキレン基を示し、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、（メタ）アクリロイルオキシ基、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、若しくは−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、（メタ）アクリロイルオキシ基、メシルオキシ基、若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以上の整数を示す。）

(In the formula, ring Z represents an aromatic hydrocarbon ring, X represents a single bond or a group represented by -S-, R ¹ represents a single bond or an alkylene group having 1 to 4 carbon atoms, and R ² represents Monovalent hydrocarbon group, hydroxyl group, group represented by -OR ^4a , group represented by -SR ^4b , acyl group, alkoxycarbonyl group, halogen atom, nitro group, cyano group, mercapto group, carboxyl group, amino group, carbamoyl Group, a group represented by -NHR ^4c , a group represented by -N (R ^4d ) ₂ , a (meth) acryloyloxy group, a sulfo group, or a monovalent hydrocarbon group, a group represented by -OR ^4a , -SR ^4b At least a part of the hydrogen atoms bonded to the carbon atom contained in the group represented by the above formula, an acyl group, an alkoxycarbonyl group, a group represented by -NHR ^4c , or a group represented by -N (R ^4d ) ₂ are monovalent carbonized. hydrogen , Hydroxyl, a group represented by ^{-OR 4a,} a group represented by ^{-SR 4b,} an acyl group, an alkoxycarbonyl group, a halogen atom, a nitro group, a cyano group, a mercapto group, a carboxyl group, an amino group, a carbamoyl group, -NHR ^4c , A group represented by —N (R ^4d ) ₂ , a (meth) acryloyloxy group, a mesyloxy group, or a group substituted with a sulfo group, R ^{4a to} R ^4d are each independently a monovalent hydrocarbon And m represents an integer of 0 or more.)

The second aspect of the present invention is a cured product obtained by curing the curable composition.
The third aspect of the present invention is a method for producing a cured film comprising a step of applying the curable composition on a substrate to form a coating film, and a step of curing the coating film.

  According to the present invention, while containing a compound containing a vinyl group in the form of a vinyloxy group or the like, a cured film having excellent storage stability and excellent pencil hardness, transparency, refractive index, and heat resistance is obtained by curing. A curable composition, a cured product thereof, and a method for producing a cured film using the curable composition can be provided.

≪Curable composition≫
The curable composition concerning this invention contains the vinyl group containing compound represented by the said General formula (1), and the alicyclic ether group containing compound which has a C2-C6 alicyclic ether group. . Hereinafter, each component contained in the curable composition according to the present invention will be described in detail.

<Vinyl group-containing compound represented by the general formula (1)>
The vinyl group-containing compound contained in the curable composition according to the present invention is represented by the general formula (1). The said vinyl group containing compound can be used individually or in combination of 2 or more types.
In the general formula (1), W ¹ and W ² independently represent a group represented by the general formula (2), a hydroxyl group, or a (meth) acryloyloxy group, provided that W ¹ and W ² are simultaneously It is not a hydroxyl group. At least one of W ¹ and W ² is preferably a group represented by the general formula (2). In the present specification, “(meth) acryloyloxy group” means both an acryloyloxy group and a methacryloyloxy group.

In the general formula (2), examples of the ring Z include a benzene ring, a condensed polycyclic aromatic hydrocarbon ring [for example, a condensed bicyclic hydrocarbon ring (for example, a C _8-20 condensed dicyclic ring such as a naphthalene ring). Condensed 2 to 4 ring aromatics such as cyclic hydrocarbon rings, preferably C _10-16 condensed bicyclic hydrocarbon rings), condensed tricyclic aromatic hydrocarbon rings (eg, anthracene ring, phenanthrene ring, etc.) Hydrocarbon ring] and the like. Ring Z is preferably a benzene ring or a naphthalene ring. In addition, when both W ¹ and W ² are groups represented by the general formula (2), the ring Z included in W ¹ and the ring Z included in W ² may be the same or different. For example, one ring may be a benzene ring and the other ring may be a naphthalene ring. The substitution position of the ring Z which both W ¹ and W ² are bonded via X to the carbon atoms directly connected 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 general formula (2), X independently represents a single bond or a group represented by -S-, and is typically a single bond.

In the general formula (2), examples of R ¹ include a single bond; an alkylene group having 1 to 4 carbon atoms such as a methylene group, an ethylene group, a trimethylene group, a propylene group, and a butane-1,2-diyl group. A single bond; a C _2-4 alkylene group (particularly a C _2-3 alkylene group such as an ethylene group or a propylene group) is preferred, and a single bond is more preferred. Note that if none ^{W 1} and ^{W 2} is a group represented by the general formula (2), the ^{R 1} contained in ^{R 1} and ^{W 2} included in ^{W 1,} may be identical, May be different.

In the general formula (2), R ² is, for example, an alkyl group (eg, a C _1-12 alkyl group such as a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, preferably a C _1-8 alkyl group). Group, more preferably C _1-6 alkyl group and the like), cycloalkyl group (C _5-10 cycloalkyl group such as cyclohexyl group, preferably C _5-8 cycloalkyl group, more preferably C _5-6 cyclo). Alkyl group etc.), aryl group (for example, C _6-14 aryl group such as phenyl group, tolyl group, xylyl group, naphthyl group, preferably C _6-10 aryl group, more preferably C _6-8 aryl group) , an aralkyl group monovalent hydrocarbon group, (benzyl, _{C 6-10} aryl _{-C 1-4} alkyl group such as a phenethyl group), a hydroxyl group, an alkoxy group (methoxy , An ethoxy group, a propoxy group, _{C 1-12} alkoxy group or a butoxy group, preferably a _{C 1-8} alkoxy group, more preferably _{C 1-6} alkoxy group, etc.), C etc. cycloalkoxy group (hexyloxy group cycloheteroalkyl _5-10 cycloalkoxy group, etc.), aryloxy group (C _6-10 aryloxy group such as phenoxy group), aralkyloxy group (for example, C _6-10 aryl-C _1-4 alkyloxy group such as benzyloxy group) A group represented by —OR ^4a such as R ^4a represents a monovalent hydrocarbon group (such as the monovalent hydrocarbon group exemplified above). An alkylthio group (a C _1-12 alkylthio group such as a methylthio group, an ethylthio group, a propylthio group or a butylthio group, preferably a C _1-8 alkylthio group, more preferably a C _1-6 alkylthio group), a cycloalkylthio 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 _6-10 aryl-C ₁₋ such as benzylthio group) _A group represented by —SR ^4b such as ₄ alkylthio group, wherein R ^4b represents a monovalent hydrocarbon group (such as the monovalent hydrocarbon group exemplified above). An acyl group (a C _1-6 acyl group such as an acetyl group); an alkoxycarbonyl group (a C _1-4 alkoxy-carbonyl group such as a methoxycarbonyl group); a halogen atom (a fluorine atom, a chlorine atom, a bromine atom, Nitro group; cyano group; mercapto group; carboxyl group; amino group; carbamoyl group; alkylamino group (C _1-12 alkylamino such as methylamino group, ethylamino group, propylamino group, butylamino group) 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 (C _6-10 arylamino group such as phenylamino group), aralkylamino group (for example, benzylamine) Groups represented by —NHR ^4c such as C _6-10 aryl-C _1-4 alkylamino group such as mino group] [wherein R ^4c is a monovalent hydrocarbon group (such as the monovalent hydrocarbon group exemplified above)] Indicates. Dialkylamino group (di (C _1-12 alkyl) amino group such as dimethylamino group, diethylamino group, dipropylamino group, dibutylamino group, preferably di (C _1-8 alkyl) amino group, more preferably Di (C _1-6 alkyl) amino group etc.), dicycloalkylamino group (di (C _5-10 cycloalkyl) amino group such as dicyclohexylamino group), diarylamino group (diphenylamino group etc. C _6-10 aryl) amino group), diaralkylamino group (for example, di (C _6-10 aryl-C _1-4 alkyl) amino group such as dibenzylamino group) and the like —N (R ^4d ) ₂ The group shown [in the formula, R ^4d independently represents a monovalent hydrocarbon group (such as the monovalent hydrocarbon group exemplified above). (Meth) acryloyloxy group; sulfo group; the above monovalent hydrocarbon group, group represented by -OR ^4a , group represented by -SR ^4b , acyl group, alkoxycarbonyl group, group represented by -NHR ^4c Or at least a part of the hydrogen atoms 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 , or —SR ^4b a group represented by an acyl group, represented alkoxycarbonyl group, a halogen atom, a nitro group, a cyano group, a mercapto group, a carboxyl group, an amino group, a carbamoyl group, a group represented by -NHR ^4c, in ^{-N (R} _{4d) 2} A group substituted with a group, a (meth) acryloyloxy group, a mesyloxy group, or a sulfo group [for example, an alkoxyaryl group (for example, a methoxyphenyl group, etc.) C _1-4 alkoxy _{C 6-10} aryl group), an alkoxycarbonyl aryl group (e.g., methoxycarbonyl phenyl group, _{C 1-4} alkoxy such as ethoxy carbonyl phenyl - mentioned carbonyl _{C 6-10} aryl group, etc.) and the like It is done.

Among these, R ² is typically 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, a cyano group. , A group represented by -NHR ^4c , a group represented by -N (R ^4d ) ₂ , or the like.

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

When m is an integer of 2 or more, R ² may be different from each other or the same. Also, if none ^{W 1} and ^{W 2} is a group represented by the general formula (2), and ^{R 2} contained in ^{R 2} and ^{W 2} included in ^{W 1,} may be identical, May be different.

In the general formula (2), the number m of ^{R 2} can be selected according to the kind of ring Z, for example, 0-4, preferably 0-3, more preferably may be 0-2. When both W ¹ and W ² are groups represented by the general formula (2), m in W ¹ and m in W ² may be the same or different.

In the general formula (1), examples of the ring Y ¹ and the ring Y ² include a benzene ring, a condensed polycyclic aromatic hydrocarbon ring [for example, a condensed bicyclic hydrocarbon ring (for example, C such as a naphthalene ring). _8-20 condensed bicyclic hydrocarbon rings, preferably C _10-16 condensed bicyclic hydrocarbon rings), condensed tricyclic aromatic hydrocarbon rings (for example, anthracene ring, phenanthrene ring, etc.) Tetracyclic aromatic hydrocarbon ring] and the like. Ring Y ¹ and ring Y ² are preferably a benzene ring or a naphthalene ring. Ring Y ¹ and ring Y ² may be the same or different. For example, one ring may be a benzene ring and the other ring may be a naphthalene ring.

In the general formula (1), R represents a single bond, a methylene group which may have a substituent, an ethylene group which may have a substituent and may contain a hetero atom between two carbon atoms,- A group represented by O-, a group represented by -NH-, or a group represented by -S- is typically represented by 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, Butyl group, C _1-6 alkyl group such as t-butyl group), aryl group (C _6-10 aryl group such as phenyl group) and the like], and the hetero atom includes, for example, oxygen atom, nitrogen atom , Sulfur atom, silicon atom and the like.

In the general formula (1), R ^3a and R ^3b are usually non-reactive substituents such as cyano groups, halogen atoms (fluorine atoms, chlorine atoms, bromine atoms, etc.), monovalent hydrocarbon groups [for example, , An alkyl group, an aryl group (C _6-10 aryl group such as a phenyl group), etc.], and the like. A cyano group or an alkyl group is preferable, and an alkyl group is particularly preferable. Examples of the alkyl group include C _1-6 alkyl groups such as a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, and a t-butyl group (for example, a C _1-4 alkyl group, particularly a methyl group). . In addition, when n1 is an integer greater than or equal to 2, ^R3a may mutually differ and may be the same. Moreover, when n2 is an integer greater than or equal to 2, ^R3b may mutually differ and may be the same. Further, R ^3a and R ^3b may be the same or different. Further, the bonding positions (substitution positions) of R ^3a and R ^{3b with} respect to ring Y ¹ and ring Y ² are not particularly limited. Preferred substitution numbers n1 and n2 are 0 or 1, in particular 0. Note that n1 and n2 may be the same as or different from each other.

  In general, condensed polycyclic compounds have various excellent functions and are used in various applications. For example, a compound having a fluorene skeleton (such as a 9,9-bisphenylfluorene skeleton) which is a condensed polycyclic aromatic compound is excellent in optical characteristics such as light transmittance and refractive index, and thermal characteristics such as heat resistance. It is known to have a function. Therefore, compounds having a fluorene skeleton are used as raw materials for optical members such as lenses, prisms, filters, image display materials, optical disk substrates, optical fibers, optical waveguides, casing materials, films, and coating materials.

The compound represented by the general formula (1) is a novel vinyl group-containing condensed polycyclic compound, and has a vinyloxy group and / or (meth) acryloyloxy while maintaining excellent optical properties and thermal properties. Since it has a group, it has high reactivity. In particular, when ring Y ¹ and ring Y ² are benzene rings and R is a single bond, the compound represented by the above general formula (1) has a fluorene skeleton, and has optical and thermal characteristics. Even better. Since such a compound represented by the general formula (1) can be polymerized, it functions as a polymerizable monomer. In particular, when both W ¹ and W ² are groups represented by the above general formula (2), the compound represented by the above general formula (1) can be cationically polymerized. Function as. On the other hand, when both W ¹ and W ² are (meth) acryloyloxy groups, the compound represented by the general formula (1) functions as a radical polymerizable monomer because it can undergo radical polymerization. The compound represented by the general formula (1) is a vinyloxy group and / or when W ¹ and W ² are independently a group represented by the general formula (2) or a (meth) acryloyloxy group. Since two vinyl groups contained in the form of a (meth) acryloyloxy group can react with different molecules, they can be suitably used as a crosslinking agent. Furthermore, the compound represented by the general formula (1) gives a cured product having high hardness, and is preferable as a base material component in the composition. The compound represented by the general formula (1) can be used in various applications such as a microlens, a prism sheet, a hologram, and a carbon hard mask.

  Among the compounds represented by the general formula (1), preferred specific examples include compounds represented by the following formulas. Especially, the compound represented by the following upper left formula and the compound represented by the following upper right formula are preferable.

  The content of the compound represented by the above formula (1) is preferably 1 to 95% by mass and more preferably 3 to 80% by mass with respect to the solid content of the composition according to the present invention. It is still more preferable that it is 5-50 mass%. By setting it as the above range, the coating film forming ability and the like are easily improved.

[Method for Producing Vinyl Group-Containing Compound Represented by General Formula (1)]
The vinyl group-containing compound represented by the general formula (1) can be synthesized by any one of the following production methods 1 to 3, for example.

(Manufacturing method 1)
The vinyl group-containing compound represented by the general formula (1) is represented by the following general formula (13) in the presence of a transition element compound catalyst and an inorganic base, for example, according to the production method described in JP-A-2008-266169. It can be synthesized by reacting the vinyl ester compound represented with the hydroxyl group-containing compound represented by the following general formula (3). The inorganic base is preferably a solid inorganic base containing 10% by weight or more of particles having a particle diameter of less than 150 μm.

_{^{R 6 -CO-O-CH =}} CH 2 (13)
(In the formula, R ⁶ represents a hydrogen atom or an organic group.)

（式中、Ｗ^３及びＷ^４は独立に下記一般式（４）で表される基又は水酸基を示し、ただし、Ｗ^３及びＷ^４は同時に水酸基ではなく、環Ｙ^１、環Ｙ^２、Ｒ、Ｒ^３ａ、Ｒ^３ｂ、ｎ１、及びｎ２は上記の通りである。）

(W ³ and W ⁴ in the formula independently represent a group or a hydroxyl group represented by the following general formula (4), provided that W ³ and W ⁴ are not hydroxyl groups at the same time, but are represented by ring Y ¹ , ring Y ² , R , R ^3a , R ^3b , n1, and n2 are as described above.)

（式中、環Ｚ、Ｘ、Ｒ^１、Ｒ^２、及びｍは上記の通りである。）

(In the formula, rings Z, X, R ¹ , R ² , and m are as described above.)

  In addition, the compound represented by the general formula (3) includes, for example, a compound represented by the following general formula (14) and / or a compound represented by the following general formula (15) in the presence of an acid catalyst, It can be synthesized by reacting with a compound represented by the following general formula (16). The desired compound represented by the above general formula (3) is appropriately adjusted by adjusting the combination of the compound represented by the following general formula (14) and the compound represented by the following general formula (15), the amount of addition, and the like. A hydroxyl group-containing compound can be obtained. Further, after the reaction, the target hydroxyl group-containing compound may be separated by a known separation method such as silica gel column chromatography.

（上記一般式（１４）、（１５）、及び（１６）中、環Ｙ^１、環Ｙ^２、環Ｚ、Ｒ、Ｒ^１、Ｒ^２、Ｒ^３ａ、Ｒ^３ｂ、ｍ、ｎ１、及びｎ２は上記の通りである。）

(In the above general formulas (14), (15), and (16), ring Y ¹ , ring Y ² , ring Z, R, R ¹ , R ² , R ^3a , R ^3b , m, n1, and n2 are As above.)

  Examples of the acid catalyst and reaction conditions used for the synthesis of the compound represented by the general formula (3) are described in claims in JP2011-201791A and JP2002-255929A, for example. What is described that it can be used for the manufacturing method of the made fluorene type compound is mentioned.

(Manufacturing method 2)
The vinyl group-containing compound represented by the general formula (1) is, for example, from the hydroxyl group-containing compound represented by the general formula (3) via the leaving group-containing compound represented by the following general formula (5). And it is also possible to synthesize | combine with the manufacturing method including obtaining the vinyl group containing compound represented by the said General formula (1).

（式中、Ｗ^５及びＷ^６は独立に下記一般式（６）で表される基又は水酸基を示し、ただし、Ｗ^５及びＷ^６は同時に水酸基ではなく、環Ｙ^１、環Ｙ^２、Ｒ、Ｒ^３ａ、Ｒ^３ｂ、ｎ１、及びｎ２は上記の通りである。）

(W ⁵ and W ⁶ in the formula independently represent a group or a hydroxyl group represented by the following general formula (6), provided that W ⁵ and W ⁶ are not hydroxyl groups at the same time, but are represented by ring Y ¹ , ring Y ² , R , R ^3a , R ^3b , n1, and n2 are as described above.)

（式中、Ｅは塩素原子、臭素原子、ヨウ素原子、メタンスルホニルオキシ基、トリフルオロメタンスルホニルオキシ基、パラトルエンスルホニルオキシ基、又はベンゼンスルホニルオキシ基で置換された炭素数１〜４のアルキルオキシ基を示し、環Ｚ、Ｘ、Ｒ^１、Ｒ^２、及びｍは上記の通りである。）

(In the formula, E represents a C1-C4 alkyloxy group substituted with a chlorine atom, a bromine atom, an iodine atom, a methanesulfonyloxy group, a trifluoromethanesulfonyloxy group, a paratoluenesulfonyloxy group, or a benzenesulfonyloxy group. And rings Z, X, R ¹ , R ² , and m are as described above.)

  The leaving group-containing compound represented by the general formula (5) can be synthesized, for example, by reacting the hydroxyl group-containing compound represented by the general formula (3) with the leaving group-containing compound. . Examples of the leaving group-containing compound include thionyl chloride, a compound represented by the following formula, and the like. Moreover, as reaction temperature, -20-150 degreeC, Preferably it is -10-140 degreeC, More preferably, 30-130 degreeC is mentioned.

  The vinyl group-containing compound represented by the general formula (1) can be synthesized, for example, by reacting the leaving group-containing compound represented by the general formula (5) with a vinylating agent. Examples of the vinylating agent include sodium hydroxide, triethylamine, diisopropylethylamine, 1,4-diazabicyclo [2.2.2] octane, diazabicycloundecene, sodium methoxide, sodium ethoxide, sodium ethoxide, potassium. -T-butoxide etc. are mentioned, Preferably diazabicycloundecene, sodium ethoxide, potassium-t-butoxide etc. are mentioned, More preferably, potassium-t-butoxide is mentioned. Moreover, as reaction temperature, -20-150 degreeC is preferable, Preferably it is -10-100 degreeC, More preferably, 0-60 degreeC is mentioned.

(Manufacturing method 3)
The compound represented by the general formula (1) is, for example, from a hydroxyalkyloxy group-containing compound represented by the following general formula (7) via a leaving group-containing compound represented by the above general formula (5). And it is also possible to synthesize | combine with the manufacturing method including obtaining the vinyl group containing compound represented by the said General formula (1).

（式中、Ｗ^７及びＷ^８は独立に下記一般式（８）で表される基又は水酸基を示し、ただし、Ｗ^７及びＷ^８は同時に水酸基ではなく、環Ｙ^１、環Ｙ^２、Ｒ、Ｒ^３ａ、Ｒ^３ｂ、ｎ１、及びｎ２は上記の通りである。）

(Wherein W ⁷ and W ⁸ independently represent a group or a hydroxyl group represented by the following general formula (8), provided that W ⁷ and W ⁸ are not hydroxyl groups at the same time, but are represented by ring Y ¹ , ring Y ² , R , R ^3a , R ^3b , n1, and n2 are as described above.)

（式中、ｌは１〜４の整数を示し、環Ｚ、Ｘ、Ｒ^１、Ｒ^２、及びｍは上記の通りである。）

(In the formula, l represents an integer of 1 to 4, and the rings Z, X, R ¹ , R ² , and m are as described above.)

  The hydroxyalkyloxy group-containing compound represented by the general formula (7) is represented by, for example, a compound represented by the following general formula (17) and / or the following general formula (18) in the presence of an acid catalyst. It can synthesize | combine by making a compound and the compound represented by the said General formula (16) react. The desired compound represented by the above general formula (7) is appropriately adjusted by adjusting the combination method and the amount of the compound represented by the following general formula (17) and the compound represented by the following general formula (18). A hydroxyalkyloxy group-containing compound can be obtained. Further, after the reaction, the target hydroxyalkyloxy group-containing compound may be separated by a known separation method such as silica gel column chromatography. Examples of the acid catalyst and reaction conditions used for the synthesis of the compound represented by the general formula (7) include those exemplified in the description of the method for synthesizing the compound represented by the general formula (3). It is done.

（上記一般式（１７）及び（１８）中、環Ｚ、Ｒ^１、Ｒ^２、及びｍは上記の通りである。）

(In the general formulas (17) and (18), the rings Z, R ¹ , R ² , and m are as described above.)

  The leaving group-containing compound represented by the general formula (5) is synthesized, for example, by reacting the hydroxyalkyloxy group-containing compound represented by the general formula (7) with the leaving group-containing compound. be able to. As a leaving group containing compound and reaction temperature, what was illustrated about the said manufacturing method 2 is mentioned, for example.

  The vinyl group-containing compound represented by the general formula (1) can be synthesized, for example, by reacting the leaving group-containing compound represented by the general formula (5) with a vinylating agent. As a vinylating agent and reaction temperature, what was illustrated about the said manufacturing method 2 is mentioned, for example.

<Calicyclic ether group-containing compound having an alicyclic ether group having 2 to 6 carbon atoms>
The alicyclic ether group-containing compound contained in the curable composition according to the present invention has an alicyclic ether group having 2 to 6 carbon atoms. A cured product of the curable composition according to the present invention is generated by a reaction between the vinyl group-containing compound represented by the general formula (1) and the alicyclic ether group-containing compound. The curable composition which concerns on this invention has the outstanding surface curability by containing the said alicyclic ether group containing compound. Moreover, the said alicyclic ether group containing compound has an effect which improves the mechanical strength of hardened | cured material. The said alicyclic ether group containing compound can be used individually or in combination of 2 or more types.

  The alicyclic ether group having 2 to 6 carbon atoms is not particularly limited, and for example, one or more, preferably one hydrogen atom bonded to a carbon atom forming a ring of a 3- to 7-membered cyclic ether. Or the group obtained by removing two is mentioned. Examples of the 3- to 7-membered cyclic ether include compounds represented by the following formulas (b-1) to (b-6).

  Among them, from the viewpoint of reactivity, an epoxy group (a group obtained by removing one or more hydrogen atoms of a 3-membered cyclic ether represented by the above formula (b-1), preferably one or two), An oxetane residue (a group obtained by removing one or more, preferably one or two hydrogen atoms of a 4-membered cyclic ether represented by the above formula (b-2)) is preferred, and an epoxy group is more preferred. An epoxy group represented by the following formula (b-1-1) or (b-1-2) is even more preferable. In the present specification, the alicyclic epoxy group is an oxygen common to two carbon atoms (usually adjacent to each other) among the carbon atoms forming the alicyclic structure of the alicyclic compound. An epoxy group formed by bonding one atom.

  Among the alicyclic ether group-containing compounds, the following epoxy compounds (i) to (viii) can be suitably used as the epoxy group-containing compound.

(I) Aromatic glycidyl ethers Aromatic glycidyl ethers are not particularly limited as long as they are compounds having an aromatic group and a glycidyl ether group in the molecule. Specific examples of aromatic glycidyl ethers include bisphenol A type epoxy resin; bisphenol F type epoxy resin; bisphenol AD type epoxy resin; phenol novolac type epoxy resin; cresol novolac type epoxy resin; biphenol type or bixylenol type epoxy resin. Or a mixture thereof; a naphthalene group-containing epoxy resin; a dicyclopentadiene skeleton-containing epoxy resin; a brominated epoxy resin; a trisphenolmethane type epoxy resin; represented by each of the following formulas (b-7) to (b-11): Examples thereof include glycidyl group-containing aromatic compounds.

(Ii) Aliphatic glycidyl ethers The aliphatic glycidyl ethers are not particularly limited as long as they are compounds having an aliphatic group and a glycidyl ether group in the molecule. Specific examples of aliphatic glycidyl ethers include hydrogenated or semi-hydrogenated epoxies obtained by subjecting aromatic glycidyl ethers to hydrogenation treatment, such as hydrogenated bisphenol A type epoxy resins and hydrogenated bisphenol F type epoxy resins. Resin; ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, 1,4-butanediol diglycidyl ether, neopentyl glycol diglycidyl ether, diethylene glycol diglycidyl ether, 1,4-cyclohexanedimethanol diglycidyl ether, 1,6 -A polyfunctional glycidyl group-containing aliphatic compound such as hexanediol diglycidyl ether, dipropylene glycol diglycidyl ether, trimethylolpropane triglycidyl ether, epoxidized soybean oil; Monofunctional glycidyl group-containing aliphatic compounds such as glycidyl ether, and the like.

(Iii) Aromatic glycidyl esters Aromatic glycidyl esters are not particularly limited as long as they are compounds having an aromatic group and a glycidyl ester group in the molecule. Specific examples of the aromatic glycidyl esters include diglycidyl phthalate and diglycidyl terephthalate.

(Iv) Aliphatic glycidyl esters The aliphatic glycidyl esters are not particularly limited as long as they are compounds having an aliphatic group and a glycidyl ester group in the molecule. Specific examples of the aliphatic glycidyl esters include 1,2-cyclohexanedicarboxylic acid bis (2,3-epoxypropyl) ester, dimer acid diglycidyl ester, tertiary carboxylic acid glycidyl ester, and the like.

(V) Alicyclic epoxy compound The alicyclic epoxy compound is not particularly limited as long as it is a compound having an alicyclic group and an epoxy group in the molecule. Specific examples of the alicyclic epoxy compound include 3,4,3 ′, 4′-diepoxybicyclohexyl, 1,2: 8,9 diepoxy limonene, and 3,4-epoxycyclohexylmethyl-3 ′, 4 ′. -Epoxycyclohexanecarboxylate, epsilon-caprolactone modified 3,4-epoxycyclohexylmethyl-3 ', 4'-epoxycyclohexanecarboxylate, bis (3,4-epoxycyclohexylmethyl) adipate, 2- (7-oxabicyclo [4 .1.0] hept-3-yl) -spiro [1,3-dione-5,3 ′-[7] oxabicyclo [4.1.0] heptane], dicyclopentadiene dioxide and the like.

(Vi) Glycidylamines Glycidylamines are not particularly limited as long as they are amines having a glycidyl group. Specific examples of glycidylamines include N, N-diglycidyl-4-glycidyloxyaniline, tetraglycidyldiaminodiphenylmethane, aniline diglycidyl ether, N- (2-methylphenyl) -N- (oxiranylmethyl) oxirane methane. An amine, N-glycidyl phthalimide, etc. are mentioned.

(Vii) Heterocyclic Epoxy Compound The heterocyclic epoxy compound is not particularly limited as long as it is a heterocyclic compound having a glycidyl group. Specific examples of the heterocyclic epoxy compound include tris (2,3-epoxypropyl) isocyanurate.

(Viii) Other epoxy group-containing compound The other epoxy group-containing compound is not particularly limited as long as it is an epoxy group-containing compound other than the above. Specific examples of other epoxy group-containing compounds include epoxides of unsaturated group-containing polymers such as epoxides of homopolymers or copolymers of butadiene; glycidyl (meth) acrylate and 3,4-epoxycyclohexylmethyl. Homopolymer or copolymer of epoxy group-containing (meth) acrylate such as (meth) acrylate; glycidyl group-containing silane (for example, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ -Glycidoxypropylmethyldimethoxysilane), alicyclic epoxy group-containing silane (for example, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltriethoxysilane) And epoxy group-containing silanes.
In the present specification, “(meth) acrylate” means both acrylate and methacrylate.

  Among the alicyclic ether group-containing compounds, the oxetane residue-containing compound is not particularly limited, and 3-ethyl-3- (hydroxymethyl) oxetane, 3-ethyl-3-[(phenoxy) methyl] oxetane, Monofunctional oxetanes such as 3-ethyl-3- (hexyloxymethyl) oxetane, 3-ethyl-3- (2-ethylhexyloxymethyl) oxetane, 3-ethyl-3- (chloromethyl) oxetane; xylylene bisoxetane , 1,4-bis [(3-ethyl-3-oxetanylmethoxy) methyl] benzene, and polyfunctional oxetanes such as bis {[1-ethyl (3-oxetanyl)] methyl} ether. The oxetane residue-containing compound can be used alone or in combination of two or more.

  It may be possible to improve the curing rate of the curable composition and the reaction rate of the cured product by mixing the oxetane residue-containing compound with the epoxy group-containing compound.

  The number of the alicyclic ether groups in the alicyclic ether group-containing compound is not particularly limited as long as it is at least one. The reactivity of the alicyclic ether group-containing compound during curing is likely to be high, and the alicyclic ether group-containing compound in the alicyclic ether group-containing compound is preferable because a three-dimensional network is easily formed in the resulting cured product. The number of ether groups is preferably at least 2.

  The alicyclic ether group-containing compound may contain a functional group other than the alicyclic ether group. The functional group is not particularly limited. When the functional group is a reactive silyl group, the alicyclic ether group-containing compound functions as a silane coupling agent.

As the alicyclic ether group-containing compound,
3,4,3 ′, 4′-diepoxybicyclohexyl; 3,4-epoxycyclohexylmethyl-3 ′, 4′-epoxycyclohexanecarboxylate; glycidyl (meth) acrylate and 3,4-epoxycyclohexylmethyl (meth) A compound having two or more alicyclic epoxy groups in the molecule, such as a homopolymer or copolymer of an epoxy group-containing (meth) acrylate such as an acrylate,
Compounds having an alicyclic epoxy group and a glycidyl group in the molecule, such as 1,2: 8,9 diepoxy limonene,
A compound having two or more glycidyl groups in the molecule, such as a bisphenol A type epoxy resin, a glycidyl group-containing aromatic compound represented by each of the above formulas (b-7) to (b-10),
A compound having two or more oxetane residues in the molecule, such as xylylene bisoxetane, is preferable, and from the viewpoint of reactivity, a compound having two or more alicyclic epoxy groups in the molecule, and A compound having two or more glycidyl groups in the molecule is more preferable.

  In the curable composition according to the present invention, the content of the alicyclic ether group-containing compound is not particularly limited, but is 5 with respect to 100 parts by mass of the vinyl group-containing compound represented by the general formula (1). -200 mass parts is preferable, 50-150 mass parts is more preferable, and 70-130 mass parts is still more preferable. When the content is from 5 to 200 parts by mass, the surface curability of the curable composition tends to be good, and at the same time, the flexibility of the resulting cured product is likely to be sufficient. The balance with is easy to improve.

<Proton donating compound>
The curable composition according to the present invention may further contain a proton donating compound. Protons generated from the proton donating compound facilitate the reaction between the vinyl group-containing compound represented by the general formula (1) and the alicyclic ether group-containing compound, and the curable composition according to the present invention Curing is facilitated. The proton donating compounds can be used alone or in combination of two or more.

  The proton donating compound is not particularly limited as long as it is a compound that can generate protons and donate protons to other compounds. Examples of proton-donating compounds include acid generators; alcohols such as methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, sec-butanol, tert-butanol, n-amyl alcohol, and tert-amyl alcohol. Aliphatic amines (eg triethanolamine, methyldiethanolamine, triisopropanolamine), aromatic amines (eg methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 4 -2-ethylhexyl dimethylaminobenzoate, 2-dimethylaminoethyl benzoate, N, N-dimethylparatoluidine, 4,4'-bis (dimethylamino) benzophenone, 4,4'-bis (diethylamino) Amines such as aromatic thiols (eg 2-mercaptobenzoxazole, 2-mercaptobenzthiazole, 2-mercaptobenzimidazole), thiols such as aliphatic thiols (eg methanethiol, ethanethiol, propanethiol); Examples thereof include inorganic acids such as hydrochloric acid and sulfuric acid; organic acids such as formic acid, acetic acid and propionic acid; hydrogen and water. Among them, acid generators are preferable from the viewpoint of reactivity and the like.

  As the acid generator, a photoacid generator that generates an acid upon irradiation with actinic rays or radiation, or a thermal acid generator that generates an acid upon heating is suitably used.

  It does not specifically limit as a photo-acid generator, A conventionally well-known photo-acid generator can be used. Specific examples of photoacid generators include onium salt acid generators such as iodonium salts and sulfonium salts, oxime sulfonate acid generators, halogen-containing triazine compounds, diazomethane acid generators, nitrobenzyl sulfonate acid generators ( Nitrobenzyl derivatives), iminosulfonate acid generators, disulfone acid generators and the like.

  Preferred examples of the sulfonium salt acid generator include a compound represented by the following general formula (t-1).

In the general formula (t-1), R ^t1 and R ^t2 may each independently have a hydrogen atom, a halogen atom, an oxygen atom, a hydrocarbon group which may have a halogen atom, or a substituent. Represents a good alkoxy group, R ^t3 represents a halogen atom or a p-phenylene group optionally having an alkyl group, R ^t4 represents a hydrocarbon group optionally having a hydrogen atom, an oxygen atom or a halogen atom, A benzoyl group which may have a substituent, or a polyphenyl group which may have a substituent, A ⁻ represents a counter ion of an onium ion.

Specific examples of A ⁻ include SbF ₆ ⁻ , PF ₆ ⁻ , AsF ₆ ⁻ , BF ₄ ⁻ , SbCl ₆ ⁻ , ClO ₄ ⁻ , CF ₃ SO ₃ ⁻ , CH ₃ SO ₃ ⁻ , FSO ₃ ⁻ and F _2. Examples thereof include PO ₂ ⁻ , p-toluenesulfonate, nonafluorobutanesulfonate, adamantanecarboxylate, tetraarylborate, and a fluorinated alkylfluorophosphate anion represented by the following general formula (t-2).

  In the general formula (t-2), Rf represents an alkyl group in which 80% or more of hydrogen atoms are substituted with fluorine atoms. g is the number and represents an integer of 1 to 5. The g Rf may be the same or different.

  Examples of the photoacid generator represented by the general formula (t-1) include 4- (2-chloro-4-benzoylphenylthio) phenyldiphenylsulfonium hexafluoroantimonate and 4- (2-chloro-4-benzoyl). Phenylthio) phenylbis (4-fluorophenyl) sulfonium hexafluoroantimonate, 4- (2-chloro-4-benzoylphenylthio) phenylbis (4-chlorophenyl) sulfonium hexafluoroantimonate, 4- (2-chloro- 4-benzoylphenylthio) phenylbis (4-methylphenyl) sulfonium hexafluoroantimonate, 4- (2-chloro-4-benzoylphenylthio) phenylbis (4- (β-hydroxyethoxy) phenyl) sulfonium hexafluoroantimonate Nate, -(2-Methyl-4-benzoylphenylthio) phenylbis (4-fluorophenyl) sulfonium hexafluoroantimonate, 4- (3-methyl-4-benzoylphenylthio) phenylbis (4-fluorophenyl) sulfonium hexafluoro Antimonate, 4- (2-fluoro-4-benzoylphenylthio) phenylbis (4-fluorophenyl) sulfonium hexafluoroantimonate, 4- (2-methyl-4-benzoylphenylthio) phenylbis (4-fluorophenyl) Sulfonium hexafluoroantimonate, 4- (2,3,5,6-tetramethyl-4-benzoylphenylthio) phenylbis (4-fluorophenyl) sulfonium hexafluoroantimonate, 4- (2,6-dichloro-4 -Be Nzoylphenylthio) phenylbis (4-fluorophenyl) sulfonium hexafluoroantimonate, 4- (2,6-dimethyl-4-benzoylphenylthio) phenylbis (4-fluorophenyl) sulfonium hexafluoroantimonate, 4- (2,3-dimethyl-4-benzoylphenylthio) phenylbis (4-fluorophenyl) sulfonium hexafluoroantimonate, 4- (2-methyl-4-benzoylphenylthio) phenylbis (4-chlorophenyl) sulfonium hexafluoro Antimonate, 4- (3-methyl-4-benzoylphenylthio) phenylbis (4-chlorophenyl) sulfonium hexafluoroantimonate, 4- (2-fluoro-4-benzoylphenylthio) phenylbis (4 Chlorophenyl) sulfonium hexafluoroantimonate, 4- (2-methyl-4-benzoylphenylthio) phenylbis (4-chlorophenyl) sulfonium hexafluoroantimonate, 4- (2,3,5,6-tetramethyl-4- Benzoylphenylthio) phenylbis (4-chlorophenyl) sulfonium hexafluoroantimonate, 4- (2,6-dichloro-4-benzoylphenylthio) phenylbis (4-chlorophenyl) sulfonium hexafluoroantimonate, 4- (2, 6-dimethyl-4-benzoylphenylthio) phenylbis (4-chlorophenyl) sulfonium hexafluoroantimonate, 4- (2,3-dimethyl-4-benzoylphenylthio) phenylbis (4-chlorophenyl) s Honium hexafluoroantimonate, 4- (2-chloro-4-acetylphenylthio) phenyldiphenylsulfonium hexafluoroantimonate, 4- (2-chloro-4- (4-methylbenzoyl) phenylthio) phenyldiphenylsulfonium hexafluoro Antimonate, 4- (2-chloro-4- (4-fluorobenzoyl) phenylthio) phenyldiphenylsulfonium hexafluoroantimonate, 4- (2-chloro-4- (4-methoxybenzoyl) phenylthio) phenyldiphenylsulfonium hexafluoro Antimonate, 4- (2-chloro-4-dodecanoylphenylthio) phenyldiphenylsulfonium hexafluoroantimonate, 4- (2-chloro-4-acetylphenylthio) phenyl Bis (4-fluorophenyl) sulfonium hexafluoroantimonate, 4- (2-chloro-4- (4-methylbenzoyl) phenylthio) phenylbis (4-fluorophenyl) sulfonium hexafluoroantimonate, 4- (2-chloro -4- (4-Fluorobenzoyl) phenylthio) phenylbis (4-fluorophenyl) sulfonium hexafluoroantimonate, 4- (2-chloro-4- (4-methoxybenzoyl) phenylthio) phenylbis (4-fluorophenyl) Sulfonium hexafluoroantimonate, 4- (2-chloro-4-dodecanoylphenylthio) phenylbis (4-fluorophenyl) sulfonium hexafluoroantimonate, 4- (2-chloro-4-acetylphenylthio) phenyl (4-chlorophenyl) sulfonium hexafluoroantimonate, 4- (2-chloro-4- (4-methylbenzoyl) phenylthio) phenylbis (4-chlorophenyl) sulfonium hexafluoroantimonate, 4- (2-chloro-4 -(4-Fluorobenzoyl) phenylthio) phenylbis (4-chlorophenyl) sulfonium hexafluoroantimonate, 4- (2-chloro-4- (4-methoxybenzoyl) phenylthio) phenylbis (4-chlorophenyl) sulfonium hexafluoroantimony 4- (2-chloro-4-dodecanoylphenylthio) phenylbis (4-chlorophenyl) sulfonium hexafluoroantimonate, 4- (2-chloro-4-benzoylphenylthio) phenyldipheny Sulfonium hexafluorophosphate, 4- (2-chloro-4-benzoylphenylthio) phenyldiphenylsulfonium tetrafluoroborate, 4- (2-chloro-4-benzoylphenylthio) phenyldiphenylsulfonium perchlorate, 4- (2-chloro -4-benzoylphenylthio) phenyldiphenylsulfonium trifluoromethanesulfonate, 4- (2-chloro-4-benzoylphenylthio) phenylbis (4-fluorophenyl) sulfonium hexafluorophosphate, 4- (2-chloro-4-benzoyl) Phenylthio) phenylbis (4-fluorophenyl) sulfonium tetrafluoroborate, 4- (2-chloro-4-benzoylphenylthio) phenylbis (4-fluorophenyl) sulfur Honium perchlorate, 4- (2-chloro-4-benzoylphenylthio) phenylbis (4-fluorophenyl) sulfonium trifluoromethanesulfonate, 4- (2-chloro-4-benzoylphenylthio) phenylbis (4-fluoro Phenyl) sulfonium p-toluenesulfonate, 4- (2-chloro-4-benzoylphenylthio) phenylbis (4-fluorophenyl) sulfonium camphorsulfonate, 4- (2-chloro-4-benzoylphenylthio) phenylbis (4 -Fluorophenyl) sulfonium nonafluorobutanesulfonate, 4- (2-chloro-4-benzoylphenylthio) phenylbis (4-chlorophenyl) sulfonium hexafluorophosphate, 4- (2-chloro-4-benzoyl) Phenylthio) phenylbis (4-chlorophenyl) sulfonium tetrafluoroborate, 4- (2-chloro-4-benzoylphenylthio) phenylbis (4-chlorophenyl) sulfonium perchlorate, 4- (2-chloro-4-benzoylphenylthio) ) Phenylbis (4-chlorophenyl) sulfonium trifluoromethanesulfonate, diphenyl [4- (phenylthio) phenyl] sulfonium trifluorotrispentafluoroethyl phosphate, diphenyl [4- (p-terphenylthio) phenyl] sulfonium hexafluoroantimonate And diphenyl [4- (p-terphenylthio) phenyl] sulfonium trifluorotrispentafluoroethyl phosphate.

  Other onium salt acid generators include, for example, triphenylsulfonium, (4-tert-butoxyphenyl) diphenylsulfonium, bis (4-tert-butoxyphenyl) for the cation moiety of the general formula (t-1). Phenylsulfonium, tris (4-tert-butoxyphenyl) sulfonium, (3-tert-butoxyphenyl) diphenylsulfonium, bis (3-tert-butoxyphenyl) phenylsulfonium, tris (3-tert-butoxyphenyl) sulfonium, (3 , 4-ditert-butoxyphenyl) diphenylsulfonium, bis (3,4-ditert-butoxyphenyl) phenylsulfonium, tris (3,4-ditert-butoxyphenyl) sulfonium, diphenyl (4-thiophene) Xylphenyl) sulfonium, (4-tert-butoxycarbonylmethyloxyphenyl) diphenylsulfonium, tris (4-tert-butoxycarbonylmethyloxyphenyl) sulfonium, (4-tert-butoxyphenyl) bis (4-dimethylaminophenyl) sulfonium, Tris (4-dimethylaminophenyl) sulfonium, 2-naphthyldiphenylsulfonium, dimethyl-2-naphthylsulfonium, 4-hydroxyphenyldimethylsulfonium, 4-methoxyphenyldimethylsulfonium, trimethylsulfonium, 2-oxocyclohexylcyclohexylmethylsulfonium, trinaphthyl Sulfonium cations such as sulfonium and tribenzylsulfonium, diphenyliodonium, bis ( -tert- butylphenyl) iodonium, include those replaced with (4-tert- butoxyphenyl) phenyliodonium, (4-methoxyphenyl) iodonium cation aryl iodonium cations such as iodonium.

Examples of the oxime sulfonate acid generator include [2- (propylsulfonyloxyimino) -2,3-dihydrothiophene-3-ylidene] (o-tolyl) acetonitrile, α- (p-toluenesulfonyloxyimino) -phenylacetonitrile. , Α- (benzenesulfonyloxyimino) -2,4-dichlorophenylacetonitrile, α- (benzenesulfonyloxyimino) -2,6-dichlorophenylacetonitrile, α- (2-chlorobenzenesulfonyloxyimino) -4-methoxyphenylacetonitrile, α- (ethylsulfonyloxyimino) -1-cyclopentenylacetonitrile and the like can be mentioned.
In addition to the above, a compound represented by the following general formula (t-3) can be given.

In the general formula (t-3), R ^t5 represents a monovalent, divalent, or trivalent organic group, and R ^t6 represents a substituted or unsubstituted saturated hydrocarbon group, unsaturated hydrocarbon group, or aromatic group. And h represents an integer of 1 to 6.
R ^t5 is particularly preferably an aromatic compound group. Examples of such an aromatic compound group include aromatic hydrocarbon groups such as a phenyl group and a naphthyl group, and heterocyclic rings such as a furyl group and a thienyl group. Groups and the like. These may have one or more suitable substituents such as a halogen atom, an alkyl group, an alkoxy group, and a nitro group on the ring. R ^t6 is particularly preferably an alkyl group having 1 to 6 carbon atoms, and examples include a methyl group, an ethyl group, a propyl group, and a butyl group. H is preferably an integer of 1 to 3, and more preferably 1 or 2.

As the photoacid generator represented by the general formula (t-3), when t = 1, R ^t5 is any one of a phenyl group, a methylphenyl group, and a methoxyphenyl group, and R ^Examples include compounds in which ^t6 is a methyl group. More specifically, as the photoacid generator represented by the general formula (t-3), α- (methylsulfonyloxyimino) -1-phenylacetonitrile, α- (methylsulfonyloxyimino) -1- ( p-methylphenyl) acetonitrile and α- (methylsulfonyloxyimino) -1- (p-methoxyphenyl) acetonitrile.

  Examples of the photoacid generator represented by the general formula (t-3) include photoacid generators represented by the following formula when h = 2.

  Examples of halogen-containing triazine compounds include 2,4-bis (trichloromethyl) -6-piperonyl-1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (2-furyl) ethenyl. ] -S-triazine, 2,4-bis (trichloromethyl) -6- [2- (5-methyl-2-furyl) ethenyl] -s-triazine, 2,4-bis (trichloromethyl) -6- [ 2- (5-ethyl-2-furyl) ethenyl] -s-triazine, 2,4-bis (trichloromethyl) -6- [2- (5-propyl-2-furyl) ethenyl] -s-triazine, 2 , 4-Bis (trichloromethyl) -6- [2- (3,5-dimethoxyphenyl) ethenyl] -s-triazine, 2,4-bis (trichloromethyl) -6- [2- (3,5-di Ethoxypheny ) Ethenyl] -s-triazine, 2,4-bis (trichloromethyl) -6- [2- (3,5-dipropoxyphenyl) ethenyl] -s-triazine, 2,4-bis (trichloromethyl) -6 -[2- (3-methoxy-5-ethoxyphenyl) ethenyl] -s-triazine, 2,4-bis (trichloromethyl) -6- [2- (3-methoxy-5-propoxyphenyl) ethenyl] -s -Triazine, 2,4-bis (trichloromethyl) -6- [2- (3,4-methylenedioxyphenyl) ethenyl] -s-triazine, 2,4-bis (trichloromethyl) -6- (3 4-methylenedioxyphenyl) -s-triazine, 2,4-bis-trichloromethyl-6- (3-bromo-4-methoxy) phenyl-s-triazine, 2,4-bis-triazine Loromethyl-6- (2-bromo-4-methoxy) phenyl-s-triazine, 2,4-bis-trichloromethyl-6- (2-bromo-4-methoxy) styrylphenyl-s-triazine, 2,4- Bis-trichloromethyl-6- (3-bromo-4-methoxy) styrylphenyl-s-triazine, 2- (4-methoxyphenyl) -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (4-Methoxynaphthyl) -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- [2- (2-furyl) ethenyl] -4,6-bis (trichloromethyl)- 1,3,5-triazine, 2- [2- (5-methyl-2-furyl) ethenyl] -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- [2- (3 , 5-Zime Toxiphenyl) ethenyl] -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- [2- (3,4-dimethoxyphenyl) ethenyl] -4,6-bis (trichloromethyl)- 1,3,5-triazine, 2- (3,4-methylenedioxyphenyl) -4,6-bis (trichloromethyl) -1,3,5-triazine, tris (1,3-dibromopropyl) -1 , 3,5-triazine, halogen-containing triazine compounds such as tris (2,3-dibromopropyl) -1,3,5-triazine, and the following general formulas such as tris (2,3-dibromopropyl) isocyanurate ( and halogen-containing triazine compounds represented by t-4).

In the general formula (t-4), R ^t7 , R ^t8 and R ^t9 each independently represent a halogenated alkyl group having 1 to 6 carbon atoms.

  Other photoacid generators include bis (p-toluenesulfonyl) diazomethane, methylsulfonyl-p-toluenesulfonyldiazomethane, 1-cyclohexylsulfonyl-1- (1,1-dimethylethylsulfonyl) diazomethane, bis (1 , 1-dimethylethylsulfonyl) diazomethane, bis (1-methylethylsulfonyl) diazomethane, bis (cyclohexylsulfonyl) diazomethane, bis (2,4-dimethylphenylsulfonyl) diazomethane, bis (4-ethylphenylsulfonyl) diazomethane, bis ( 3-methylphenylsulfonyl) diazomethane, bis (4-methoxyphenylsulfonyl) diazomethane, bis (4-fluorophenylsulfonyl) diazomethane, bis (4-chlorophenylsulfonyl) diazo Bissulfonyldiazomethanes such as tan, bis (4-tert-butylphenylsulfonyl) diazomethane; 2-methyl-2- (p-toluenesulfonyl) propiophenone, 2- (cyclohexylcarbonyl) -2- (p-toluenesulfonyl) ) Sulfonylsulfonyl alkanes such as propane, 2-methanesulfonyl-2-methyl- (p-methylthio) propiophenone, 2,4-dimethyl-2- (p-toluenesulfonyl) pentan-3-one; -Toluenesulfonyl-1-cyclohexylcarbonyldiazomethane, 1-diazo-1-methylsulfonyl-4-phenyl-2-butanone, 1-cyclohexylsulfonyl-1-cyclohexylcarbonyldiazomethane, 1-diazo-1-cyclohexylsulfonyl-3,3 -Dimethyl 2-butanone, 1-diazo-1- (1,1-dimethylethylsulfonyl) -3,3-dimethyl-2-butanone, 1-acetyl-1- (1-methylethylsulfonyl) diazomethane, 1-diazo- 1- (p-toluenesulfonyl) -3,3-dimethyl-2-butanone, 1-diazo-1-benzenesulfonyl-3,3-dimethyl-2-butanone, 1-diazo-1- (p-toluenesulfonyl) -3-methyl-2-butanone, 2-diazo-2- (p-toluenesulfonyl) acetate cyclohexyl, 2-diazo-2-benzenesulfonylacetate-tert-butyl, 2-diazo-2-methanesulfonylacetate isopropyl, 2 -Diazo-2-benzenesulfonylacetate cyclohexyl, 2-diazo-2- (p-toluenesulfonyl) acetate-tert-butyl Sulfonylcarbonyldiazomethanes such as p-toluenesulfonic acid-2-nitrobenzyl, p-toluenesulfonic acid-2,6-dinitrobenzyl, p-trifluoromethylbenzenesulfonic acid-2,4-dinitrobenzyl, etc. Derivatives: pyrogallol methane sulfonate, pyrogallol benzene sulfonate, pyrogallol p-toluene sulfonate, pyrogallol p-methoxybenzene sulfonate, pyrogallol mesitylene sulfonate, pyrogallol benzyl sulfonate, gallic acid Alkyl methanesulfonate ester, alkyl gallate benzenesulfonate ester, alkyl gallate p-toluenesulfonate ester, alkyl gallate (alkyl group charcoal) The number of which is 1 to 15), such as p-methoxybenzene sulfonate ester, alkyl gallate mesitylene sulfonate ester, alkyl gallate benzyl sulfonate ester, and the like, and ester of aliphatic or aromatic sulfonic acid And the like.

  Examples of the thermal acid generator include 2,4,4,6-tetrabromocyclohexadienone, benzoin tosylate, 2-nitrobenzyl tosylate, and other alkyl esters of organic sulfonic acid. Specific examples include onium salts such as sulfonium salts, iodonium salts, benzothiazonium salts, ammonium salts, and phosphonium salts. Among these onium salts, iodonium salts, sulfonium salts, and benzothiazonium salts are preferable. Specific examples of the sulfonium salt and benzothiazonium salt include 4-acetoxyphenyldimethylsulfonium hexafluoroarsenate, benzyl-4-hydroxyphenylmethylsulfonium hexafluoroantimonate, 4-acetoxyphenylbenzylmethylsulfonium hexafluoroantimonate, Examples thereof include dibenzyl-4-hydroxyphenylsulfonium hexafluoroantimonate, 4-acetoxyphenylbenzylsulfonium hexafluoroantimonate, 3-benzylbenzothiazolium hexafluoroantimonate, and a compound represented by the following formula.

  In the curable composition according to the present invention, the content of the proton donating compound is not particularly limited, but a total of 100 of the vinyl group-containing compound represented by the general formula (1) and the alicyclic ether group-containing compound is 100. 0.1-50 mass parts is preferable with respect to mass parts, 0.5-30 mass parts is more preferable, and 1-20 mass parts is especially preferable. When the content is 0.1 to 50 parts by mass, the curability of the curable composition is easily improved.

<Organic solvent>
The curable composition according to the present invention may further contain an organic solvent. Examples of the organic solvent include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol-n-propyl ether, ethylene glycol mono-n-butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl 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, propylene glycol mono-n-butyl ether, di Propylene glycol monomethyl ether, zip (Poly) alkylene glycol monoalkyl ethers such as pyrene glycol monoethyl ether, dipropylene glycol mono-n-propyl ether, dipropylene glycol mono-n-butyl ether, tripropylene glycol monomethyl ether, tripropylene glycol monoethyl ether; ethylene (Poly) alkylene glycol monoalkyl ether acetates such as 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 acetate; diethylene glycol dimethyl Other ethers such as ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether and tetrahydrofuran; ketones such as methyl ethyl ketone, cyclohexanone, 2-heptanone and 3-heptanone; methyl 2-hydroxypropionate, ethyl 2-hydroxypropionate, etc. Lactic acid alkyl esters; ethyl 2-hydroxy-2-methylpropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl ethoxyacetate, hydroxyacetic acid Ethyl, 2-hydroxy-3-methyl methyl carbonate, 3-methyl-3-methoxybutyl acetate, 3-methyl-3-methoxybutylpropionate, ethyl acetate, n-acetate Propyl, 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 , Other esters such as n-propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, ethyl 2-oxobutanoate; aromatic hydrocarbons such as toluene, xylene; N-methylpyrrolidone, N, N-dimethylformamide, Examples thereof include amides such as N, N-dimethylacetamide. An organic solvent can be used individually or in combination of 2 or more types.

  The content of the organic solvent is preferably such that the solid content concentration of the curable composition according to the present invention is 1 to 50% by mass, and more preferably 5 to 30% by mass.

<Other ingredients>
The curable composition according to the present invention includes a surfactant, a photopolymerization initiator, a photopolymerizable monomer, an acid crosslinkable substance, a base generator (a photobase generator, a thermal base generator, etc.), a colorant, if desired. , Dispersants, sensitizers, and other various additives.

<Preparation of curable composition>
The curable composition which concerns on this invention is prepared by mixing said each component with a stirrer. In addition, you may filter using a membrane filter etc. so that the prepared curable composition may become uniform.

≪Hardened product≫
A cured product can be obtained by curing the curable composition according to the present invention. The curable composition according to the present invention can be cured by heating, for example. Although heating conditions are not specifically limited, As heating temperature, 200-250 degreeC is mentioned, for example, As heating time, about 2-120 minutes is mentioned, for example. When the curable composition according to the present invention contains a photosensitive component such as a photoacid generator, it can also be cured by irradiation with actinic rays or radiation. Examples of the actinic ray or radiation used for exposure include ultraviolet rays, electron beams, and laser beams emitted from low-pressure mercury lamps, high-pressure mercury lamps, metal halide lamps, g-line steppers, i-line steppers, and the like. The exposure amount varies depending on the light source used, the thickness of the coating film, and the like, but is preferably 1 to 1000 mJ / cm ² , more preferably 10 to 500 mJ / cm ² .

≪Curing film, insulating film, color filter, display device, optical member, etc.≫
A cured film, an insulating film, and a color filter can be formed using the curable composition according to the present invention.
For example, a cured film can be obtained by a production method including a step of forming a coating film by applying a curable composition onto a substrate and a step of curing the coating film.
More specifically, first, a coating film is formed by an appropriate coating method. For example, a composition is applied onto a substrate using a contact transfer type coating device such as a roll coater, reverse coater, bar coater, or a non-contact type coating device such as a spinner (rotary coating device) or a curtain flow coater, and then dried. Thus, a coating film can be formed. The drying method is not particularly limited. For example, (1) a method of pre-baking at a temperature of 80 to 120 ° C., preferably 90 to 100 ° C. for 60 to 120 seconds on a hot plate, (2) at room temperature And a method of leaving for several hours to several days, and (3) a method of removing the solvent by leaving it in a warm air heater or an infrared heater for several tens of minutes to several hours.

  The thickness of the coating film is not particularly limited. Typically, the thickness of the coating film is preferably 2 to 100 μm, and more preferably 3 to 50 μm. The thickness of the coating film can be appropriately controlled by adjusting the coating method and the solid content concentration and viscosity of the curable composition.

  The substrate is not particularly limited, and a conventionally known substrate can be used. Examples thereof include a glass substrate, a substrate made of a transparent conductive material such as ITO, and a resin substrate containing a resin such as polyethylene terephthalate (PET). It is done.

  Next, the cured film is obtained by curing the coating film. The coating film can be cured by the same method as curing the curable composition.

  When a curable composition containing no colorant is used, a transparent cured film or insulating film can be obtained. Such a cured film or insulating film is used, for example, as a planarizing film for a liquid crystal display or an organic EL display, or as an interlayer insulating film or a carbon hard mask.

  In addition, when the thing containing photosensitive components, such as a photo-acid generator, is used as a curable composition, the said cured film and the said insulating film may be patterned. As described later, a patterned cured film or insulating film can be obtained by irradiating a developing film with actinic rays or radiation in a predetermined pattern and developing it. The patterned cured film is used, for example, as a spacer or partition wall for a liquid crystal display or an organic EL display.

Further, a coating film is formed using a curable composition containing a colorant and a photosensitive component such as a photoacid generator, and the coating film is irradiated with actinic rays or radiation in a predetermined pattern, and developed. By doing so, for example, pixels of a color filter of a liquid crystal display and a black matrix can be formed.
Such a cured film, an insulating film, and a color filter can be used for a display device. That is, the display device includes the cured film, the insulating film, and / or the color filter. Examples of the display device include a liquid crystal display and an organic EL display.

  Furthermore, an optical member such as a lens (for example, a microlens), an optical fiber, an optical waveguide, a prism sheet, or a hologram can be obtained by molding and curing the curable composition according to the present invention.

≪Pattern formation method≫
The curable composition concerning this invention can be used suitably for the pattern formation method, when photosensitive components, such as a photo-acid generator, are contained. In this pattern forming method, a coating film is formed using a curable composition containing a photosensitive component such as a photoacid generator, and the coating film is irradiated with actinic rays or radiation in a predetermined pattern, and developed. To do.

More specifically, first, a coating film is formed in the same manner as described above.
Next, the coating film is exposed to actinic rays or radiation in a predetermined pattern. The actinic ray or radiation may be irradiated through a negative mask or directly. The type of actinic light or radiation, the exposure amount, etc. are as described above.
Next, the coated film after exposure is developed into a desired shape by developing with a developer. The development method is not particularly limited, and for example, an immersion method, a spray method, or the like can be used. Examples of the developer include organic ones such as monoethanolamine, diethanolamine, and triethanolamine, and aqueous solutions such as sodium hydroxide, potassium hydroxide, sodium carbonate, ammonia, and quaternary ammonium salts.
It is preferable to perform post-baking at about 200 to 250 ° C. for the developed pattern.

  EXAMPLES Hereinafter, although an Example is shown and this invention is demonstrated further more concretely, the scope of the present invention is not limited to these Examples.

≪Material≫
The materials used in the examples and comparative examples are as follows.
<Vinyl group-containing compound (compound represented by formula (1) and comparative compound)>
As the compound represented by the general formula (1), compounds 1 and 2 which are vinyl ether compounds represented by the following formula were prepared. Moreover, the comparison compounds 1-3 which are vinyl ether compounds represented by a following formula were prepared for the comparison.

  A synthesis method of Compound 1 is shown below (Synthesis Example 1). The materials used in the synthesis examples are as follows.

[Inorganic base]
(1) Light ash sodium carbonate particle size distribution: 250 μm or more; 3% by weight
150 μm or more and less than 250 μm; 15% by weight
75 μm or more and less than 150 μm; 50% by weight
<75 μm; 32% by weight
In addition, the above particle size distribution is classified by using 60 mesh (250 μm), 100 mesh (150 μm), and 200 mesh (75 μm) sieves, and finally obtained on the sieving component and the sieving component. Calculated by measuring the weight.

[Transition element compound catalyst]
(1) Di-μ-chlorobis (1,5-cyclooctadiene) diiridium (I): [Ir (cod) Cl] ₂

[Hydroxy compounds]
(1) 9,9′-bis (6-hydroxy-2-naphthyl) fluorene

[Vinyl ester compounds]
(1) Vinyl propionate

[Synthesis Example 1] Synthesis of Compound 1 Into a 1000 ml reaction vessel equipped with a cooling tube and a decanter for separating the condensate and returning the organic layer to the reaction vessel and discharging the aqueous layer out of the system, -Chlorobis (1,5-cyclooctadiene) diiridium (I) [Ir (cod) Cl] ₂ (839 mg, 1.25 mmol), light ash sodium carbonate (12.7 g, 0.12 mol), 9,9 ' -After charging bis (6-hydroxy-2-naphthyl) fluorene (225 g, 0.5 mol), vinyl propionate (125 g, 1.25 mol), and toluene (300 ml), a stirring blade having a surface area of 10 cm ² was used. The number of revolutions was set to 250 rpm, and the temperature was gradually raised and refluxed while stirring. The reaction was carried out for 5 hours under reflux while removing by-product water with a decanter. When the reaction solution was analyzed by gas chromatography, the conversion of 9,9′-bis (6-hydroxy-2-naphthyl) fluorene was 100%, and 9,9′-bis (6-hydroxy-2-naphthyl). ) Based on fluorene, 9,9′-bis (6-vinyloxy-2-naphthyl) fluorene (Compound 1) was produced in a yield of 81% and bis6-naphtholfluorene monovinyl ether in a yield of 4%.
¹ H-NMR (CDCl ₃ ): 4.47 (dd, 2H, J = 1.5 Hz, 5.0 Hz), 4.81 (dd, 2H, J = 3.5 Hz, 12.0 Hz), 6.71 (Dd, 2H, J = 6.0 Hz), 7.12-7.82 (m, 20H)

<Calicyclic ether group-containing compound having an alicyclic ether group having 2 to 6 carbon atoms>
As the alicyclic ether group-containing compound having an alicyclic ether group having 2 to 6 carbon atoms, the following compounds 3 to 8 were used.

Compound 4 is an epoxy resin having a structural unit represented by the above formulas I to IV (molar ratio of each structural unit I / II / III / IV = 20/30/30/20, mass average molecular weight = 7000).
<Photo acid generator>

<< Preparation of photosensitive composition >>
5 parts by mass of the vinyl group-containing compound described in Table 1, 5 parts by mass of the alicyclic ether group-containing compound described in Table 1, and 0.5 part by mass of the photoacid generator 1 are mixed, and propylene glycol monomethyl ether A solution was obtained by dissolving in 58 parts by mass of acetate. The obtained solution was filtered using a polyethylene filter having a pore size of 0.10 μm and a polyethylene filter having a pore size of 0.05 μm to prepare a curable composition.

≪Evaluation≫
<Storage stability>
The obtained curable composition was allowed to stand at 40 ° C. or 50 ° C. for 2 weeks, and the presence or absence of a precipitate was visually confirmed. When the precipitate is confirmed even when left at 40 ° C. and 50 ° C., the storage stability is judged as poor (×), and when the precipitate is confirmed only when left at 50 ° C., the storage stability is slightly poor ( (Triangle | delta)) and it was judged that storage stability was favorable ((double-circle)), when the deposit was not confirmed even if left at 40 degreeC and 50 degreeC. The results are shown in Table 1.

<Pencil hardness, transparency, refractive index, and heat resistance>
The obtained curable composition was allowed to stand at 25 ° C. for 3 days, and the left curable composition was applied onto a glass substrate with a coater. Heating (prebaking) was performed for 2 minutes at 100 ° C. on a hot plate to obtain a coating film. This coating film was exposed with broadband light. Heating (PEB) was performed at 100 ° C. for 2 minutes on a hot plate to obtain a cured film.

  The obtained cured film was subjected to a hardness test of 5 kg with a load of 1 kg ± 50 g using a pencil, and the presence or absence of scratches after applying the load was observed. Of the pencil hardnesses in which the cured film was not damaged in five tests, the hardest pencil hardness was taken as the test result. The results are shown in Table 1.

About the said cured film, the transmittance | permeability in wavelength 400nm was measured using the spectrometer (MCPD-3000, Otsuka Electronics Co., Ltd.) as an optical parameter, and transparency was evaluated on the following references | standards. The results are shown in Table 1.
A: The transmittance is 95% or more, B: 90% or more and less than 95%, and X: less than 90%.

About the said cured film, the refractive index in wavelength 633nm was further measured as an optical parameter, and the following references | standards evaluated. The results are shown in Table 1.
A: 1.65 or more, Δ: 1.60 or more and less than 1.65, x: less than 1.60

In order to evaluate the heat resistance of the cured film, the cured film is heated from room temperature (about 20 ° C.) at a rate of 10 ° C. per minute and subjected to thermogravimetric analysis in the atmosphere. The temperature T _{d5% at} which the mass was reduced by 5 _% was measured based on the mass of and was evaluated according to the following criteria. The results are shown in Table 1.
A: 200 ° C. or higher, Δ: 160 ° C. or higher and lower than 200 ° C., X: lower than 160 ° C.

  As can be seen from Table 1, the curable composition containing Compound 1 or 2 has storage stability, pencil hardness, transparency, refractive index, and heat resistance, regardless of which alicyclic ether group-containing compound is used. Excellent in all of the sex. In particular, the curable composition containing Compound 1 showed a tendency to have an excellent refractive index as compared with the curable composition containing Compound 2. On the other hand, the curable composition containing any one of the comparative compounds 1 to 3, even when any alicyclic ether group-containing compound is used, compared with the photosensitive composition containing the compound 1, Storage stability, pencil hardness, transparency, refractive index, and heat resistance are all inferior, and storage stability, pencil hardness, transparency, refraction compared to the photosensitive composition containing Compound 2 It was inferior to 4 or all of rate and heat resistance.

Claims (8)

A curable composition containing a vinyl group-containing compound represented by the following general formula (1) and an alicyclic ether group-containing compound having an alicyclic ether group having 2 to 6 carbon atoms.

(W ¹ and W ² independently represent a group represented by the following general formula (2), a hydroxyl group, or a (meth) acryloyloxy group, provided that W ¹ and W ² are not a hydroxyl group but a ring. Y ¹ and ring Y ² represent the same or different aromatic hydrocarbon rings, and R represents a single bond, a methylene group which may have a substituent, or a substituent, which may have two substituents. Represents an ethylene group that may contain a hetero atom, a group represented by -O-, a group represented by -NH-, or a group represented by -S-, wherein R ^3a and R ^3b independently represent a cyano group, a halogen atom Or a monovalent hydrocarbon group, and n1 and n2 independently represent an integer of 0 to 4.)

(In the formula, ring Z represents an aromatic hydrocarbon ring, X represents a single bond or a group represented by -S-, R ¹ represents a single bond or an alkylene group having 1 to 4 carbon atoms, and R ² represents Monovalent hydrocarbon group, hydroxyl group, group represented by -OR ^4a , group represented by -SR ^4b , acyl group, alkoxycarbonyl group, halogen atom, nitro group, cyano group, mercapto group, carboxyl group, amino group, carbamoyl Group, a group represented by -NHR ^4c , a group represented by -N (R ^4d ) ₂ , a (meth) acryloyloxy group, a sulfo group, or a monovalent hydrocarbon group, a group represented by -OR ^4a , -SR ^4b At least a part of the hydrogen atoms bonded to the carbon atom contained in the group represented by the above formula, an acyl group, an alkoxycarbonyl group, a group represented by -NHR ^4c , or a group represented by -N (R ^4d ) ₂ are monovalent carbonized. hydrogen , Hydroxyl, a group represented by ^{-OR 4a,} a group represented by ^{-SR 4b,} an acyl group, an alkoxycarbonyl group, a halogen atom, a nitro group, a cyano group, a mercapto group, a carboxyl group, an amino group, a carbamoyl group, -NHR ^4c , A group represented by —N (R ^4d ) ₂ , a (meth) acryloyloxy group, a mesyloxy group, or a group substituted with a sulfo group, R ^{4a to} R ^4d are each independently a monovalent hydrocarbon And m represents an integer of 0 or more.)   The curable composition according to claim 1, wherein the ring Z is a benzene ring or a naphthalene ring. The curable composition according to claim 1 or 2, wherein R ¹ is a single bond. The curable composition according to any one of claims 1 to 3, wherein at least one of W ¹ and W ² is a group represented by the general formula (2).   The curable composition according to claim 1, wherein the alicyclic ether group is an epoxy group.   Furthermore, the curable composition of any one of Claims 1-5 containing a proton donating compound.   Hardened | cured material formed by hardening | curing the curable composition of any one of Claims 1-6. Applying the curable composition according to any one of claims 1 to 6 on a substrate to form a coating film;
And a step of curing the coating film.