TWI791629B - Curable composition, cured film, and method for producing cured product - Google Patents

Abstract

[Problem] The present invention provides a curable composition having an excellent refractive index and yellowing resistance, a cured film formed from a cured product of the above curable composition, and production of a cured product using the above curable composition method. [Solution] A curable composition, which is a cation-curable or anion-curable curable composition, is characterized by, The aforementioned curable composition contains (C) an ionic liquid with a melting point of 140° C. or lower, which can provide a cured film with a refractive index of 1.60 or more and 2.20 or less for light with a wavelength of 550 nm.

Description

Curable composition, cured film, and method for producing cured product

The present invention relates to a curable composition, a cured film formed from a cured product of the curable composition, and a method for producing a cured product using the curable composition.

Conventionally, a cationically polymerizable curable composition containing a cationically polymerizable compound such as an epoxy compound as a curable component has been used in various applications.

These curable compositions are known, for example, containing an aromatic ring-containing alicyclic epoxy compound, a cationic polymerizable compound other than an aromatic ring-containing alicyclic epoxy compound, and a thermal cationic polymerization initiator. Cationic polymerizable thermosetting composition (Patent Document 1). Using this curable composition can form a cured product with high glass transition temperature, transparency (reduced coloring due to heat yellowing resistance), and excellent substrate adhesion. [Prior Art Literature] [Patent Document]

[Patent Document 1] JP-A-2014-156522 [Patent Document 2] International Publication No. 2014/157675

[Problem to be solved by the invention]

When the curable composition described in Patent Document 1 is used, a cured product exhibiting a high glass transition temperature and having good heat resistance from the viewpoint of thermal deformation can be formed. However, there is still room for improvement in terms of both high refractive index and heat yellowing resistance, especially in heat yellowing resistance.

環等的折射率的結構之材料(例如，專利文獻2)。 另一方面，使用含有含芳香族烴基，或三

環等的材料之硬化性組成物所形成的硬化物時，多會發生因存在芳香族烴基、三

環等原因，而於接受到光或熱時容易產生黃化等問題。即，於形成高折射率的硬化物所使用的以往的硬化性組成物中，有關硬化物的折射率，與硬化物的耐黃化性之關係中，即會發生提高其中一者時，另一者則會降低之相對關係的極大問題。In addition, in the past, in order to form a cured product with a high refractive index, it is often used to have an aromatic hydrocarbon group, three

The material of the structure of the refractive index of a ring etc. (for example, patent document 2). On the other hand, the use of aromatic hydrocarbon groups, or three

When the hardened product formed by the hardening composition of materials such as rings, it often occurs due to the presence of aromatic hydrocarbon groups, three

For reasons such as rings, it is prone to problems such as yellowing when exposed to light or heat. That is, in the conventional curable composition used to form a cured product with a high refractive index, in the relationship between the refractive index of the cured product and the yellowing resistance of the cured product, one of them will be improved, and the other will be improved. One would reduce the great problem of the relative relationship.

In view of the above problems, the present invention proposes a curable composition capable of forming a cured product with excellent refractive index and yellowing resistance, and a cured film formed from the cured product of the above curable composition. , and a method for producing a cured product using the aforementioned curable composition. [How to solve the problem]

(C) The ionic liquid is a liquid with excellent ion conductivity and a melting point below 140°C, so it can be uniformly diffused in the curable composition. In addition, (C) the thermal decomposition temperature of the ionic liquid is also relatively high. The present inventors discovered that a curable composition containing (C) an ionic liquid has a low dependence on cationic polymerization or anionic polymerization and uniformly accelerates the curing reaction. As a result, the above-mentioned problems can be solved. The present invention is accomplished in view of the above understanding. That is, the present invention has the following contents.

A first aspect of the present invention is a curable composition, which is a cation-curable or anion-curable curable composition, characterized by: The above-mentioned curable composition contains (C) an ionic liquid having a melting point of 140° C. or lower, which can provide a cured film with a refractive index of 1.60 to 2.20 for light with a wavelength of 550 nm.

環結構、異三聚氰酸環結構及環狀矽氧烷結構所成群中所選出之至少1種。The second aspect of the present invention is a curable composition, which is a cation-curable or anion-curable curable composition, characterized by containing: A curable composition of (A) a curable compound having a functional group of at least one element selected, and (C) an ionic liquid with a melting point below 140°C;

At least one selected from the group consisting of ring structure, isocyanuric acid ring structure and cyclic siloxane structure.

A third aspect of the present invention is a cured film characterized by being formed of a cured product of the curable composition of the first or second aspect.

The fourth aspect of the present invention is a method for producing a cured product, which is characterized by comprising: the step of molding the curable composition of the first aspect into a specific shape, and A step of heating, exposing, or exposing and heating the formed curable composition. [Effect of Invention]

The curable composition of the present invention can form a cured product with excellent refractive index and yellowing resistance. Also, according to the present invention, a cured film formed from a cured product of the above-mentioned curable composition, and a method for producing a cured product using the above-mentioned curable composition can be provided. The above cured products are suitable for various applications. [Mode of Implementing the Invention]

Hereinafter, the embodiments of the present invention will be described in detail, but the present invention is not limited by the following embodiments, and can be implemented with appropriate changes within the scope of the purpose of the present invention. Moreover, in this specification, "~" means the above to the following unless it is specifically limited.

≪Curing composition≫ The curable composition of the first aspect is a cation-curable or anion-curable curable composition, wherein the curable composition contains (C) an ionic liquid with a melting point of 140° C. Cured film with a refractive index of 1.60 to 2.20 at 550nm.

環結構、異三聚氰酸環結構及環狀矽氧烷結構所成群中所選出之至少1種。 第2態樣的硬化性組成物，以可提供對波長550nm之光線的折射率為1.60以上、2.20以下之硬化膜為佳。 以下，有關第1態樣的硬化性組成物及第2態樣的硬化性組成物，亦僅稱為「硬化性組成物」。 硬化性組成物，就具有高折射率之觀點，以可提供對波長550nm之光線的折射率為1.65以上、2.10以下之硬化膜者為佳，以可提供1.70以上、2.00以下之硬化膜者為較佳。 本發明中，折射率，於無特別限定下，係指依後述實施例的測定條件所測得者。The curable composition of the second aspect is a cation-curable or anion-curable curable composition containing at least one element selected from the group consisting of N, O, S, and Si (A) hardening compound of functional group, and (C) hardening composition of ionic liquid whose melting point is below 140°C;

At least one selected from the group consisting of ring structure, isocyanuric acid ring structure and cyclic siloxane structure. The curable composition of the second aspect preferably provides a cured film with a refractive index of 1.60 or more and 2.20 or less for light having a wavelength of 550 nm. Hereinafter, the curable composition of the first aspect and the curable composition of the second aspect are also simply referred to as "curable composition". From the viewpoint of high refractive index, the curable composition is preferably one that can provide a cured film with a refractive index of 1.65 or more and 2.10 or less for light with a wavelength of 550nm, and one that can provide a cured film with a refractive index of 1.70 or more and 2.00 or less. better. In the present invention, the refractive index refers to the one measured under the measurement conditions of the examples described later, unless otherwise specified.

When the curable composition contains (C) ionic liquid, in the curable composition, the dependence on cationic polymerization or anionic polymerization is low, and the curing reaction can be promoted uniformly. Chemical resistance (especially yellowing resistance), and has good heat resistance and adhesion to the substrate. Hereinafter, essential or optional components contained in the curable composition will be described.

＜(A) Hardening compound＞ The curable composition of the first aspect further contains a compound composed of N, O, S, and Si from the viewpoint of refractive index and yellowing resistance, and from the viewpoint of heat resistance and adhesion to the substrate. The (A) curable compound is preferably a functional group of at least one element selected from the group.

(A) The curable compound having a functional group containing at least one element selected from the group consisting of N, O, S and Si tends to have a high refractive index. (A) Hardening compounds, from the viewpoint of high refractive index, preferably have a functional group containing at least one element selected from the group consisting of N, S, and O, and preferably have a functional group containing at least one element selected from the group consisting of N and S A functional group of at least one element selected from among is preferred.

環結構、異三聚氰酸環結構、咔唑基、醯亞胺基、腈基等。具有含有N之官能基的(A)硬化性化合物，可列舉如，具有三

環之聚合物、後述之式(a1-I)所表示的化合物、聚乙烯咔唑(PVK)、聚醯亞胺等。具有三

環之聚合物，就其結構得知，其為具有較高的折射率(1.70以上)，而為特佳。The functional group containing N, can enumerate such as, three

Ring structure, isocyanuric acid ring structure, carbazolyl, imide, nitrile, etc. (A) curable compounds having N-containing functional groups include, for example, three

Ring polymers, compounds represented by formula (a1-I) described later, polyvinylcarbazole (PVK), polyimide, and the like. has three

The ring polymer is particularly preferred because it has a relatively high refractive index (above 1.70) in view of its structure.

The functional group containing O includes, for example, epoxy group, isocyanuric acid ring structure, carboxyl group, ester group, ketone group, hydroxyl group and the like. The (A) curable compound having an O-containing functional group includes, for example, compounds represented by formula (a1) described below, compounds represented by formula (a1-I) described below, epoxy compounds described below, and the like.

The functional group containing S includes, for example, thiopyranyl group, sulfonyl group (-SO ₂ -), thiol group, thioester group and the like. The (A) curable compound having a functional group containing S includes, for example, a compound represented by the formula (a1) described later, polyethersulfone (PES), polysulfone, polyphenylsulfone, and the like. The (A) curable compound having a functional group containing Si includes, for example, a siloxane compound having a siloxane skeleton composed of siloxane bonds (Si—O—Si). The siloxane skeleton in the siloxane compound, for example, a cyclic siloxane skeleton or a cage-type or trapezoid-type polysilsesquioxane skeleton.

環結構、異三聚氰酸環結構及環狀矽氧烷結構所成群中所選出之至少1種為佳。 第2態樣的硬化性組成物，為具有含有由N、O、S及Si所成群中所選出之至少1種元素之官能基，其包含含有由芳香族基、三

環結構、異三聚氰酸環結構及環狀矽氧烷結構所成群中所選出之至少1種的(A)硬化性化合物。 上述芳香族基，可列舉如，折射率及耐黃化性之觀點、又，耐熱性及對基板的密著性之觀點，以形成軸節型結構的芳香族基為佳。(A) The curable compound contains an aromatic group, three

At least one selected from the group consisting of a ring structure, an isocyanuric acid ring structure and a cyclic siloxane structure is preferred. The curable composition of the second aspect is a functional group having at least one element selected from the group consisting of N, O, S, and Si, including aromatic groups, three

(A) Hardening compound of at least one kind selected from the group consisting of ring structure, isocyanuric acid ring structure and cyclic siloxane structure. The above-mentioned aromatic groups include, for example, from the viewpoints of refractive index and yellowing resistance, and also from the viewpoints of heat resistance and adhesion to the substrate, aromatic groups forming an axonal structure are preferable.

環結構之聚合物、後述之式(a1-I)所表示的化合物及後述之式(a1-III)所表示的矽氧環氧化合物所成群中所選出之至少1種為佳。(A) The curable compound contains a compound represented by the following formula (a1) and has three

At least one selected from the group consisting of a polymer having a ring structure, a compound represented by the formula (a1-I) described below, and a silicone epoxy compound represented by the formula (a1-III) described below is preferred.

(式(a1)中，W¹ 及W² 各自獨立為，下述式(a2)：

所表示之基， 式(a2)中，環Z表示芳香族烴環；X表示單鍵或-S-所示之基；R⁰¹ 表示單鍵、碳原子數為1以上、4以下之伸烷基，或碳原子數為1以上、4以下之伸烷氧基；R⁰¹ 為伸烷氧基時，伸烷氧基中之氧原子為與環Z鍵結；R⁰² 表示1價烴基、羥基、-OR^4a 所示之基、-SR^4b 所示之基、醯基、烷氧羰基、鹵素原子、硝基、氰基、氫硫基、羧基、胺基、胺甲醯基、-NHR^4c 所示之基、-N(R^4d )₂ 所示之基、磺酸基；或1價烴基、-OR^4a 所示之基、-SR^4b 所示之基、醯基、烷氧羰基、-NHR^4c 所示之基，或-N(R^4d )₂ 所示之基所含的碳原子所鍵結的氫原子中之至少一部份被1價烴基、羥基、-OR^4a 所示之基、-SR^4b 所示之基、醯基、烷氧羰基、鹵素原子、硝基、氰基、氫硫基、羧基、胺基、胺甲醯基、-NHR^4c 所示之基、-N(R^4d )₂ 所示之基、甲磺醯氧基，或磺酸基所取代之基；R^4a ~R^4d 獨立表示1價烴基；m表示0以上之整數；R⁰³ 為氫原子、乙烯基、噻喃-2-甲基，或縮水甘油基， W¹ 與W² 等二者中之R⁰³ 並不具有氫原子； 環Y¹ 及環Y² 表示相同或相異的芳香族烴環；R表示單鍵、可具有取代基之伸甲基、可具有取代基，且2個碳原子間可含有雜原子之伸乙基、-O-所示之基、-NH-所示之基，或-S-所示之基；R^3a 及R^3b 獨立表示氰基、鹵素原子，或1價烴基；n1及n2獨立表示0以上、4以下之整數)。(compound represented by formula (a1))

(In the formula (a1), W ¹ and W ² are each independently, the following formula (a2):

The base represented, in the formula (a2), the ring Z represents an aromatic hydrocarbon ring; X represents a single bond or the base represented by ^-S- ; group, or an alkoxyl group with 1 to 4 carbon atoms; when R ⁰¹ is an alkoxyl group, the oxygen atom in the alkoxyl group is bonded to the ring Z; R ⁰² represents a monovalent hydrocarbon group, a hydroxyl 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 mercapto group, a carboxyl group, an amino group, a carbamoyl group, -NHR ^4c The group shown, the group represented by -N(R ^4d ) ₂ , the sulfonic acid group; or the monovalent hydrocarbon group, the group represented by -OR ^4a , the group represented by -SR ^4b , acyl group, alkoxycarbonyl group, - A group represented by NHR ^4c , or a group represented by a monovalent hydrocarbon group, a hydroxyl group, or a group represented by -OR ^4a in which at least a part of hydrogen atoms bonded to carbon atoms contained in a group represented by -N(R ^4d ) ₂ , the base shown in -SR ^4b , acyl group, alkoxycarbonyl, halogen atom, nitro, cyano, mercapto, carboxyl, amino, carbamoyl, the base shown in -NHR ^4c , -N( R ^4d ) The group represented by ₂ , methanesulfonyloxy group, or a group substituted by a sulfonic acid group; R ^4a ~ R ^4d independently represent a monovalent hydrocarbon group; m represents an integer greater than 0; R ⁰³ represents a hydrogen atom, a vinyl group , thiopyran-2-methyl, or glycidyl, R ⁰³ in W ¹ and W ² does not have a hydrogen atom; Ring Y ¹ and Ring Y ² represent the same or different aromatic hydrocarbon rings; R represents a single bond, a methylene group that may have a substituent, an ethylylene group that may have a substituent and may contain a heteroatom between two carbon atoms, a group represented by -O-, a group represented by -NH-, Or a group represented by -S-; R ^3a and R ^3b independently represent a cyano group, a halogen atom, or a monovalent hydrocarbon group; n1 and n2 independently represent an integer between 0 and 4).

In the above formula (a2), the ring Z is, for example, a benzene ring, a condensed polycyclic aromatic hydrocarbon ring [for example, a condensed bicyclic hydrocarbon ring (for example, a C _8-20 condensed bicyclic hydrocarbon ring such as a naphthalene ring, Preferred are C _10-16 condensed bicyclic hydrocarbon rings), condensed tricyclic aromatic hydrocarbon rings (eg, anthracycline, phenanthrene ring, etc.), condensed 2 to 4 cyclic aromatic hydrocarbon rings], and the like. Ring Z is preferably a benzene ring or a naphthalene ring, more preferably a naphthalene ring. Also, since W ¹ and W ² in the formula (a1) are each independently a group represented by the following formula (a2), each of W ¹ and W ² contains a ring Z. The ring Z contained in ^W1 and the ring Z contained in ^W2 may be the same or different, for example, the ring of one may be a benzene ring, and the ring of the other may be a naphthalene ring, etc., and It is particularly preferred that any one of the rings is a naphthalene ring.

Also, the substitution position of the carbon atom to which both ^W1 and ^W2 are directly bonded, and the ring Z bonded via X is not particularly limited. For example, when the ring Z is a naphthalene ring, the group corresponding to the above-mentioned carbon atom-bonded ring Z may be 1-naphthyl, 2-naphthyl or the like.

In the above formula (a2), X represents an independent single bond or a group represented by -S-, more typically, a single bond.

In the above formula (a2), R ⁰¹ is, for example, a single bond; the number of carbon atoms of methylene, ethylylene, trimethylene, propylylene, butane-1,2-diyl, etc. is 1 or more, 4 or more. The following alkylene groups; methoxyl, ethoxyl, propoxyl, etc. have more than 1 and less than 4 carbon atoms; alkoxyl, etc.; single bond; C _2-4 alkylene (especially alkylene C _2-3 alkylene such as ethyl, propylene, etc.); C _2-4 alkylene (especially C _2-3 alkylene such as ethoxy, propyleneoxy, etc.) is preferred, Again, a single bond is preferred. Also, when R ⁰¹ is an alkylene group, the oxygen atom in the alkylene group is bonded to the ring Z. Also, since W ¹ and W ² in formula (a1) are each independently a group represented by the following formula (a2), W ¹ and W ² each contain a divalent group R ⁰¹ . R ⁰¹ included in W ¹ and R ⁰¹ included in W ² may be the same or different.

In the above formula (a2), R ⁰² is, for example, an alkyl group (for example, a C _1-12 alkyl group such as methyl, ethyl, propyl, isopropyl, butyl, etc., preferably a C _1-8 alkyl group, More preferably C _1-6 alkyl, etc.), cycloalkyl (C _5-10 cycloalkyl such as cyclohexyl, preferably C _5-8 cycloalkyl, more preferably C _5-6 cycloalkyl, etc. ), aryl (for example, C _6-14 aryl of phenyl, tolyl, xylyl, naphthyl, etc., preferably C _6-10 aryl, more preferably C _6-8 aryl, etc.), Monovalent hydrocarbon groups such as aralkyl (benzyl, phenethyl, C _6-10 aryl-C _1-4 alkyl, etc.); hydroxyl; alkoxy (methoxy, ethoxy, propoxy , butoxy and other C _1-12 alkoxy groups, preferably C _1-8 alkoxy groups, more preferably C _1-6 alkoxy groups, etc.), cycloalkoxy groups (C 1-12 alkoxy groups such as cyclohexyl groups) _5-10 cycloalkoxy, etc.), aryloxy (C _6-10 aryloxy such as phenoxy), aralkyloxy (for example, C _6-10 aryl-C _{1- 4} alkoxy) etc. -OR ^4a [wherein, R ^4a represents a monovalent hydrocarbon group (monovalent hydrocarbon group exemplified above, etc.)]; alkylthio (methylthio, ethylthio, propylthio C _1-12 alkylthio groups such as butylthio, preferably C _1-8 alkylthio, more preferably C _1-6 alkylthio, etc.), cycloalkylthio (cyclohexylthio, etc. C _5-10 cycloalkylthio, etc.), arylthio (C _6-10 arylthio such as phenylthio), aralkylthio (for example, C _6-10 aryl-C _1-4 alkylthio) etc. -SR ^4b group [wherein, R ^4b represents a monovalent hydrocarbon group (monovalent hydrocarbon group exemplified above)]; acyl group (C _1-6 of acetyl group etc. acyl, etc.); alkoxycarbonyl (C _1-4 alkoxy-carbonyl such as methoxycarbonyl, etc.); halogen atom (fluorine atom, chlorine atom, bromine atom, iodine atom, etc.); nitro group; cyano group; hydrogen Sulfuryl; Carboxyl; Amino; Aminoformyl; Alkylamino (C _1-12 alkylamino such as methylamino, ethylamino, propylamine, butylamino, etc., preferably C _1-8 alkylamine group, more preferably C _1-6 alkylamino group, etc.), cycloalkylamino group (C _5-10 cycloalkylamino group such as cyclohexylamino group, etc.), arylamine group (C _6-10 aromatic group such as aniline group, etc.) Amino group), aralkylamino group (for example, C _6-10 aryl-C _1-4 alkylamino group such as benzylamino group) etc. -NHR ^4c represented by [wherein, R ^4c represents monovalent Hydrocarbon group (monovalent hydrocarbon group exemplified above _, etc.)]; Preferably two (C _1-8 alkyl) amino groups, more preferably two (C _1-6 alkyl) amino groups, etc.), bicycloalkylamino groups (bis (C _5-10 cycloalkyl) amino group, etc.), diarylamine group (di(C _6-10 aryl) amino group such as diphenylamino group), diarylalkylamino group (for example, di(C _6-10 aryl) amino group such as dibenzylamino group, etc.) A group represented by -N(R ^4d ) ₂ such as _-10aryl -C _1-4 alkyl)amino group) [wherein, R ^4d represents an independent monovalent hydrocarbon group (such as the monovalent hydrocarbon group exemplified above)] ; (meth)acryloyloxy group; sulfonic acid group; the above-mentioned 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 carbon-bonded hydrogen atoms contained in the group represented by -N(R ^4d ) ₂ is represented by the above-mentioned monovalent hydrocarbon group, hydroxyl group, group represented by -OR ^4a , or -SR ^4b The group represented by, acyl group, alkoxycarbonyl group, halogen atom, nitro group, cyano group, mercapto group, carboxyl group, amino group, carbamoyl group, the group represented by -NHR ^4c , the group represented by -N(R ^4d ) ₂ The group shown, (meth)acryloxy group, methanesulfonyloxy group, or a group substituted by a sulfonic acid group [for example, alkoxyaryl group (for example, C _1-4 alkoxy group of methoxyphenyl group, etc. C _6-10 aryl), alkoxycarbonyl aryl (for example, C _1-4 alkoxy-carbonyl C _6-10 aryl such as methoxycarbonylphenyl, ethoxycarbonylphenyl, etc.)] wait.

Among these, in representative examples, R ⁰² may also be 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 and the like.

Preferable R ⁰² can include, for example, monovalent hydrocarbon groups [for example, alkyl (for example, C _1-6 alkyl), cycloalkyl (for example, C _5-8 cycloalkyl), aryl (for example, C _{6 -10} aryl), aralkyl (for example, C _6-8 aryl-C _1-2 alkyl) etc.], alkoxy (C _1-4 alkoxy etc.) and the like. In _particular , R ⁰² is a monovalent hydrocarbon group ₍ especially is an alkyl group) is preferred.

Also, when m is an integer of 2 or more, the plural R ⁰² may be different from each other or the same. In addition, R ⁰² included in W ¹ and R ⁰² included in W ² may be the same or different.

In the above formula (a2), the number m of ^R02 can be selected according to the type of ring Z, for example, 0 to 4, preferably 0 to 3, more preferably 0 to 2. Also, m in W ¹ and m in W ² may be the same or different.

In the above formula (a3), R ⁰³ is a hydrogen atom, a vinyl group, a thiopyran-2-methyl group, or a glycidyl group. Also, R ⁰³ in both W ¹ and W ² does not have a hydrogen atom. Vinyl, thiopyran-2-methyl, and glycidyl are all cationic polymerizable functional groups. Therefore, the compound represented by formula (a1) is a cationically polymerizable compound having one or two cationically polymerizable functional groups. R ⁰³ contained in W ¹ and R ⁰³ contained in W ² may be the same or different when neither is a hydrogen atom. R ⁰³ contained in W ¹ and R ⁰³ contained in W ² are preferably vinyl, thiopyran-2-methyl, or glycidyl, and both are composed of vinyl, thiopyran-2-methyl, The same base selected from the group formed by the glycidyl group and the glycidyl group is preferred. R ⁰³ is preferably a vinyl group or a glycidyl group from the viewpoint of the ease of synthesis or acquisition of the compound represented by the formula (a1).

In the above formula (a1), the ring Y ¹ and the ring Y ² are, for example, a benzene ring, a condensed polycyclic aromatic hydrocarbon ring [for example, a condensed bicyclic hydrocarbon ring (for example, a C _8-20 condensed dihydrocarbon ring such as a naphthalene ring, etc. Cyclic hydrocarbon ring, preferably C _10-16 condensed bicyclic hydrocarbon ring), condensed tricyclic aromatic hydrocarbon ring (for example, anthracycline, phenanthrene ring, etc.) ]wait. The ring Y ¹ and the ring Y ² are preferably a benzene ring or a naphthalene ring, and more preferably a benzene ring. In addition, the ring Y ¹ and the ring Y ² may be the same or different, for example, one of the rings may be a benzene ring, and the other ring may be a naphthalene ring.

In the above formula (a1), R represents a single bond, a methylene group that may have a substituent, an ethylylene group that may have a substituent and may contain a heteroatom between two carbon atoms, a group represented by -O-, - A group represented by NH-, or a group represented by -S-; more typically, a single bond. Among them, substituents, for example, cyano group, halogen atom (fluorine atom, chlorine atom, bromine atom, etc.), 1-valent hydrocarbon group [for example, alkyl group (methyl, ethyl, propyl, isopropyl, butyl, t -C _1-6 alkyl such as butyl), aryl (C _6-10 aryl such as phenyl), etc.], etc.; heteroatoms, for example, oxygen atom, nitrogen atom, sulfur atom, silicon atom, etc.

In the above-mentioned formula (a1), R ^3a and R ^3b are usually non-reactive substituents, for example, cyano group, halogen atom (fluorine atom, chlorine atom, bromine atom, etc.), monovalent hydrocarbon group [for example, alkyl, aryl ( _C6-10 aryl such as phenyl) etc.] etc.; and cyano or alkyl is preferred, and alkyl is particularly preferred. Alkyl, for example, C _1-6 alkyl (for example, C _1-4 alkyl, especially methyl) such as methyl, ethyl, propyl, isopropyl, butyl, t-butyl and so on. Also, when n1 is an integer of 2 or more, R ^3a may be different from or the same as each other. Also, when n2 is an integer of 2 or more, R ^3b may be different from each other or the same. Also, R ^3a and R ^3b may be the same or different. Also, the bonding position (substitution position) of R ^3a and R ^3b for ring Y ¹ and ring Y ² is not particularly limited. Preferable substitution numbers n1 and n2 are 0 or 1, especially 0. Also, 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 can maintain excellent optical and thermal properties and has a cationic polymerizable functional group. In particular, when ring ^Y1 and ring ^Y2 are benzene rings and R is a single bond, the compound represented by the above formula (a1) has a fennel skeleton, so that the optical and thermal properties can be improved. In addition, the compound represented by the above-mentioned formula (a1) can improve a cured product with high hardness, so it is suitable as a base material component in the composition.

Among the compounds represented by the above-mentioned formula (a1), particularly preferred specific examples include, for example, 9,9-bis[4-[2-(glycidyloxy)ethoxy]phenyl]-9H-fennel, 9, 9-bis[4-[2-(glycidyloxy)ethyl]phenyl]-9H-fennel, 9,9-bis[4-(glycidyloxy)-3-methylphenyl]-9H-tertilene , 9,9-bis[4-(glycidyloxy)-3,5-xylyl]-9H-fennel, 9,9-bis(6‐glycidyl ether naphthalene-1-yl)-9H- Oxyprofen and 9,9-bis(5-glycidyletherylnaphthalen-2-yl)-9H-fennel and other epoxy group-containing fennel compounds; and compounds represented by the following formulas, etc.

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

(A) When the curable compound contains the compound represented by the above formula (a1), the amount of the compound represented by the above formula (a1) in the (A) curable compound is preferably 50% by mass or more, and preferably 70% by mass. The mass % or more is preferable, 80 mass % or more is more preferable, 90 mass % or more is especially preferable, and 100 mass % is most preferable.

(epoxy compound) Examples of the above-mentioned epoxy compounds include, for example, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bisphenol AD type epoxy resin, naphthalene type epoxy resin, and Bifunctional epoxy resins such as biphenyl-type epoxy resins; phenol-novolak-type epoxy resins, brominated phenol-novolac-type epoxy resins, o-cresol-novolak-type epoxy resins, bisphenol A novolak-type epoxy resins Type epoxy resin, and novolak epoxy resin such as bisphenol AD novolak type epoxy resin; Cycloaliphatic epoxy resin such as epoxy of dicyclopentadiene type phenol resin; Naphthalene type phenol resin Aromatic epoxy resins such as epoxides; glycidyl dimer acid esters, and glycidyl ester epoxy resins such as triglycidyl esters; tetraglycidylaminodiphenylmethane, triglycidyl-p-aminophenol , tetraglycidyl methyl xylene diamine, and glycidyl amine epoxy resins such as tetraglycidyl diamine methyl cyclohexane; heterocyclic epoxy resins such as triglycidyl isocyanurate; Phloroglucinol triglycidyl ether, trihydroxybiphenyl triglycidyl ether, trihydroxyphenylmethane triglycidyl ether, glycerol triglycidyl ether, 2-[4-(2,3-epoxypropoxy base)phenyl]-2-[4-[1,1-bis[4-(2,3-epoxypropoxy)phenyl]ethyl]phenyl]propane, and 1,3-bis[4 -[1-[4-(2,3-Glycidyloxy)phenyl]-1-[4-[1-[4-(2,3-Glycidyloxy)phenyl]-1- Trifunctional epoxy resins such as methyl ethyl] phenyl] ethyl] phenoxy] -2-propanol; Tetrahydroxyphenyl ethane tetraglycidyl ether, tetraglycidyl benzophenone, bis Quaternary functional epoxy resins such as quinone tetraglycidyl ether and tetraglycidoxy biphenyl; 1,2-epoxy group of 2,2-bis(hydroxymethyl)-1-butanol 4-(2-oxiranyl)cyclohexane adduct, etc. 1,2-epoxy-4-(2-oxiranyl) cyclohexane adduct of 2,2-bis(hydroxymethyl)-1-butanol is EHPE-3150 (DAICEL company system) sold in the market.

Also, an oligomer or polymer type polyfunctional epoxy compound is preferably used as (A) curable compound. Typical examples include, for example, phenol-novolak-type epoxy compounds, brominated phenol-novolak-type epoxy compounds, o-cresol-novolak-type epoxy compounds, xylenol-novolak-type epoxy compounds, Naphthol-novolac epoxy compound, bisphenol A novolak epoxy compound, bisphenol AD novolak epoxy compound, dicyclopentadiene phenol resin epoxy, naphthalene phenol resin epoxy compounds etc.

Other examples of preferable epoxy compounds include, for example, polyfunctional alicyclic epoxy compounds having an alicyclic epoxy group. (A) When the curable compound contains an alicyclic epoxy compound, when the curable composition is used, it will easily form a cured product with excellent transparency.

Specific examples of the alicyclic epoxy compound, for example, 2-(3,4-epoxycyclohexyl-5,5-spiro-3,4-epoxy)cyclohexane-methyl-dioxane, 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-epoxycyclohexyl-3',4 '-Epoxycyclohexane carboxylate, trimethylcaprolactone modified 3,4-epoxycyclohexyl-3',4'-epoxycyclohexane carboxylate, β-methyl- δ-valerolactone modified 3,4-epoxycyclohexyl-3',4'-epoxycyclohexane carboxylate, methylene bis(3,4-epoxycyclohexane), ethyl Diol bis(3,4-epoxycyclohexyl) ether, ethylidene bis(3,4-epoxycyclohexanecarboxylate), and polyfunctional epoxy with oxidized tricyclodecenyl Compounds, or compounds represented by the following formulas (a1-1) to (a1-5), etc. These alicyclic epoxy compounds may be used alone or in combination of two or more.

(式(a1-1)中，Z表示單鍵或連結基(具有1個以上原子的二價之基)；R^a1 ~R^a18 各自獨立為由氫原子、鹵素原子，及有機基所成之群所選擇之基)。

(In the formula (a1-1), Z represents a single bond or a linking group (a divalent base having more than one atom); R ^a1 ~ R ^a18 are each independently formed by a hydrogen atom, a halogen atom, and an organic group basis of group selection).

Linking group Z, for example, consists of divalent hydrocarbon group, -O-, -O-CO-, -S-, -SO-, -SO ₂ -, -CBr ₂ -, -C(CBr ₃ ) ₂ -, - A divalent group selected from the group formed by C(CF ₃ ) ₂ -, and -R ^a19 -O-CO-, a group formed by bonding a plurality of these groups, and the like.

The divalent hydrocarbon group of the linking group Z is, for example, a linear or branched alkylene group having 1 to 18 carbon atoms, a divalent alicyclic hydrocarbon group, and the like. A linear or branched chain alkylene group having 1 to 18 carbon atoms, for example, methylene, methylethylene, dimethylylene, dimethylene, trimethylene, etc. The above divalent alicyclic hydrocarbon groups, for example, 1,2-cyclopentyl, 1,3-cyclopentyl, cyclopentylene, 1,2-cyclohexyl, 1,3-cyclohexyl, 1, 4-cyclohexyl, cycloalkylene such as cyclohexylene (including cycloalkylene), and the like.

R ^a19 is an alkylene group having 1 to 8 carbon atoms, preferably a methylene group or an ethylene group.

(In the formula (a1-2), R ^a1 to R ^a12 are selected from the group consisting of a hydrogen atom, a halogen atom, and an organic group).

(式(a1-3)中，R^a1 ~R^a10 為由氫原子、鹵素原子，及有機基所成之群所選擇之基；R^a2 及R^a8 可互相鍵結)。

(In the formula (a1-3), R ^a1 ~R ^a10 is a group selected from a hydrogen atom, a halogen atom, and an organic group; R ^a2 and R ^a8 can be bonded to each other).

(式(a1-4)中，R^a1 ~R^a12 為由氫原子、鹵素原子，及有機基所成之群所選擇之基；R^a2 及R^a10 可互相鍵結)。

(In the formula (a1-4), R ^a1 ~R ^a12 is a group selected from a hydrogen atom, a halogen atom, and an organic group; R ^a2 and R ^a10 can be bonded to each other).

(式(a1-5)中，R^a1 ~R^a12 為由氫原子、鹵素原子，及有機基所成之群所選擇之基)。

(In formula (a1-5), R ^a1 to R ^a12 are selected from the group consisting of hydrogen atom, halogen atom, and organic group).

In formula (a1-1)～(a1-5), when R ^a1 ～R ^a18 is an organic group, as long as the organic group is within the range that does not hinder the purpose of the present invention, there is no special limitation, and it can be hydrocarbon group, A group formed by a carbon atom and a halogen atom, or a group formed by a carbon atom and a hydrogen atom and containing a heteroatom such as a halogen atom, an oxygen atom, a sulfur atom, a nitrogen atom, or a silicon atom may be used. Examples of halogen atoms include chlorine atoms, bromine atoms, iodine atoms, and fluorine atoms.

Organic groups include, for example, groups formed with hydrocarbon groups, carbon atoms, hydrogen atoms, and oxygen atoms; groups formed with halogenated hydrocarbon groups, carbon atoms, oxygen atoms, and halogen atoms; groups formed with carbon atoms, hydrogen atoms , an oxygen atom, and a group formed by a halogen atom are preferred. 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 or an aliphatic skeleton. The number of carbon atoms in the organic group is preferably from 1 to 20, more preferably from 1 to 10, and particularly preferably from 1 to 5.

Specific examples of hydrocarbon groups, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, 2-ethylhexyl, n-nonyl, n-decyl, n-undecyl, n-tridecyl, n-tetradecyl, n-pentadecanyl Chain alkyl groups such as n-hexadecyl, n-heptadecyl, n-octadecyl, n-nonadecyl, and n-eicosyl; vinyl, 1-propene 2-n-propenyl (allyl), 1-n-butenyl, 2-n-butenyl, and chain alkenyl such as 3-n-butenyl; cyclopropyl, ring Cycloalkyl groups such as butyl, cyclopentyl, cyclohexyl, and cycloheptyl; phenyl, o-tolyl, m-tolyl, p-tolyl, α-naphthyl, β-naphthyl, biphenyl -4-yl, biphenyl-3-yl, biphenyl-2-yl, anthracenyl, and aryl such as phenanthrenyl; benzyl, phenethyl, α-naphthylmethyl, β-naphthylmethyl, α Aralkyl groups such as -naphthylethyl and β-naphthylethyl, etc.

Specific examples of halogenated hydrocarbon groups, for example, chloromethyl, dichloromethyl, trichloromethyl, bromomethyl, dibromomethyl, tribromomethyl, fluoromethyl, difluoromethyl, trifluoromethyl, 2,2,2-Trifluoroethyl, pentafluoroethyl, heptafluoropropyl, perfluorobutyl, and perfluoropentyl, perfluorohexyl, perfluoroheptyl, perfluorooctyl, perfluorononyl , and halogenated chain alkyl such as perfluorodecyl; 2-chlorocyclohexyl, 3-chlorocyclohexyl, 4-chlorocyclohexyl, 2,4-dichlorocyclohexyl, 2-bromocyclohexyl, 3-bromocyclohexyl Cyclohexyl, and halogenated cycloalkyl such as 4-bromocyclohexyl; 2-chlorophenyl, 3-chlorophenyl, 4-chlorophenyl, 2,3-dichlorophenyl, 2,4-dichlorobenzene Base, 2,5-dichlorophenyl, 2,6-dichlorophenyl, 3,4-dichlorophenyl, 3,5-dichlorophenyl, 2-bromophenyl, 3-bromophenyl, 4-bromophenyl, 2-fluorophenyl, 3-fluorophenyl, 4-fluorophenyl, etc. halogenated aryl; 2-chlorobenzyl, 3-chlorobenzyl, 4-chlorobenzyl, Aralkyl halides such as 2-bromobenzyl, 3-bromobenzyl, 4-bromobenzyl, 2-fluorobenzyl, 3-fluorobenzyl and 4-fluorobenzyl.

Specific examples of groups formed of carbon atoms, hydrogen atoms, and oxygen atoms, for example, hydroxymethyl, 2-hydroxyethyl, 3-hydroxy-n-propyl, and 4-hydroxy-n-butyl, etc. Hydroxy chain alkyl; 2-hydroxycyclohexyl, 3-hydroxycyclohexyl, and halogenated cycloalkyl such as 4-hydroxycyclohexyl; 2-hydroxyphenyl, 3-hydroxyphenyl, 4-hydroxyphenyl, 2 ,3-dihydroxyphenyl, 2,4-dihydroxyphenyl, 2,5-dihydroxyphenyl, 2,6-dihydroxyphenyl, 3,4-dihydroxyphenyl, and 3,5-dihydroxyphenyl Hydroxyaryl such as hydroxyphenyl; hydroxyaralkyl such as 2-hydroxybenzyl, 3-hydroxybenzyl, and 4-hydroxybenzyl; methoxy, ethoxy, n-propoxy , isopropoxy, n-butoxy, isobutoxy, sec-butoxy, tert-butoxy, n-pentyloxy, n-hexyloxy, n-heptyloxy, n-octyl Oxygen, 2-ethylhexyloxy, n-nonyloxy, n-decyloxy, n-undecyloxy, n-tridecyloxy, n-tetradecyloxy, n-pentadecyloxy Chain alkoxy groups such as alkoxy, n-hexadecyloxy, n-heptadecyloxy, n-octadecyloxy, n-nonadecyloxy, and n-eicosyloxy Ethyleneoxy, 1-propyleneoxy, 2-n-propyleneoxy (allyloxy), 1-n-buteneoxy, 2-n-buteneoxy, and 3-n-butene Chain alkenyloxy such as alkenyloxy; phenoxy, o-methylphenoxy, m-methylphenoxy, p-methylphenoxy, α-naphthyloxy, β-naphthyloxy, biphenyl-4- Oxygen, biphenyl-3-oxyl, biphenyl-2-oxyl, anthracenyloxy, and aryloxy such as phenanthrenyloxy; benzyloxy, phenethoxy, α-naphthylmethoxy, β -Naphthalene methoxy, α-naphthylethoxy, and β-naphthylethoxy aralkyloxy; methoxymethyl, ethoxymethyl, n-propoxymethyl, 2-methoxyethyl , 2-ethoxyethyl, 2-n-propoxyethyl, 3-methoxy-n-propyl, 3-ethoxy-n-propyl, 3-n-propoxy-n-propane Alkoxyalkyl groups such as 4-methoxy-n-butyl, 4-ethoxy-n-butyl, and 4-n-propoxy-n-butyl; methoxymethoxy, Ethoxymethoxy, n-propoxymethoxy, 2-methoxyethoxy, 2-ethoxyethoxy, 2-n-propoxyethoxy, 3-methoxy-n -propoxy, 3-ethoxy-n-propoxy, 3-n-propoxy-n-propoxy, 4-methoxy-n-butoxy, 4-ethoxy-n -butoxy, and alkoxyalkoxy such as 4-n-propoxy-n-butoxy; 2-methoxyphenyl, 3-methoxyphenyl, and 4-methoxyphenyl, etc. Alkoxyaryl group; 2-methoxyphenoxy, 3-methoxyphenoxy, and 4-methoxyphenoxy alkoxyaryloxy; formyl, acetyl , propionyl, butyryl, pentyl, hexyl, heptyl, octyl, nonyl, and aliphatic acyl such as decanyl; benzoyl, α-naphthyl, and β- Aromatic acyl groups such as naphthyl; methoxycarbonyl, ethoxycarbonyl, n-propoxycarbonyl, n-butoxycarbonyl, n-pentyloxycarbonyl, n-hexyloxycarbonyl, n-heptyloxycarbonyl, n- Chain alkoxycarbonyl such as octyloxycarbonyl, n-nonyloxycarbonyl, and n-decyloxycarbonyl; aryloxycarbonyl such as phenoxycarbonyl, α-naphthyloxycarbonyl, and β-naphthyloxycarbonyl; formyloxy , Acetyloxy, Propionyloxy, Butyloxy, Pentyloxy, Hexyloxy, Heptyloxy, Octyloxy, Nonyloxy, and Decyloxy, etc. Acyloxy; aromatic acyloxy groups such as benzoyloxy, α-naphthyloxy, and β-naphthyloxy.

R ^a1 to R ^a18 are independently selected from the group consisting of a hydrogen atom, a halogen atom, an alkyl group with 1 to 5 carbon atoms, and an alkoxy group with 1 to 5 carbon atoms. Preferably, especially from the viewpoint of easily forming a cured film with mechanical properties, it is more preferable that all of R ^a1 to R ^a18 are hydrogen atoms.

In formulas (a1-2) to (a1-5), R ^a1 to R ^a12 are the same as R ^a1 to R ^a12 in formula (a1-1). In formula (a1-2) and formula (a1-4), a divalent group formed when R ^a2 and R ^a10 are mutually bonded, for example, -CH ₂ -, -C(CH ₃ ) ₂ -, etc. In formula (a1-3), a divalent group formed when R ^a2 and R ^a8 are mutually bonded, for example, -CH ₂ -, -C(CH ₃ ) ₂ -, etc.

Among the alicyclic epoxy compounds represented by formula (a1-1), specific examples of preferred compounds include, for example, the following formula (a1-1a), the following formula (a1-1b), and the following formula ( a1-1c) represented cycloaliphatic epoxy compound, or 2,2-bis(3,4-epoxycyclohexane-1-yl) propane [=2,2-bis(3,4-epoxy Cyclohexyl) propane] and so on.

Among the alicyclic epoxy compounds represented by formula (a1-2), specific examples of preferred compounds are, for example, bicyclododecene diepoxides represented by the following formula (a1-2a), or bis- Cyclododecene diepoxide, etc.

Among the alicyclic epoxy compounds represented by the formula (a1-3), specific examples of preferred compounds are, for example, S-spiro[3-oxatricyclo[3.2.1.0 ^2,4 ]octane-6,2 '-Ethylene oxide] and so on.

Among the alicyclic epoxy compounds represented by the formula (a1-4), specific examples of preferred compounds include, for example, 4-vinylcyclohexene dioxide, dipentene dioxide, limonene dioxide, 1-methyl-4-(3-methyloxiran-2-yl)-7-oxabicyclo[4.1.0]heptane, etc.

Among the alicyclic epoxy compounds represented by the formula (a1-5), specific examples of preferable compounds include, for example, 1,2,5,6-diepoxycyclooctane and the like.

(式(a1-I)中，X^a1 、X^a2 ，及X^a3 各自獨立為，氫原子，或可含有環氧基的有機基，X^a1 、X^a2 ，及X^a3 所具有的環氧基之總數為2以上)。(compound represented by formula (a1-I))

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

(式(a1-II)中，R^a20 ~R^a22 為由直鏈狀、支鏈狀或環狀之伸烷基、伸芳基、-O-、-C(=O)-、-NH-及該些的組合所形成的基，其可分別為同亦可、相異亦可。E¹ ~E³ 為由環氧基、氧環丁烷基、乙烯性不飽合基、烷氧矽烷基、異氰酸酯基、嵌段異氰酸酯基、硫醇基、羧基、羥基及琥珀酸酐基所成之群所選出之至少1種的取代基或氫原子。但，E¹ ~E³ 中之至少2個，為由環氧基及氧環丁烷基所成之群所選出之至少1種)。Among the compounds represented by the above formula (a1-I), compounds represented by the following formula (a1-II) are preferred.

(In the formula (a1-II), R ^a20 ~ R ^a22 are linear, branched or cyclic alkylene, aryl, -O-, -C(=O)-, -NH- And the groups formed by the combination of these can be the same or different respectively. E ¹ ~ E ³ are epoxy groups, oxetane groups, ethylenically unsaturated groups, alkoxysilanes group, isocyanate group, blocked isocyanate group, thiol group, carboxyl group, hydroxyl group and succinic anhydride group, at least one substituent or hydrogen atom selected from the group. However, at least two of E ¹ to E ³ , is at least one selected from the group consisting of epoxy group and oxetanyl group).

In formula (a1-II), the groups represented by R ^a20 and E ¹ , R ^a21 and E ² , and R ^a22 and E ³ are, for example, at least two groups represented by the following formula (a1-IIa) More preferably, all are groups represented by the following formulas (a1-IIa) respectively. The groups represented by the plural formula (a1-IIa) to which one compound is bonded are preferably the same group. -LC ^a (a1-IIa) (In the formula (a1-IIa), L is a linear, branched or cyclic alkylene group, arylylene group, -O-, -C(=O)-, -NH- and the group formed by the combination thereof, C ^a is an epoxy group. In the formula (a1-IIa), L and C ^a may be bonded to form a ring structure).

In the formula (a1-IIa), the straight-chain, branched or cyclic alkylene group of L is preferably an alkylene group having 1 to 10 carbon atoms, and the arylylene group of L, For example, an aryl group having 5 to 10 carbon atoms is preferable. In the formula (a1-IIa), L is a linear chain with 1 to 3 carbon atoms, alkylene, phenylene, -O-, -C(=O)-, -NH-, and these The group formed by combination is preferably at least one of straight-chain alkylene and phenylene groups having 1 to 3 carbon atoms such as a methylene group, or these are combined with -O-, The group formed by the combination of at least one of -C(=O)- and NH- is more preferable.

(式(a1-IIb)中，R^a23 為氫原子或甲基)。In the formula (a1-IIa), when L and C ^a are bonded to form a ring structure, for example, a branched chain alkylene group is bonded to an epoxy group to form a ring structure (an epoxy group structure with an alicyclic structure) In this case, it is an organic group or the like represented by the following formulas (a1-IIb) to (a1-IId).

(In the formula (a1-IIb), R ^a23 is a hydrogen atom or a methyl group).

Hereinafter, although the oxirane group of the compound represented by formula (a1-II) or the epoxy compound which has an alicyclic epoxy group is illustrated, it is not limited to these content.

(Silicone epoxy compound represented by formula (a1-III)) Among the above-mentioned siloxane compounds, compounds having a cyclic siloxane skeleton represented by the following formula (a1-III) (hereinafter also referred to as When it is "cyclosiloxane"), it is preferred.

In formula (a1-III), R ^a24 and R ^a25 represent a monovalent group or an alkyl group containing an epoxy group. However, in the compound represented by the formula (a1-III), at least two of x1 R ^a24 and x1 R ^a25 are monovalent groups containing an epoxy group. In addition, x1 in formula (a1-III) represents an integer of 3 or more. In addition, in the compound represented by formula (a1-III), R ^a24 and R ^a25 may be the same or different. In addition, plural R ^a24 may be the same or different. Plural R ^a25 may be the same or different. The above-mentioned alkyl group, for example, a methyl group, an ethyl group, a propyl group, an isopropyl group, etc. have a carbon number of 1 to 18 (preferably a carbon number of 1 to 6, particularly preferably a carbon number of 1 or more) , 3 or less) straight-chain or branched-chain alkyl group.

x1 in the formula (a1-III) represents an integer of 3 or more, and an integer of 3 or more and 6 or less is preferable from the viewpoint of excellent crosslinking reactivity when forming a cured film.

The number of epoxy groups in the molecule of the siloxane compound is 2 or more, and from the viewpoint of better cross-linking reactivity when forming a cured film, preferably 2 or more and 6 or less, Most preferably, there are 2 or more and 4 or less.

(上述式中，D¹ 及D² 各自獨立表示伸烷基；ms表示0以上、2以下之整數；*表示鍵結鍵)。 上述伸烷基，例如，伸甲基、甲基伸甲基、二甲基伸甲基、伸二甲基、伸三甲基等的碳原子數為1以上、18以下之直鏈狀或支鏈狀的伸烷基等。The above-mentioned monovalent bases containing epoxy groups can include, for example, alicyclic epoxy groups, glycidyl ether groups, etc., and alicyclic epoxy groups are preferred, with the following formula (a1-IIIa) or the following The alicyclic epoxy group represented by the formula (a1-IIIb) is preferable.

(In the above formula, ^D1 and ^D2 each independently represent an alkylene group; ms represents an integer between 0 and 2; * represents a bond). The above-mentioned alkylene group, for example, a straight chain or branched chain having 1 to 18 carbon atoms such as methylene, methyl methylene, dimethyl methylene, dimethyl methylene, tri methylene, etc. alkylene etc.

The curable composition, in addition to the siloxane compound represented by formula (a1-III), may also contain alicyclic epoxy group-containing cyclic siloxane, the alicyclic siloxane described in JP-A-2008-248169 Polysiloxane resins containing epoxy groups, and organic polysilsesquioxane resins having at least two epoxy functional groups in one molecule described in JP-A-2008-19422, etc., compounds having a siloxane skeleton .

More specifically, the siloxane compound includes, for example, cyclic siloxane having two or more epoxy groups in the molecule represented by the following formula, but the present invention is not limited thereto. In addition, silicone compounds, for example, can use trade names "X-40-2670", "X-40-2701", "X-40-2728", "X-40-2738", "X-40- 2740" (above, manufactured by Shin-Etsu Chemical Co., Ltd.).

(cyclic sulfide compound) The type of cyclic sulfide compound is not particularly limited as long as it does not hinder the object of the present invention. Preferable cyclic thioether compounds are, for example, compounds in which the oxygen atom in the epoxy group is replaced by a sulfur atom among the aforementioned epoxy compounds.

(vinyl ether compound) (A) The curable compound may or may not contain an ethyleneoxy group-containing vinyl ether compound. The vinyl ether compound is not particularly limited as long as it has a vinyloxy group and is cationically polymerizable. The vinyl ether compound may or may not contain an aromatic group. From the viewpoint of good thermal decomposition resistance of the cured product, the vinyl ether compound is preferably a compound having a vinyloxy group bonded to an aromatic group.

Preferred specific examples of vinyl ether compounds include, for example, vinylphenyl ether, 4-vinyloxytoluene, 3-vinyloxytoluene, 2-vinyloxytoluene, 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-ethyleneoxy Base-3,5-dimethylbenzene, 1-vinyloxynaphthalene, 2-vinyloxynaphthalene, 2-vinyloxystilbene, 3-vinyloxystilbene, 4-vinyloxy-1,1'- Biphenyl, 3-vinyloxy-1,1'-biphenyl, 2-vinyloxy-1,1'-biphenyl, 6-vinyloxytetralin, and 5-vinyloxytetralin, etc. Aromatic monovinyl ether compounds; 1,4-divinyloxybenzene, 1,3-divinyloxybenzene, 1,2-divinyloxybenzene, 1,4-divinyloxynaphthalene, 1, 3-divinyloxynaphthalene, 1,2-divinyloxynaphthalene, 1,5-divinyloxynaphthalene, 1,6-divinyloxynaphthalene, 1,7-divinyloxynaphthalene, 1, 8-divinyloxynaphthalene, 2,3-divinyloxynaphthalene, 2,6-divinyloxynaphthalene, 2,7-divinyloxynaphthalene, 1,2-divinyloxynaphthalene, 3, 4-divinyloxydiphenyl, 2,7-divinyloxydiphenyl, 4,4'-divinyloxybiphenyl, 3,3'-divinyloxybiphenyl, 2,2'-divinyloxy Aryl biphenyl, 3,4'-divinyloxybiphenyl, 2,3'-divinyloxybiphenyl, 2,4'-divinyloxybiphenyl, and bisphenol A divinyl ether, etc. family of divinyl ether compounds, etc. These vinyl ether compounds may be used in combination of two or more.

環結構之聚合物) 具有三

環結構之聚合物，以與以上說明的其他的(A)硬化性化合物混合使用者為佳。 上述具有三

環結構之聚合物(以下亦簡稱為「含三

環之聚合物」)之例如，下述式(t1)~(t16)所示者等。(with three

polymers with ring structure) have three

The ring-structured polymer is preferably used in combination with other (A) hardening compounds described above. The above has three

Ring-structured polymers (hereinafter also referred to as "three-containing

Ring polymer"), for example, those represented by the following formulas (t1) to (t16).

上述式中，R及R’，各自獨立表示氫原子、烷基、烷氧基、芳基或芳烷基，就使折射率更為提升之觀點，以皆為氫原子為佳；R¹ ~R³ 及R^1’ ~R^4’ ，各自獨立表示氫原子、鹵素原子、羧基、磺酸基、碳原子數1以上、10以下的可具有分支結構之烷基，或碳原子數1以上、10以下的可具有分支結構之烷氧基；R¹⁰² 及R¹⁰³ 表示互相獨立的碳原子數1以上、5以下之烷基)。

In the above formula, R and R' each independently represent a hydrogen atom, an alkyl group, an alkoxy group, an aryl group or an aralkyl group, and it is preferable that they are all hydrogen atoms in order to improve the refractive index; R ¹ ~ R ³ and R ^1' ~R ^4' each independently represent a hydrogen atom, a halogen atom, a carboxyl group, a sulfonic acid group, an alkyl group with 1 to 10 carbon atoms that may have a branched structure, or an alkyl group with 1 or more carbon atoms, An alkoxy group of 10 or less which may have a branched structure; R ¹⁰² and R ¹⁰³ represent mutually independent alkyl groups with 1 to 5 carbon atoms).

(式中，R、R’、R¹ ~R³ 、R^1’ ~R^4’ 、R¹⁰² 及R¹⁰³ ，表示與上述為相同之意義)。

(In the formula, R, R', R ¹ to R ³ , R ^1' to R ^4' , R ¹⁰² and R ¹⁰³ have the same meaning as above).

(式中，R、R’、R¹ ~R³ 及R^1’ ~R^4’ ，表示與上述為相同之意義)。

(In the formula, R, R', R ¹ to R ³ and R ^1' to R ^4' represent the same meaning as above).

(式中，R、R’、R¹ ~R³ 及R^1’ ~R^4’ ，表示與上述為相同之意義，R⁴ 表示氫原子、鹵素原子、羧基、磺酸基、碳原子數1以上、10以下的具有分支結構之烷基，或碳原子數1以上、10以下的具有分支結構之烷氧基；R¹⁰² 及R¹⁰³ 表示互相獨立的碳原子數1以上、5以下之烷基)。

(In the formula, R, R', R ¹ ~ R ³ and R ^1' ~ R ^4' represent the same meaning as above, and R ⁴ represents a hydrogen atom, a halogen atom, a carboxyl group, a sulfonic acid group, and a carbon atom number of 1 An alkyl group with a branched structure of 1 to 10, or an alkoxy group with a branched structure with 1 to 10 carbon atoms; R ¹⁰² and R ¹⁰³ represent mutually independent alkyl groups with 1 to 5 carbon atoms ).

(式中，R、R’、R¹ ~R⁴ 、R^1’ ~R^4’ 、R¹⁰² 及R¹⁰³ ，表示與上述為相同之意義)。

(In the formula, R, R', R ¹ to R ⁴ , R ^1' to R ^4' , R ¹⁰² and R ¹⁰³ have the same meaning as above).

(式中，R、R’、R¹ ~R⁴ 及R^1’ ~R^4’ ，表示與上述為相同之意義)。

(In the formula, R, R', R ¹ to R ⁴ and R ^1' to R ^4' represent the same meaning as above).

(式中，R、R’、R¹ ~R³ 及R^1’ ~R^4’ ，表示與上述為相同之意義，R¹⁰² 及R¹⁰³ 表示互相獨立的碳原子數1以上、5以下之烷基)。

(In the formula, R, R', R ¹ to R ³ and R ^1' to R ^4' represent the same meaning as above, R ¹⁰² and R ¹⁰³ represent mutually independent alkanes with 1 to 5 carbon atoms base).

(式中，R、R’、R¹ ~R³ 、R^1’ ~R^4’ 、R¹⁰² 及R¹⁰³ ，表示與上述為相同之意義)。

(In the formula, R, R', R ¹ to R ³ , R ^1' to R ^4' , R ¹⁰² and R ¹⁰³ have the same meaning as above).

(式中，R、R’、R¹ ~R³ 及R^1’ ~R^4’ ，表示與上述為相同之意義)。

(In the formula, R, R', R ¹ to R ³ and R ^1' to R ^4' represent the same meaning as above).

(式中，R、R’、R¹ ~R⁴ 及R^1’ ~R^4’ ，表示與上述為相同之意義，R¹⁰² 及R¹⁰³ 表示互相獨立的碳原子數1以上、5以下之烷基)。

(In the formula, R, R', R ¹ to R ⁴ and R ^1' to R ^4' represent the same meaning as above, R ¹⁰² and R ¹⁰³ represent mutually independent alkanes with 1 to 5 carbon atoms base).

(式中，R、R’、R¹ ~R⁴ 、R^1’ ~R^4’ 、R¹⁰² 及R¹⁰³ ，表示與上述為相同之意義)。

(In the formula, R, R', R ¹ to R ⁴ , R ^1' to R ^4' , R ¹⁰² and R ¹⁰³ have the same meaning as above).

(式中，R、R’、R¹ ~R⁴ 及R^1’ ~R^4’ ，表示與上述為相同之意義)。

(In the formula, R, R', R ¹ to R ⁴ and R ^1' to R ^4' represent the same meaning as above).

環之聚合物之重量平均分子量(Mw)，並未有特別限定者，一般以500以上、500,000以下為佳，又以500以上、100,000以下為更佳，就達成本發明效果之觀點，以2,000以上為佳，就可使溶解性更為提高、所得之溶液的黏度降低之觀點，以50,000以下為佳，以30,000以下為較佳，又更以10,000以下為佳。 又，本發明中之Mw為使用凝膠滲透色層分析(以下，GPC)分析所得之標準聚苯乙烯換算的平均分子量。Contains three

The weight average molecular weight (Mw) of the polymer of the ring is not particularly limited. Generally, it is more than 500 and less than 500,000, and it is more preferably more than 500 and less than 100,000. From the viewpoint of achieving the effect of the present invention, 2,000 The above is preferable, and the solubility can be further improved and the viscosity of the obtained solution can be lowered. It is preferably 50,000 or less, more preferably 30,000 or less, and more preferably 10,000 or less. In addition, Mw in the present invention is an average molecular weight in terms of standard polystyrene as analyzed by gel permeation chromatography (hereinafter, GPC).

環之聚合物，例如，可依國際公開第2010/128661號所揭示之方法製得。Contains three

Ring polymers, for example, can be prepared according to the method disclosed in International Publication No. 2010/128661.

環之聚合物，以具有至少1個二胺末端，且該二胺末端中至少一個被醯基、烷氧羰基、芳烷氧羰基或芳氧羰基等的含羰基之基所密封者為佳。如此，經被含羰基之基密封末端時，可抑制含三

環之聚合物的著色。Also, including three

The ring polymer preferably has at least one diamine terminal, and at least one of the diamine terminals is sealed with a carbonyl-containing group such as an acyl group, an alkoxycarbonyl group, an aralkoxycarbonyl group, or an aryloxycarbonyl group. In this way, when the end is sealed by a carbonyl-containing group, it can inhibit the

Coloring of ring polymers.

Specific examples of the acyl group include, for example, an acetyl group, an ethylcarbonyl group, an acryl group, a methacryl group, and a benzoyl group. Specific examples of the alkoxycarbonyl group include methoxycarbonyl, ethoxycarbonyl, t-butoxycarbonyl and the like. Specific examples of aralkoxycarbonyl include benzyloxycarbonyl and the like. Specific examples of aryloxycarbonyl include, for example, phenoxycarbonyl and the like. Among these, terminal sealing groups such as acyl group are preferable, and acryl group, methacryl group, and acetyl group are more preferable in consideration of the ease of obtaining reagents.

As a method of sealing the ends, a known method may be used, for example, treatment with an acid halide, an acid anhydride, or the like may be used. At this time, the amount of the terminal sealant used is preferably 0.05 equivalent or more and 10 equivalent or less, and preferably 0.1 equivalent or more and 5 It is preferably not more than an equivalent, and more preferably not less than 0.5 equivalents and not more than 2 equivalents.

(A) The hardening compound may be used individually or in mixture of several types. In the curable composition, the content of the (A) curable compound is not particularly limited as long as it is within the range that does not hinder the object of the present invention. The content of (A) the curable compound in the curable composition is preferably not less than 60 parts by mass and not more than 99.9 parts by mass, and preferably not less than 75 parts by mass, It is preferably not more than 99.5 parts by mass, and particularly preferably not less than 90 parts by mass and not more than 99 parts by mass.

＜(B) Cationic polymerization initiator＞ The curable composition may or may not contain a polymerization initiator, but it is preferable to contain a polymerization initiator from the viewpoint of accelerating curing. However, in the present invention, the polymerization initiator does not include an ionic liquid corresponding to (C) described later. The polymerization initiator may be used alone or in combination of plural kinds. The above-mentioned polymerization initiators are preferably (B) cationic polymerization initiators or anionic polymerization initiators from the viewpoint of whether the curable composition is cation-curable or anion-hardenable, and (B) cationic polymerization initiators is better.

(式(b1)中，R^b1 、R^b2 、R^b3 及R^b4 各自獨立為，可具有取代基之烴基或雜環基，R^b1 、R^b2 、R^b3 ，及R^b4 中之至少一個為可具有取代基之芳香族烴基)。(Cerium salt (B1)) (B) The cationic polymerization initiator is composed of a cationic part and an anionic part, and the anion part is an anion represented by the following formula (b1) from the viewpoint of curability. (B1) is preferred.

(In formula (b1), R ^b1 , R ^b2 , R ^b3 , and R ^b4 are each independently a hydrocarbon group or a heterocyclic group that may have a substituent, and at least one of R ^b1 , R ^b2 , R ^b3 , and R ^b4 is an aromatic hydrocarbon group which may have a substituent).

In the above-mentioned percolium salt (B1), the cation portion is a counter cation to the anion represented by the above-mentioned formula (b1), and is not particularly limited as long as it can well cure the curable composition. For cations, for example, those shown in the following formula (b2): (R ^b5 ) _t+1 -R ^b6+ ･･･(b2) (In formula (b2), R ^b5 is a monovalent organic group; R ^b6 is Elements of group 15~17 (IUPAC label) with atomic valence t. t is an integer between 1 and 3. Plural R ^b5 can be the same or different, and plural R ^b5 can be bonded to R ^b6 together form a ring).

The number of carbon atoms of the hydrocarbon group or heterocyclic group of R ^b1 to R ^b4 in the formula (b1) is not particularly limited, and it is preferably 1 or more and 50 or less, preferably 1 or more and 30 or less. More than 1 and less than 20 are especially good. Specific examples of the hydrocarbon groups of R ^b1 to R ^b4 include, for example, straight-chain or branched alkyl groups, straight-chain or branched alkenyl groups, straight-chain or branched alkynyl groups, aromatic hydrocarbon groups, Alicyclic hydrocarbon group, and aralkyl group, etc. As mentioned above, at least one of R ^b1 to R ^b4 is an aromatic group that may have a substituent, and preferably three or more of R ^b1 to R ^b4 are aromatic groups that may have a substituent. It is particularly preferable that all of R ^b1 to R ^b4 are aromatic groups which may have substituents.

The substituents that the hydrocarbon groups or heterocyclic groups of R ^b1 to R ^b4 may have include, for example, halogenated alkyl groups with 1 to 18 carbon atoms, halogenated aliphatic rings with 3 to 18 carbon atoms group, nitro group, hydroxyl group, cyano group, alkoxy group with 1 to 18 carbon atoms, aryloxy group with 6 to 14 carbon atoms, aliphatic acyl group with 2 to 19 carbon atoms, Aromatic acyloxy group with 7 to 15 carbon atoms, aliphatic acyloxy group with 2 to 19 carbon atoms, aromatic acyloxy group with 7 to 15 carbon atoms, 1 or more carbon atoms, Alkylthio groups of 18 or less, arylthio groups of 6 or more and 14 or less carbon atoms, amines in which one or two hydrogen atoms bonded to nitrogen atoms may be substituted by hydrocarbon groups of 1 or more and 18 or less carbon atoms groups, and halogen atoms, etc. When the hydrocarbon groups of R ^b1 to R ^b4 are aromatic hydrocarbon groups, the aromatic hydrocarbon groups can be composed of alkyl groups with 1 to 18 carbon atoms, alkenyl groups with 2 to 18 carbon atoms, and 2 or more carbon atoms , 18 or less alkynyl groups are substituted with one or more substituents selected from the group.

When the hydrocarbon groups of R ^b1 to R ^b4 have substituents, the number of substituents is not particularly limited, and it may be 1 or a plurality of 2 or more. When the number of substituents is plural, the plural substituents may be the same or different.

Preferred specific examples when R ^b1 to R ^b4 are alkyl groups include, for example, methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-octyl, n -Nonyl, n-decyl, n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, n - Straight-chain alkyl groups such as heptadecyl, n-octadecyl, n-nonadecyl, and n-eicosyl; isopropyl, isobutyl, sec-butyl, tert-butyl branched alkyl groups such as isopentyl, neopentyl, tert-pentyl, isohexyl, 2-ethylhexyl, and 1,1,3,3-tetramethylbutyl, etc.

Desirable examples when R ^b1 to R ^b4 are alkenyl or alkynyl include, for example, alkenyl and alkynyl corresponding to the above-mentioned preferred groups as an alkyl group.

Preferred examples of R ^b1 to R ^b4 are aromatic hydrocarbon groups, such as phenyl, α-naphthyl, β-naphthyl, biphenyl-4-yl, biphenyl-3-yl, biphenyl-2- Base, anthracenyl, and phenanthrenyl, etc.

Preferred examples of R ^b1 to R ^b4 are alicyclic hydrocarbon groups, such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclopentyl, cyclooctyl, cyclononyl, and cyclodecyl Cycloalkyl groups such as cycloalkyl groups; norbornyl, adamantyl, tricyclodecanyl, and pinenyl and other cross-linked aliphatic cyclic hydrocarbon groups.

Preferred examples of R ^b1 to R ^b4 are aralkyl groups, such as benzyl, phenethyl, α-naphthylmethyl, β-naphthylmethyl, α-naphthylethyl, and β-naphthylethyl wait.

基、吲哚基、苯併呋喃基、苯併噻吩基、喹啉基、異喹啉基、喹噁啉基、喹唑啉基、咔唑基、吖啶基、酚噻

基、吩

基、呫噸基、噻嗯基、啡噁

基、啡噁噻基、苯并2氫哌喃基、異苯并2氫哌喃基、二苯併噻吩基、氧葱酮基、硫氧葱酮基，及二苯併呋喃基等。Preferred examples of R ^b1 to R ^b4 are heterocyclic groups, such as thienyl, furyl, selenophyl, pyryl, pyrrolyl, oxazolyl, thiazolyl, pyridyl, pyrimidyl, pyrimidyl,

Base, indolyl, benzofuryl, benzothienyl, quinolinyl, isoquinolyl, quinoxalinyl, quinazolinyl, carbazolyl, acridyl, phenothiazyl

base, phen

Xanthenyl, Xanthenyl, Thienyl, Phenyloxanthyl

phenanthienyl, benzo2hydropyranyl, isobenzo2hydropyranyl, dibenzothienyl, oxanthione, thioxanthione, and dibenzofuryl, etc.

When the hydrocarbon group of R ^b1 to R ^b4 or the substituent that the heterocyclic group may have is a halogenated alkyl group, preferred examples of the halogenated alkyl group include, for example, trifluoromethyl, trichloromethyl, pentafluoroethyl, 2,2,2-Trichloroethyl, 2,2,2-trifluoroethyl, 1,1-difluoroethyl, heptafluoro-n-propyl, 1,1-difluoro-n-propyl , 3,3,3-trifluoro-n-propyl, nonafluoro-n-butyl, 3,3,4,4,4-pentafluoro-n-butyl, perfluoro-n-pentyl, and Straight-chain halogenated alkyl groups such as perfluoro-n-octyl; branched-chain halogenated alkyl groups such as hexafluoroisopropyl, hexachloroisopropyl, hexafluoroisobutyl, and nonafluoro-tert-butyl, etc.

When the hydrocarbon group of R ^b1 to R ^b4 or the substituent that the heterocyclic group may have is a halogenated aliphatic ring group, preferred examples of the halogenated aliphatic ring group include, for example, pentafluorocyclopropyl, nonafluorocyclopropyl Butyl, perfluorocyclopentyl, perfluorocyclohexyl, and perfluoroadamantyl, etc.

When the hydrocarbon group of R ^b1 to R ^b4 or the substituent that the heterocyclic group may have is an alkoxy group, preferable examples of the alkoxy group include, for example, methoxy, ethoxy, n-propoxy, n -butoxy, n-pentyloxy, n-hexyloxy, n-octyloxy, n-nonyloxy, n-decyloxy, n-undecyloxy, n-dodecyloxy , n-tridecyloxy, n-tetradecyloxy, n-pentadecyloxy, n-hexadecyloxy, n-heptadecyloxy, and n-octadecyloxy, etc. Linear alkoxy; isopropoxy, isobutoxy, sec-butoxy, tert-butoxy, isopentyloxy, neopentyloxy, tert-pentyloxy, isohexyloxy, 2- Ethylhexyloxy, branched alkoxy such as 1,1,3,3-tetramethylbutoxy, etc.

When the hydrocarbon group of R ^b1 to R ^b4 or the substituent that the heterocyclic group may have is an aryloxy group, preferable examples of the aryloxy group include, for example, phenoxy, α-naphthyloxy, and β-naphthyloxy , Biphenyl-4-oxyl, biphenyl-3-oxyl, biphenyl-2-oxyl, anthracenyloxy, and phenanthryloxy, etc.

When the hydrocarbon group of R ^b1 to R ^b4 or the substituent that the heterocyclic group may have is an aliphatic acyl group, preferable examples of the aliphatic acyl group include, for example, acetyl, propionyl, butyryl, and pentyl. , hexyl, heptyl, and octyl, etc.

When the hydrocarbon group of R ^b1 to R ^b4 or the substituent that the heterocyclic group may have is an aromatic acyl group, preferable examples of the aromatic acyl group include, for example, benzoyl, α-naphthyl, β- Naphthyl, biphenyl-4-carbonyl, biphenyl-3-carbonyl, biphenyl-2-carbonyl, anthracene carbonyl, and phenanthrene carbonyl, etc.

When the hydrocarbon group of R ^b1 to R ^b4 or the substituent that the heterocyclic group may have is an aliphatic acyloxy group, preferred examples of the aliphatic acyloxy group include, for example, acetyloxy, acryloxy, butyl Acyloxy, pentyloxy, hexyloxy, heptyloxy, and octyloxy, etc.

When the hydrocarbon group of R ^b1 to R ^b4 or the substituent that the heterocyclic group may have is an aromatic acyloxy group, preferable examples of the aromatic acyloxy group include, for example, benzoyloxy, α-naphthyloxy Base, β-naphthyloxy, biphenyl-4-ylcarbonyloxy, biphenyl-3-ylcarbonyloxy, biphenyl-2-ylcarbonyloxy, anthracenylcarbonyloxy, and phenanthrenylcarbonyloxy Base etc.

When the substituents that the hydrocarbon groups or heterocyclic groups of R ^b1 to R ^b4 may have are alkylthio groups or arylthio groups, preferred examples of alkylthio groups or arylthio groups include, for example, the aforementioned alkoxy groups , or a group obtained by replacing an oxygen atom in a preferable group of an aryloxy group with a sulfur atom, etc.

When the hydrocarbon group of R ^b1 to R ^b4 or the substituent that the heterocyclic group may have is an amino group that may be substituted by a hydrocarbon group, preferred examples of the amino group that may be substituted by a hydrocarbon group include, for example, an amino group, a methylamino group, Ethylamino, n-propylamino, dimethylamino, diethylamino, methylethylamino, di-n-propylamino, piperidinyl, etc.

When the substituent that the hydrocarbon groups or heterocyclic groups of R ^b1 to R ^b4 may have is a halogen atom, preferable examples of the halogen atom include, for example, a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

Among the hydrocarbon groups of R ^b1 to R ^b4 described above, or the substituents that the heterocyclic group may have, when the initiator is the perjuly salt (B1), it has high activity, and the number of carbon atoms is 1 to 8. The halogenated alkyl group, halogen atom, nitro group, and cyano group are preferable, and the fluorinated alkyl group with 1 to 8 carbon atoms is more preferable.

R ^b5 in the formula (b2) represents an organic group bonded to R ^b6 . They may be the same or different; R ^b5 includes, for example, an aromatic hydrocarbon group having 6 to 14 carbon atoms, an alkyl group having 1 to 18 carbon atoms, and an alkyl group having 2 or more to 18 carbon atoms. The following alkenyl groups, and the alkynyl groups having 2 to 18 carbon atoms, etc. The aromatic hydrocarbon group can also be replaced by, for example, an alkyl group with 1 to 18 carbon atoms, an alkenyl group with 2 to 18 carbon atoms, an alkynyl group with 2 to 18 carbon atoms, a carbon number with 6 or more, Aryl group of 14 or less, nitro, hydroxyl, cyano, alkoxy group of 1 to 18 carbon atoms, aryloxy group of 6 or more but 14 carbon atoms, aliphatic group of 2 or more and 19 or less carbon atoms Aromatic acyl group, aromatic acyl group with 7 to 15 carbon atoms, aliphatic acyloxy group with 2 to 19 carbon atoms, aromatic acyloxy group with 7 to 15 carbon atoms, carbon atom An alkylthio group with a number of 1 to 18, an arylthio group with a carbon number of 6 to 14, and one or two hydrogen atoms bonded to a nitrogen atom may be substituted with a hydrocarbon group with a carbon number of 1 to 18 Amino groups, and halogen atoms are substituted. Desirable examples of these substituents are, for example, the same as those of the hydrocarbon groups of R ^b1 to R ^b4 in the formula (b1), or the substituents that may have a heterocyclic group.

In the formula (b2), when there are plural R ^b5 , the plural R ^b5 may form a ring together with R ^b6 . The ring formed by plural R ^b5 and R ^b6 may contain -O-, -S-, -SO-, -SO ₂ -, -NH-, -CO-, -COO- in the intermediate structure , and one or more bonds selected from the group formed by -CONH-.

The cation part in the permeicium salt (B1) is preferably a cation represented by the aforementioned formula (b2). R ^b6 in formula (b2) is an element of group 15 to group 17 (IUPAC mark) with atomic valence t. t is an integer of 1 to 3. R ^b6 bonds with the organic group R ^b5 to form an onium ion [R ^b6+ ]. Among the elements of Groups 15 to 17, O (oxygen), N (nitrogen), P (phosphorus), S (sulfur), or I (iodine) are preferable, for example. The corresponding onium ions include, for example, oxonium ions, ammonium ions, phosphonium ions, perium ions, and iodonium ions. Among them, ammonium ions, phosphonium ions, perium ions, and iodonium ions are preferred from the standpoint of easy and stable treatment, and ions such as phosphonium ions and iodonium ions are preferred from the viewpoint of excellent cationic polymerization performance or excellent cross-linking reaction performance. better.

Specific examples of positive oxygen ions, for example, positive oxygen ions such as trimethyl positive oxygen ions, diethylmethyl positive oxygen ions, triethyl positive oxygen ions, tetramethylmethyl positive oxygen ions, etc.; Pyrylium, 2,4,6-trimethylpyrylium, 2,6-di-tert-butylpyrylium, 2,6-diphenylpyrylium, etc.; 2,4- Benzopyrylium such as dimethylbenzopyrylium and 1,3-dimethylisobenzopyrylium, isobenzopyrylium, and the like.

Specific examples of ammonium ions, such as tetramethylammonium, ethyltrimethylammonium, diethyldimethylammonium, triethylmethylammonium, and tetraalkylammonium such as tetraethylammonium; Methylpyrrolidinium, N-ethyl-N-methylpyrrolidinium, and pyrrolidinium such as N,N-diethylpyrrolidinium salt; N,N'-dimethylimidazolinium, N ,N'-diethylimidazolinium, N-ethyl-N'-methylimidazolinium, 1,3,4-trimethylimidazolinium, and 1,2,3,4-tetramethyl Imidazolinium such as imidazolinium; tetrahydropyrimidinium such as N,N'-dimethyltetrahydropyrimidinium; morpholinium such as N,N'-dimethylmorpholinium; N,N'- Piperidinium such as diethylpiperidinium; pyridinium such as N-methylpyridinium, N-benzylpyridinium, and N-benzylformylpyridinium; N,N'-dimethyl Imidazolium such as imidazolium; N-methylquinolinium, N-benzylquinolinium, and quinolinium such as N-benzylformylquinolinium; N-methylisoquinolinium, etc. Isoquinolinium; benzylbenzothiazolium, and thiazolium such as benzylformylbenzothiazolium; benzylacridinium, and acridinium such as benzylformylacridinium wait.

Specific examples of phosphonium ions, for example, tetraphenylphosphonium, tetra-p-tolylphosphonium, tetrakis(2-methoxyphenyl)phosphonium, tetrakis(3-methoxyphenyl)phosphonium, and tetrakis(4-methoxyphenyl)phosphonium Tetraarylphosphonium such as phenyl)phosphonium; triarylphosphonium such as triphenylbenzylphosphonium, triphenylbenzylformylphosphonium, triphenylmethylphosphonium, and triphenylbutylphosphonium; triethylphosphonium benzylphosphonium, tributylbenzylphosphonium, tetraethylphosphonium, tetrabutylphosphonium, tetrahexylphosphonium, triethylbenzylformylphosphonium, tributylbenzylformylphosphonium, etc. Tetraalkylphosphonium, etc.

Specific examples of percited ions, for example, triphenylcolumbite, tri-p-toluenecolumbite, tris-o-toluenecolumbite, tris(4-methoxyphenyl)columbite, 1-naphthyldibenzocolumbite, 2-naphthylbiscolumbium Benzene percolium, Tris(4-fluorophenyl) percolium, Tris-1-naphthalene permeate, Tris-2-naphthalene permeate, Tris(4-hydroxyphenyl) permeate, 4-(phenylthio)phenyl dibenzo permeate, 4-(p-tolylthio)phenyldi-p-toluene, 4-(4-methoxyphenylthio)phenylbis(4-methoxyphenyl)colum, 4-(phenylthio) Phenylbis(4-fluorophenyl)columbite, 4-(phenylthio)phenylbis(4-methoxyphenyl)columbite, 4-(phenylthio)phenylbis-p-toluenecolumbite, [4 -(4-Biphenylsulfanyl)phenyl]-4-biphenylbenzol Sulfuryl)phenyl]sulfide, bis[4-{bis[4-(2-hydroxyethoxy)phenyl]dihydrothio}phenyl]sulfide, bis{4-[bis(4- Fluorophenyl)dihydrothio]phenyl}sulfide, bis{4-[bis(4-methylphenyl)dihydrothio]phenyl}sulfide, bis{4-[bis(4-methoxybenzene Base) dihydrogenthio] phenyl} sulfide, 4-(4-benzoyl-2-chlorophenylthio)phenyl bis(4-fluorophenyl) percolium, 4-(4-benzoyl Base-2-chlorophenylsulfanyl)phenyldibenzoyl, 4-(4-benzoylphenylthio)phenylbis(4-fluorophenyl)pyridium, 4-(4-benzoylphenyl) Thio)phenyldibenzocondium, 7-isopropyl-9-oxa-10-thio-9,10-dihydroanthracene-2-ylbis-p-toluene, 7-isopropyl-9- Oxa-10-thio-9,10-dihydroanthracene-2-yldibenzoperium, 2-[(di-p-tolyl)dihydrothio]thioxanthone, 2-[(diphenyl) Dihydromercapto] thioxanthone, 4-(9-oxa-9H-thioxanth-2-yl)thiophenyl-9-oxa-9H-thioxanthene-2-benzoconium, 4-[ 4-(4-tert-butylbenzoyl)phenylthio]phenyldi-p-toluene, 4-[4-(4-tert-butylbenzoyl)phenylthio]phenyl Dibenzoylium, 4-[4-(benzoylphenylthio)]phenyldi-p-toluene, 4-[4-(benzoylphenylthio)]phenyldibenzoyl, 5 -(4-methoxyphenyl)thianthracenium, 5-phenylthianthracenium, 5-tolylthianthracenium, 5-(4-ethoxyphenyl)thianthracenium, and 5-(2,4 , 6-Trimethylphenyl) thianthracene and other triaryl peroxides; Benzyl benzyl, 4-hydroxybenzyl benzyl, 4-methoxybenzyl benzyl, 4-acetylcarbonyloxybenzyl benzyl, 4-hydroxyphenyl ( 2-naphthylmethyl)formazolium, 2-naphthylmethylbenzylconium, 2-naphthylmethyl(1-ethoxycarbonyl)acetoconium, benzylbenzylformazolium, 4-hydroxybenzylbenzyl Methylformylformyl, 4-methoxybenzylbenzylformyl, 4-acetylcarbonyloxybenzylbenzylformyl, 2-naphthylmethylbenzylformyl, 2- Naphthyloctadecylbenzylformyl, and 9-anthracenemethylbenzylformyl, such as monoaromatic; dimethylbenzylformyl, benzylformyltetrahydrothiophene Onium, dimethylbenzylconium, benzyltetrahydrothiophenium, and octadecylbenzylformylformyl and other trialkylconium.

Also, the permeic salt (B1) may contain an anion part of an anion represented by the above-mentioned formula (b1), and a permeic salt formed by a cation part of a permeic ion represented by the formula (c1) described later is also preferable.

Specific examples of iodonium ions, for example, diphenyliodonium, di-p-tolueneiodonium, bis(4-dodecylphenyl)iodonium, bis(4-methoxyphenyl)iodonium, (4-octyloxyphenyl)iodonium ) benzodiazepines, bis(4-decyloxy)benzodiazepines, 4-(2-hydroxytetradecyloxy)phenylbenzodiazepines, 4-cumyl (p-tolyl) benzodiazepines, and 4-iso Odonium ions such as butylphenyl (p-tolyl)iodonium, etc.

Preferable specific examples of the anion represented by the formula (b1) described above include, for example, tetrakis(4-nonafluorobiphenyl)gallate anion, tetrakis(1-heptafluoronaphthyl)gallate anion, , tetra(pentafluorophenyl) gallate anion, tetrakis(3,4,5-trifluorophenyl) gallate anion, tetrakis(2-nonaphenylbiphenyl) gallate anion, four (2-Heptafluoronaphthyl)gallate anion, tetrakis(7-nonafluoroanthracenyl)gallate anion, tetrakis(4'-(methoxy)octafluorobiphenyl)gallate anion, Tetrakis(2,4,6-tris(trifluoromethyl)phenyl)gallate anion, tetrakis(3,5-bis(trifluoromethyl)phenyl)gallate anion, tetrakis(2, 3-bis(pentafluoroethyl)naphthyl)gallate anion, tetrakis(2-isopropoxy-hexafluoronaphthyl)gallate anion, tetrakis(9,10-bis(heptafluoropropyl) ) heptafluoroanthracenyl) gallate anion, tetrakis(9-nonafluorophenanthryl) gallate anion, tetrakis(4-[tri(isopropyl)silyl]-tetrafluorophenyl)gallate Acid anion, tetrakis(9,10-bis(p-tolyl)-heptafluorophenanthrenyl) gallate anion, tetrakis(4-[dimethyl(t-butyl)silyl]-tetrafluorophenyl ) gallic acid anion, monophenyl tris(pentafluorophenyl) gallic acid anion, and monoperfluorobutyl tris(pentafluorophenyl) gallic acid anion, etc., more preferably, the following anions wait.

Preferred specific examples of the counter cation represented by the formula (b2) described above include, for example, 4-isopropylphenyl (p-tolyl)iodonium, 4-isobutylphenyl (p-tolyl) iodonium ions, etc.; [4-(2-Thioanthronethio)phenyl]dibenzocaldium, 2-[(Di-p-tolyl)dihydromercapto]thioxanthone, 2-[(Diphenyl)dihydromercapto]thioxanthone, 4-(9-Oxa-9H-thioxanth-2-yl)thiophenyl-9-oxa-9H-thioxanthene-2-benzene Containing the thioxanthone skeleton of the calcite ion; The perulium ion listed in the specific example of the cation represented by the formula (c1) described later; The percited ions listed in the specific examples of the cation part of the percited salt represented by the formula (c1') described later; Others, such as the permeic ion shown below; etc.

A columium salt (B1) is formed by using the above-mentioned anion exemplified as a preferred example of the anion represented by the formula (b1) and the above-mentioned cation exemplified by a preferred example of the counter cation represented by the formula (b2) Salt is better. As a preferred specific example of the counter cation represented by the formula (b2), a combination of two or more types can also be used.

The content of the (B) cationic polymerization initiator in the curable composition is not particularly limited as long as it is within the range that does not hinder the object of the present invention. In the curable composition, the content of the (B) cationic polymerization initiator is the total amount of the columium salt (B1) and other cationic polymerization initiators (B2) described later, relative to 100 mass of the (A) hardening compound Parts, preferably 0.01 to 5 parts by mass, preferably 0.05 to 3 parts by mass, particularly preferably 0.1 to 2 parts by mass. Furthermore, the content of the permeic acid salt (B1) is preferably at least 10% by mass, and more preferably at least 50% by mass, relative to the total amount of the permeic acid salt (B1) and other cationic polymerization initiators (B2) described later. , more than 70% by mass is more preferred, more than 90% by mass is particularly preferred, and 100% by mass is the best. When (B) cationic polymerization initiator is used in the amount within this range, a cured product with excellent refractive index and yellowing resistance can be formed, and it is also easy to obtain It is also a curable composition with good adhesion.

(Other cationic polymerization initiators (B2) different from the permeic acid salt (B1)) (B) Among the cationic polymerization initiators, other cationic polymerization initiators (B2) (hereinafter, also simply referred to as "other cationic polymerization initiators (B2)") different from the cobaltium salt (B1) . It may be contained simultaneously with the permeic acid salt (B1), or may be contained alone or not. In the curable composition, when the cobalt salt (B1) is contained together with other cationic polymerization initiators (B2), a cured product with excellent refractive index and yellowing resistance can be formed, and it is also easy to form a cured product with A curable composition with good heat resistance (resistance to thermal decomposition) and good adhesion to the substrate.

Other cationic polymerization initiators (B2) can be thermal cationic polymerization initiators (B2-1) also can, photocationic polymerization initiators (B2-2) also can, again with photocationic polymerization initiators ( B2-2) is preferred. Hereinafter, thermal cationic polymerization initiator (B2-1) and photocationic polymerization initiator (B2-2) will be demonstrated.

・Thermal cationic polymerization initiator (B2-1) Thermal cationic polymerization initiators (B2-1), for example, diphenyliodonium hexafluoroarsenate, diphenyliodonium hexafluorophosphate, diphenyliodonium trifluoromethanesulfonate, triphenylinium tetrafluoroborate, Tris-p-tolueneconium hexafluorophosphate, tris-p-tolueneconium trifluoromethanesulfonate, bis(cyclohexylsulfonyl)diazomethane, bis(tert-butylsulfonyl)diazomethane, Bis(p-toluenesulfonyl)diazomethane, triphenylpermetrifluoromethanesulfonate, diphenyl-4-toluenesulfonyl trifluoromethanesulfonate, diphenyl-2,4,6-trimethylbenzene Acerium-p-toluenesulfonate, and diphenyl-p-phenylthiobenzoinium hexafluorophosphate, etc. These can be used in combination of 2 or more types.

Commercially available thermal cationic polymerization initiators, for example, AMERICURE series (manufactured by American・Can), ULTRASET series (manufactured by Adeka), WPAG series (manufactured by Wako Pure Chemical Industries, Ltd.), etc.; UVE series (manufactured by General Electric), FC series (manufactured by 3M), UV9310C (manufactured by GE Toshiba Silicone), and WPI series (manufactured by Wako Pure Chemical Industries, Ltd.); CYRACURE series ( Union Carbide), UVI series (General Electric), FC series (3M), CD series (Sartomer), OPTOMER SP series (Adeka), OPTOMER CP series (Adeka), San - Aid SI series (manufactured by Sanshin Chemical Industry Co., Ltd.), CI series (manufactured by Nippon Soda Co., Ltd.), WPAG series (manufactured by Wako Pure Chemical Industries, Ltd.), CPI series (manufactured by San-Apro Co., Ltd.), etc. wait.

(式(c-I)中，R^c01 、R^c02 ，及R^c03 各自獨立為碳原子數為1以上、6以下烷基)。The thermal cationic polymerization initiator (B2-1) is composed of a cation part and an anion part, and the above-mentioned cation part is preferably a compound containing a cation represented by the following formula (cI). When this thermal cationic polymerization initiator (B2-1) is used, the curable compound (A) can be well cured to form a cured product having excellent refractive index and yellowing resistance, and it is also easy to produce A curable composition with good heat resistance (resistance to thermal decomposition) and good adhesion to the substrate.

(In formula (cI), R ^c01 , R ^c02 , and R ^c03 are each independently an alkyl group having 1 to 6 carbon atoms).

In formula (cI), preferred examples of R ^c01 , R ^c02 , and R ^c03 alkyl groups include, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl , sec-butyl, tert-butyl, n-pentyl, and n-hexyl, etc. The alkyl group, for example, is preferably methyl or ethyl, more preferably methyl; especially preferably all of R ^c01 , R ^c02 , and R ^c03 are methyl.

That is, the cation represented by the formula (cI) is preferably a cation represented by the following formula (c-II).

The counter anion of the cation represented by the formula (cI), for example, AsF ₆ ^- , SbF ₆ ^- , PF ₆ ^- , and ((C ₆ F ₅ ) ₄ B) ^- , etc. Among them, ((C ₆ F ₅ ) ₄ B) ^- is preferable. Also, "C ₆ F ₅ " means pentafluorophenyl.

As the compound formed of the cation part and the anion part represented by the above-mentioned formula (c-I), commercially available compounds can be used. As a commercial item, for example, CXC-1821 (manufactured by King Industries) and the like.

Preferable specific examples of the compound formed by the cation moiety represented by the formula (cI) and the anion moiety include, for example, the compound formed by the cation moiety represented by the formula (c-II) and AsF ₆ ^- The quaternary ammonium salt of the cation represented by the formula (c-II), the quaternary ammonium salt formed by the cation represented by the formula (c- _II ⁾ , and the quaternary ammonium salt formed by the cation represented by the formula (c-II), and the quaternary ammonium salt formed by the PF ₆ ^- A quaternary ammonium salt, a cation represented by formula (c-II), and a quaternary ammonium salt formed with ((C ₆ F ₅ ) ₄ B) ^- , etc. Among them, the quaternary ammonium salt formed by the cation represented by the formula (c-II) and ((C ₆ F ₅ ) ₄ B) ^- is more preferable.

The cation part which consists of a cation represented by formula (c-I), and the compound which consists of an anion part may be used individually by 1 type, or may be used in combination of 2 or more types.

・Photocationic polymerization initiator (B2-2) The photocationic polymerization initiator (B2-2) is not particularly limited as long as it is a polymerization initiator other than the perjuly salt (B1) used for photocuring the cationically polymerizable curable composition. , and both can be used. Desirable examples of the photocationic polymerization initiator (B2-2) include, for example, iodonium salts and permeic acid salts.

Specific examples of iodonium salts include, for example, diphenyliodonium tetrakis(pentafluorophenyl) borate, diphenyliodonium hexafluorophosphate, diphenyliodonium hexafluoroantimonate, bis(4-nonylphenyl) Fluorophosphate etc.

The photocationic polymerization initiator (B2-2) is preferably a permeic acid salt. Among the percited salts, the percited salt (hereinafter, also referred to as "conium salt (Q)") formed by the cation part formed by the cation represented by the following formula (c1) and the anion part When (B1) is a percited salt having a cation part formed of a cation represented by the following formula (c1), it is preferable to classify the percited salt as a percited salt (B1)). In particular, when cobalt (Q) is contained in the curable composition, the curable composition can be easily cured favorably.

(式(c1)中，R^c1 及R^c2 獨立表示可被鹵素原子所取代的烷基或下述式(c2)所表示之基；R^c1 及R^c2 可相互鍵結並與式中之硫原子共同形成環，R^c3 表示下述式(c3)所表示之基或下述式(c4)所表示之基；A^c1 表示S、O，或Se；其中，R^c1 及R^c2 不同時為可被鹵素原子所取代的烷基)。

(In formula (c1), R ^c1 and R ^c2 independently represent an alkyl group that can be substituted by a halogen atom or a group represented by the following formula (c2); R ^c1 and R ^c2 can be bonded to each other and with the sulfur in the formula Atoms form a ring together, R ^c3 represents the base represented by the following formula (c3) or the base represented by the following formula (c4); A ^c1 represents S, O, or Se; wherein, R ^c1 and R ^c2 are not at the same time an alkyl group which may be substituted by a halogen atom).

(式(c2)中，環Z^c1 表示芳香族烴環；R^c4 表示可被鹵素原子取代之烷基、羥基、烷氧基、烷羰基、烷氧羰基、醯氧基、烷硫基、噻吩基、噻吩羰基、呋喃基、呋喃羰基、硒吩基、硒吩羰基、脂肪族雜環基、烷基亞磺醯基、烷基磺醯基、羥基(聚)伸烷氧基、可被取代的胺基、氰基、硝基，或鹵素原子；m1表示0以上之整數)。

(In the formula (c2), the ring Z ^c1 represents an aromatic hydrocarbon ring; R ^c4 represents an alkyl, hydroxyl, alkoxy, alkylcarbonyl, alkoxycarbonyl, acyloxy, alkylthio, thiophene group that can be substituted by a halogen atom group, thiophenecarbonyl, furyl, furancarbonyl, selenophene, selenophene carbonyl, aliphatic heterocyclic group, alkylsulfinyl, alkylsulfonyl, hydroxy (poly) alkyleneoxy, can be substituted Amino group, cyano group, nitro group, or halogen atom; m1 represents an integer of 0 or more).

(式(c3)中，R^c5 表示羥基、烷氧基、烷羰基、芳羰基、烷氧羰基、芳氧羰基、芳基硫羰基、醯氧基、芳硫基、烷硫基、芳基、雜環基、芳氧基、烷基亞磺醯基、芳基亞磺醯基、烷基磺醯基、芳基磺醯基、羥基(聚)伸烷氧基、可被取代的胺基、氰基、硝基，或可被鹵素原子取代的伸烷基或下述式(c5)所表示之基；R^c6 表示羥基、烷氧基、烷羰基、芳羰基、烷氧羰基、芳氧羰基、芳基硫羰基、醯氧基、芳硫基、烷硫基、芳基、雜環基、芳氧基、烷基亞磺醯基、芳基亞磺醯基、烷基磺醯基、芳基磺醯基、羥基(聚)伸烷氧基、可被取代的胺基、氰基、硝基，或可被鹵素原子取代的烷基或下述式(c6)所表示之基；A^c2 表示單鍵、S、O、亞磺醯基，或羰基；m2表示0或1)。

(In the formula (c3), R ^C5 represents hydroxyl, alkoxy, alkylcarbonyl, arylcarbonyl, alkoxycarbonyl, aryloxycarbonyl, arylthiocarbonyl, acyloxy, arylthio, alkylthio, aryl, Heterocyclic group, aryloxy group, alkylsulfinyl group, arylsulfinyl group, alkylsulfonyl group, arylsulfonyl group, hydroxy(poly)alkylene group, amino group which may be substituted, A cyano group, a nitro group, or an alkylene group which may be substituted by a halogen atom or a group represented by the following formula (c5); R ^c6 represents a hydroxyl group, an alkoxyl group, an alkylcarbonyl group, an arylcarbonyl group, an alkoxycarbonyl group, an aryloxycarbonyl group , arylthiocarbonyl, acyloxy, arylthio, alkylthio, aryl, heterocyclyl, aryloxy, alkylsulfinyl, arylsulfinyl, alkylsulfonyl, aryl Sulfonyl group, hydroxy (poly) alkoxyl group, amino group, cyano group, nitro group that can be substituted, or alkyl group that can be substituted by halogen atom or the group represented by the following formula (c6); A ^c2 Represents a single bond, S, O, sulfinyl, or carbonyl; m2 represents 0 or 1).

(式(c4)中，R^c7 及R^c8 獨立表示羥基、烷氧基、烷羰基、芳羰基、烷氧羰基、芳氧羰基、芳基硫羰基、醯氧基、芳硫基、烷硫基、芳基、雜環基、芳氧基、烷基亞磺醯基、芳基亞磺醯基、烷基磺醯基、芳基磺醯基、羥基(聚)伸烷氧基、可被取代的胺基、氰基、硝基，或可被鹵素原子取代的伸烷基或下述式(c5)所表示之基；R^c9 及R^c10 獨立表示可被鹵素原子取代的烷基或上述式(c2)所表示之基；R^c9 及R^c10 可相互鍵結並與式中之硫原子共同形成環；A^c3 表示單鍵、S、O、亞磺醯基，或羰基；m3表示0或1；其中，R^c9 及R^c10 不同時為可被鹵素原子所取代的烷基)。

(In formula (c4), R ^c7 and R ^c8 independently represent hydroxyl, alkoxyl, alkylcarbonyl, arylcarbonyl, alkoxycarbonyl, aryloxycarbonyl, arylthiocarbonyl, acyloxy, arylthio, alkylthio , aryl, heterocyclyl, aryloxy, alkylsulfinyl, arylsulfinyl, alkylsulfonyl, arylsulfonyl, hydroxy(poly)alkoxyl, can be substituted Amino, cyano, nitro, or alkylene groups that may be substituted by halogen atoms or groups represented by the following formula (c5); R ^c9 and R ^c10 independently represent alkyl groups that may be substituted by halogen atoms or the above formula The base represented by (c2); R ^c9 and R ^c10 can be bonded to each other and form a ring together with the sulfur atom in the formula; A ^c3 represents a single bond, S, O, sulfinyl, or carbonyl; m3 represents 0 or 1; wherein, R ^c9 and R ^c10 are not both alkyl groups that may be substituted by halogen atoms).

(式(c5)中，環Z^c2 表示芳香族烴環；R^c11 表示可被鹵素原子取代的烷基，或羥基、烷氧基、烷羰基、芳羰基、烷氧羰基、芳氧羰基、芳基硫羰基、醯氧基、芳硫基、烷硫基、芳基、雜環基、芳氧基、烷基亞磺醯基、芳基亞磺醯基、烷基磺醯基、芳基磺醯基、羥基(聚)伸烷氧基、可被取代的胺基、氰基、硝基，或鹵素原子；m4表示0以上之整數)。

(式(c6)中，環Z^c3 表示芳香族烴環；R^c12 表示可被鹵素原子取代的烷基，或羥基、烷氧基、烷羰基、芳羰基、烷氧羰基、芳氧羰基、芳基硫羰基、醯氧基、芳硫基、烷硫基、噻吩羰基、呋喃羰基、硒吩羰基、芳基、雜環基、芳氧基、烷基亞磺醯基、芳基亞磺醯基、烷基磺醯基、芳基磺醯基、羥基(聚)伸烷氧基、可被取代的胺基、氰基、硝基，或鹵素原子；m5表示0以上之整數)。

(In the formula (c5), the ring Z ^c2 represents an aromatic hydrocarbon ring; R ^c11 represents an alkyl group that may be substituted by a halogen atom, or a hydroxyl group, an alkoxyl group, an alkylcarbonyl group, an arylcarbonyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an aromatic Alkylthiocarbonyl, acyloxy, arylthio, alkylthio, aryl, heterocyclyl, aryloxy, alkylsulfinyl, arylsulfinyl, alkylsulfonyl, arylsulfonyl Acyl group, hydroxy (poly) alkoxyl group, amino group that may be substituted, cyano group, nitro group, or halogen atom; m4 represents an integer of 0 or more).

(In formula (c6), ring Z ^c3 represents an aromatic hydrocarbon ring; R ^c12 represents an alkyl group that may be substituted by a halogen atom, or a hydroxyl group, an alkoxyl group, an alkylcarbonyl group, an arylcarbonyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an aromatic Alkylthiocarbonyl, acyloxy, arylthio, alkylthio, thiophenecarbonyl, furancarbonyl, selenophenecarbonyl, aryl, heterocyclyl, aryloxy, alkylsulfinyl, arylsulfinyl , alkylsulfonyl group, arylsulfonyl group, hydroxyl (poly)alkoxyl group, amino group that may be substituted, cyano group, nitro group, or a halogen atom; m5 represents an integer of 0 or more).

(Cerium Salt (Q)) Hereinafter, the percite salt (Q) will be described. The cobalt salt (Q) is characterized in that a methyl group is bonded to a carbon atom that is ortho to the carbon atom to which A ^c1 is bonded in the benzene ring in the above formula (c1). When the permeic salt (Q) has a methyl group at the above-mentioned position, it can easily generate protons and improve the sensitivity to active energy rays such as ultraviolet rays, compared with conventional permeic salts.

In the above formula (c1), both R ^c1 and R ^c2 are preferably groups represented by the above formula (c2); and R ^c1 and R ^c2 may be the same or different from each other. In the above formula (c1), when R ^c1 and R ^c2 are bonded to each other and form a ring together with the sulfur atom in the formula, in the formed ring, the number of atoms constituting the ring is preferably 3 or more and 10 or less including the sulfur atom , preferably more than 5 and less than 7. The formed ring may be polycyclic, and those obtained by condensation of 5-7 membered rings are preferred. In the above formula (c1), R ^c1 and R ^c2 are preferably both phenyl groups. In the above formula (c1), R ^c3 is preferably a group represented by the above formula (c3). In the above formula (c1), A ^c1 is preferably S or O, and S is more preferred.

In the above formula (c2), R ^c4 is preferably an alkyl group that may be substituted by a halogen atom, or a hydroxyl group, an alkyl carbonyl group, a thiophene carbonyl group, a furyl carbonyl group, a selenophene carbonyl group, an amino group that may be substituted, or a nitro group, and it is better to use a nitro group that may be substituted. An alkyl group substituted by a halogen atom, or an alkylcarbonyl group, or a thiophenecarbonyl group is preferred. In the above formula (c2), m1 can be appropriately selected according to the type of ring Z ^c1 , for example, it is an integer between 0 and 4; it is preferably an integer between 0 and 3, more preferably it can be 0 or more, An integer of 2 or less.

In above-mentioned formula (c3), R ^C5 is with alkylene; Hydroxyl, the amino group that can be substituted, or the alkylene group substituted by nitro; Or the group represented by above-mentioned formula (c5) is preferably, with above-mentioned formula ( The group represented by c5) is preferable. In above-mentioned formula (c3), R ^C6 is with alkyl; Hydroxyl, the amino group that can be substituted, or the alkyl that is substituted by nitro; Or the group represented by above-mentioned formula (c6) is preferably, with above-mentioned formula (c6) The indicated basis is preferred. In the above formula (c3), A ^c2 is preferably S or O, more preferably S. In the above formula (c3), m2 is preferably 0.

In the above formula (c4), R ^C7 and R ^C8 are independently alkylene groups; hydroxyl groups, amino groups that may be substituted, or alkylene groups substituted by nitro groups; or groups represented by the above formula (a5), The group represented by the above formula (c5) is preferable; R ^c7 and R ^c8 may be the same or different from each other. In the above formula (c4), it is preferable that both R ^c9 and R ^c10 are groups represented by the above formula (c2); R ^c9 and R ^c10 may be the same or different from each other. In the above formula (c4), when R ^c9 and R ^c10 are bonded to each other and form a ring together with the sulfur atom in the formula, in the formed ring, the number of atoms constituting the ring is preferably 3 or more and 10 or less including the sulfur atom , preferably more than 5 and less than 7. The formed ring may be polycyclic, and those obtained by condensation of 5-7 membered rings are preferred. In the above formula (c4), A ^c3 is preferably S or O, more preferably S. In the above formula (c4), m3 is preferably 0.

In the above formula (c5), R ^c11 is preferably an alkyl group that may be substituted by a halogen atom, or a hydroxyl group, an amino group that may be substituted, or a nitro group, and is more preferably an alkyl group that may be substituted by a halogen atom. In the above formula (c5), m4 can be appropriately selected according to the type of ring Z ^c2 , for example, it is an integer between 0 and 4; it is preferably an integer between 0 and 3, more preferably it can be 0 or more, An integer of 2 or less.

In the above formula (c6), R ^c12 is preferably an alkyl group that may be substituted by a halogen atom, or a hydroxyl group, an alkylcarbonyl group, a thiophene carbonyl group, a furan carbonyl group, a selenophene carbonyl group, an amino group that may be substituted, or a nitro group, and may be substituted by An alkyl group substituted with a halogen atom, or an alkylcarbonyl group, or a thiophenecarbonyl group is preferred. In the above formula (c6), m5 can be appropriately selected according to the type of ring ^Zc3 , for example, it is an integer between 0 and 4; it is preferably an integer between 0 and 3, more preferably it can be 0 or more, An integer of 2 or less.

The cation represented by the above formula (c1) can usually form a salt together with the monovalent anion ^X- . X ^- is a monovalent anion corresponding to the acid (HX) produced in the permeic salt (Q) by irradiation with active energy (heat, visible light, ultraviolet rays, electron rays, and X-rays, etc.). X ^- is preferably exemplified by monovalent polyatomic anions, and MY _a ^- , (Rf) _b PF _6-b ^- , R ^x1 _c BY _4-c ^- , R ^x2 SO ₃ ^- , (R ^x2 SO ₂ ) ₃ C ^- , or an anion represented by (R ^x2 SO ₂ ) ₂ N ^- is preferred. In addition, X ^- may also be a halogen anion, for example, fluoride ion, chloride ion, bromide ion, iodide ion and the like.

M represents a phosphorus atom, a boron atom, or an antimony atom. Y represents a halogen atom (preferably a fluorine atom).

Rf represents an alkyl group in which more than 80 mol% of hydrogen atoms are substituted by fluorine atoms (preferably an alkyl group with a carbon number of 1 or more and 8 or less). Alkyl groups that are substituted by fluorine to form Rf include, for example, straight-chain alkyl groups (methyl, ethyl, propyl, butyl, pentyl, and octyl, etc.), branched-chain alkyl groups (isopropyl, isobutyl, etc.) group, sec-butyl group and tert-butyl group, etc.) and cycloalkyl groups (cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl groups, etc.); in Rf, the hydrogen atoms in these alkyl groups are replaced by fluorine atoms The ratio of substitution is preferably at least 80 mol%, more preferably at least 90%, and most preferably at least 100%, based on the number of moles of hydrogen atoms possessed by the orthoalkyl group. When the substitution ratio of the fluorine atoms is within these preferred ranges, the light sensitivity of the cobalt salt (Q) can be improved. Particularly preferred Rf can be, for example, CF ₃ -, CF ₃ CF ₂ ^- , (CF ₃ ) ₂ CF ^- , CF ₃ CF ₂ CF ₂ ^- , CF ₃ CF 2 CF _{2 CF 2 -} ^, (CF ₃ ) ₂ CFCF ₂ ^- , CF ₃ CF ₂ (CF ₃ )CF ^- and (CF ₃ ) ₃ C ^- etc. The b Rfs are independent of each other, so they may be the same or different from each other.

P represents a phosphorus atom, and F represents a fluorine atom.

R ^x1 represents a phenyl group in which at least a part of hydrogen atoms is substituted by an element or an electron-withdrawing group. Examples of these one element include, for example, a halogen atom, a fluorine atom, a chlorine atom, and a bromine atom. The electron withdrawing group includes, for example, a trifluoromethyl group, a nitro group, a cyano group, and the like. Among these, a phenyl group in which at least one hydrogen atom is substituted by a fluorine atom or a trifluoromethyl group is preferable. Since the c pieces of R ^x1 are mutually independent, they may be the same or different from each other.

B represents a boron atom.

R ^x2 represents an alkyl group with 1 to 20 carbon atoms, a fluoroalkyl group with 1 to 20 carbon atoms, or an aryl group with 6 to 20 carbon atoms; the alkyl and fluoroalkyl groups can be Any of linear, branched or cyclic may be used, and the alkyl group, fluoroalkyl group, or aryl group may have no substituent or may have a substituent. The above-mentioned substituents include, for example, a hydroxyl group, an amino group that may be substituted (for example, those exemplified in the description of the above-mentioned formulas (c2) to (c6), etc.), a nitro group, and the like. In addition, the carbon chain in the alkyl group, fluoroalkyl group or aryl group represented by ^Rx2 may have heteroatoms such as oxygen atom, nitrogen atom, sulfur atom and the like. In particular, the carbon chain in the alkyl group or fluoroalkyl group represented by R ^x2 may also have a divalent functional group (for example, an ether bond, a carbonyl bond, an ester bond, an amine bond, an amide bond) , imide bond, sulfonyl bond, sulfonyl amide bond, sulfonyl imide bond, urethane bond, etc.). When the alkyl group, fluoroalkyl group or aryl group represented by R ^x2 has the above-mentioned substituents, heteroatoms, or functional groups, the number of the above-mentioned substituents, heteroatoms, or functional groups may be one or two. The above are also available.

S represents a sulfur atom, O represents an oxygen atom, C represents a carbon atom, and N represents a nitrogen atom. a represents an integer between 4 and 6. b is preferably an integer of 1 to 5, more preferably an integer of 2 to 4; particularly preferably 2 or 3. c is preferably an integer of 1 to 4, more preferably 4.

The anion represented by MY _a ^- includes, for example, an anion represented by SbF ₆ ^- , PF ₆ ^-, or BF ₄ ^- .

Anions represented by (Rf) _b PF _6-b ^- include, for example, (CF ₃ CF ₂ ) ₂ PF ₄ ^- , (CF ₃ CF ₂ ) ₃ PF ₃ ^- , ((CF ₃ ) ₂ CF) ₂ PF ₄ ^- , ((CF ₃ ) ₂ CF) ₃ PF ₃ ^- , (CF ₃ CF ₂ CF ₂ ) ₂ PF ₄ ^- , (CF ₃ CF ₂ CF ₂ ) ₃ PF ₃ ^- , ((CF ₃ ) ₂ CFCF ₂ ) ₂ PF ₄ ^- , ((CF ₃ ) ₂ CFCF ₂ ) ₃ PF ₃ ^- , (CF ₃ CF ₂ CF ₂ CF ₂ ) ₂ PF ₄ ^- or (CF ₃ CF ₂ CF ₂ CF ₂ ) ₃ PF ₃ ^- Represented anions, etc. Among them, (CF ₃ CF ₂ ) ₃ PF ₃ ^- , (CF ₃ CF ₂ CF ₂ ) ₃ PF ₃ ^- , ((CF ₃ ) ₂ CF) ₃ PF ₃ ^- , ((CF ₃ ) ₂ The anion represented by CF) ₂ PF ₄ ^- , ((CF ₃ ) ₂ CFCF ₂ ) ₃ PF ₃ ^- or ((CF ₃ ) ₂ CFCF ₂ ) ₂ PF ₄ ^- is preferable.

Anion represented by R ^x1 _c BY _4-c ^- , preferably R ^x1 _c BY _4-c ^- (wherein, R ^x1 represents benzene in which at least a part of the hydrogen atoms are replaced by halogen atoms or electron-withdrawing groups group; Y represents a halogen atom; c represents an integer of 1 to 4). , for example, ((C ₆ F ₅ ) ₄ B) ^- , (((CF ₃ ) ₂ C ₆ H ₃ ) ₄ B) ^- , ((CF ₃ C ₆ H ₄ ) ₄ B) ^- , ((C ₆ Anion represented by F ₅ ) ₂ BF ₂ ) ^- , (C ₆ F ₅ BF ₃ ) ^- or ((C ₆ H ₃ F ₂ ) ₄ B) ^- , etc. Among these, an anion represented by ((C ₆ F ₅ ) ₄ B) ^- or (((CF ₃ ) ₂ C ₆ H ₃ ) ₄ B) ^- is preferable.

The anion represented by R ^x2 SO ₃ ^- includes, for example, trifluoromethanesulfonic acid anion, pentafluoroethanesulfonic acid anion, heptafluoropropanesulfonic acid anion, nonafluorobutanesulfonic acid anion, pentafluorophenylsulfonic acid anion, p-Toluenesulfonic acid anion, benzenesulfonic acid anion, camphorsulfonic acid anion, methanesulfonic acid anion, ethanesulfonic acid anion, propanesulfonic acid anion, butanesulfonic acid anion, etc. Among these, trifluoromethanesulfonic acid anion, nonafluorobutanesulfonic acid anion, methanesulfonic acid anion, butanesulfonic acid anion, camphorsulfonic acid anion, benzenesulfonic acid anion or p-toluenesulfonic acid anion are used as good.

Anions represented by (R ^x2 SO ₂ ) ₃ C ^- include, for example, (CF ₃ SO ₂ ) ₃ C ^- , (C ₂ F ₅ SO ₂ ) ₃ C ^- , (C ₃ F ₇ SO ₂ ) ₃ C ^- or an anion represented by (C ₄ F ₉ SO ₂ ) ₃ C ^- , etc.

Anion represented by (R ^x2 SO ₂ ) ₂ N ^- , for example, (CF ₃ SO ₂ ) ₂ N ^- , (C ₂ F ₅ SO ₂ ) ₂ N ^- , (C ₃ F ₇ SO ₂ ) ₂ N ^- or an anion represented by (C ₄ F ₉ SO ₂ ) ₂ N ^- and the like.

Monovalent polyatomic anions, except MY _a ^- , (Rf) _b PF _6-b ^- , R ^x1 _c BY _4-c ^- , R ^x2 SO ₃ ^- , (R ^x2 SO ₂ ) ₃ C ^- or (R ^x2 In addition to the anions represented by SO ₂ ) ₂ N ^- , perhalogenate ions (ClO ₄ ^- , BrO ₄ ^-, etc.), halogenated sulfonate ions (FSO ₃ ^- , ClSO ₃ ^-, etc.), sulfate ions (CH ₃ SO ₄ ^- , CF ₃ SO ₄ ^- , HSO ₄ ^-, etc.), carbonate ions (HCO ₃ ^- , CH ₃ CO ₃ ^-, etc.), aluminate ions (AlCl ₄ ^- , AlF ₄ ^-, etc.), hexafluorobismuth ions (BiF ₆ ^- ), carboxylate ions (CH ₃ COO ^- , CF ₃ COO ^- , C ₆ H ₅ COO ^- , CH ₃ ^C ₆ H ₄ COO - , C ₆ F ₅ COO ^- , CF ₃ C ₆ H ₄ COO ^- etc.), aryl borate ion (B(C ₆ H ₅ ) ₄ ^- , CH ₃ CH ₂ CH ₂ CH ₂ B(C ₆ H ₅ ) ₃ ^- etc.), thiocyanate ion (SCN ^- ) and nitrate ion (NO ₃ ^- ) and so on.

Among these X ^- , from the viewpoint of cationic polymerization performance, MY _a ^- , (Rf) _b PF _6-b ^- , R ^x1 _c BY _4-c ^- , and (R ^x2 SO ₂ ) ₃ C ^- are represented The anions of are preferably SbF ₆ ^- , PF ₆ ^- , (CF ₃ CF ₂ ) ₃ PF ₃ ^- , ((C ₆ F ₅ ) ₄ B) ^- , (((CF ₃ ) ₂ C ₆ H ₃ ) ₄ B) ^- , and (CF ₃ SO ₂ ) ₃ C ^- are preferred.

In the above formulas (c2), (c5), and (c6), the aromatic hydrocarbon rings include, for example, benzene rings, condensed polycyclic aromatic hydrocarbon rings [for example, condensed bicyclic hydrocarbon rings (for example, naphthalene rings] etc. C _8-20 condensed bicyclic hydrocarbon ring, preferably C _10-16 condensed bicyclic hydrocarbon ring), condensed tricyclic aromatic hydrocarbon ring (for example, anthracycline, phenanthrene ring, etc.) etc. to 4-ring aromatic hydrocarbon ring] and the like. The aromatic hydrocarbon ring is preferably a benzene ring or a naphthalene ring, more preferably a benzene ring.

In the above formulas (c1) to (c6), the halogen atom is, for example, a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

In above-mentioned formula (c1)～(c6), alkyl group, can enumerate, for example, the straight-chain alkyl group (methyl, ethyl, n-propyl group, n-butyl group, n-butyl group, n -pentyl, n-octyl, n-decyl, n-dodecyl, n-tetradecyl, n-hexadecyl, and n-octadecyl, etc.), with 3 or more carbon atoms , Branched chain alkyl groups below 18 (isopropyl, isobutyl, sec-butyl, tert-butyl, isopentyl, neopentyl, tert-pentyl, isohexyl, and isostearyl, etc. ), and cycloalkyl groups with 3 to 18 carbon atoms (cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, and 4-decylcyclohexyl, etc.), etc. In particular, in the above-mentioned formulas (c1), (c2), and (c4)~(c6), the alkyl group that may be substituted by a halogen atom means an alkyl group and an alkyl group substituted by a halogen atom. The alkyl group substituted by a halogen atom includes, for example, a group in which at least one hydrogen atom in the above-mentioned linear alkyl group, branched chain alkyl group, or cycloalkyl group is replaced by a halogen atom (monofluoromethyl, difluoromethyl, Fluoromethyl, trifluoromethyl, etc.) etc. Among the alkyl groups that may be substituted by halogen atoms, trifluoromethyl is particularly preferred for R ^c1 , R ^c2 , R ^c9 , or R ^c10 , and methyl is preferred for R ^c4 , R ^c6 , R ^c11 , or R ^c12 Excellent.

In the above formulas (c2) to (c6), the alkoxy group can be, for example, a straight chain or branched chain alkoxy group (methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, sec-butoxy, tert-butoxy, hexyloxy, decyloxy, dodecyloxy, and octadecyloxy, etc.) etc.

In the above formulas (c2)~(c6), the alkyl group in the alkylcarbonyl group can include, for example, the above-mentioned straight-chain alkyl groups with 1 to 18 carbon atoms, branched alkyl groups with 3 or more carbon atoms and 18 or less carbon atoms. Alkaline alkyl group, or cycloalkyl group with 3 to 18 carbon atoms, etc.; alkylcarbonyl group, for example, linear, branched or cyclic alkylcarbonyl group with 2 to 18 carbon atoms (Acetyl, propionyl, butyryl, 2-methylpropionyl, heptyl, 2-methylbutyryl, 3-methylbutyryl, octyl, decyl, dodecyl, octadecyl Alkyl, cyclopentyl, and cyclohexyl, etc.) etc.

In the above formulas (c3) to (c6), the arylcarbonyl group includes, for example, an arylcarbonyl group having 7 to 11 carbon atoms (benzoyl, naphthyl, etc.) and the like.

In the above formulas (a2) to (a6), the alkoxycarbonyl group can be, for example, a straight-chain or branched alkoxycarbonyl group (methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, isopropoxycarbonyl, butoxycarbonyl, isobutoxycarbonyl, sec-butoxycarbonyl, tert-butoxycarbonyl, octyloxycarbonyl, tetradecyloxycarbonyl, and octadecyloxycarbonyl, etc.) etc.

In the above formulas (c3) to (c6), the aryloxycarbonyl group includes, for example, an aryloxycarbonyl group having 7 to 11 carbon atoms (phenoxycarbonyl, naphthyloxycarbonyl, etc.) and the like.

In the above formulas (c3) to (c6), the arylthiocarbonyl group includes, for example, arylthiocarbonyl groups having 7 to 11 carbon atoms (phenylthiocarbonyl, naphthyloxythiocarbonyl, etc.) and the like.

In the above formulas (c2)~(c6), the acyloxy group can be, for example, a straight chain or branched acyloxy group (acetyloxy, ethylcarbonyloxy, propaneoxy) with carbon atoms of 2 or more and 19 or less. ylcarbonyloxy, isopropylcarbonyloxy, butylcarbonyloxy, isobutylcarbonyloxy, sec-butylcarbonyloxy, tert-butylcarbonyloxy, octylcarbonyloxy, tetradecane carbonyloxy, and octadecylcarbonyloxy, etc.), etc.

In the above-mentioned formulas (c3)~(c6), the arylthio group can include, for example, an arylthio group (phenylthio, 2-methylphenylthio, 3-methylbenzene) having 6 or more and 20 or less carbon atoms. Thio, 4-methylphenylthio, 2-chlorophenylthio, 3-chlorophenylthio, 4-chlorophenylthio, 2-bromophenylthio, 3-bromophenylthio, 4-bromobenzene Thio, 2-fluorophenylthio, 3-fluorophenylthio, 4-fluorophenylthio, 2-hydroxyphenylthio, 4-hydroxyphenylthio, 2-methoxyphenylthio, 4-methyl Oxyphenylthio, 1-naphthylthio, 2-naphthylthio, 4-[4-(phenylthio)benzoyl]phenylthio, 4-[4-(phenylthio)phenoxy ]phenylthio, 4-[4-(phenylthio)phenyl]phenylthio, 4-(phenylthio)phenylthio, 4-benzoylphenylthio, 4-benzoyl- 2-Chlorophenylthio, 4-benzoyl-3-chlorophenylthio, 4-benzoyl-3-methylthiophenylthio, 4-benzoyl-2-methylthiophenyl Thio, 4-(4-methylthiobenzoyl)phenylthio, 4-(2-methylthiobenzoyl)phenylthio, 4-(p-methylthiobenzoyl)phenyl Thio, 4-(p-ethylbenzoyl)phenylthio, 4-(p-isopropylbenzoyl)phenylthio, and 4-(p-tert-butylbenzoyl) phenylthio, etc.), etc.

In the above formulas (c2) to (c6), the alkylthio group can be, for example, a straight chain or branched chain alkylthio group (methylthio, ethylthio, propylthio, Isopropylthio, butylthio, isobutylthio, sec-butylthio, tert-butylthio, pentylthio, isopentylthio, neopentylthio, tert-pentylthio, octylthio, Decylthio, Dodecylthio, Isoctadecylthio, etc.) etc.

In the above formulas (c3) to (c6), the aryl group includes, for example, an aryl group having 6 to 10 carbon atoms (phenyl, tolyl, xylyl, and naphthyl, etc.) and the like.

In the above formula (c2), the aliphatic heterocyclic group includes, for example, an aliphatic heterocyclic group (pyrrolidine, tetrahydrofuranyl, tetrahydro Thienyl, piperidinyl, tetrahydropyranyl, tetrahydrothiopyranyl, morpholinyl, etc.) and the like.

基、吲哚基、苯併呋喃基、苯併噻吩基、喹啉基、異喹啉基、喹噁啉基、喹唑啉基、咔唑基、吖啶基、酚噻

基、吩

基、呫噸基、噻嗯基、啡噁

基、啡噁噻、苯并2氫哌喃基、異苯并2氫哌喃基、二苯併噻吩基、氧葱酮、硫氧葱酮，及二苯併呋喃基等)等。In the above formulas (c3) to (c6), the heterocyclic group can be, for example, a heterocyclic group with a carbon number of 4 or more and 20 or less (thienyl, furyl, selenyl, pyranyl, pyrrolyl, oxa Azolyl, Thiazolyl, Pyridyl, Pyrimidinyl, Pyridine

Base, indolyl, benzofuryl, benzothienyl, quinolinyl, isoquinolyl, quinoxalinyl, quinazolinyl, carbazolyl, acridyl, phenothiazyl

base, phen

Xanthenyl, Xanthenyl, Thienyl, Phenyloxanthyl

base, phenanthione, benzo2hydropyranyl, isobenzo2hydropyranyl, dibenzothienyl, anthrone, thioxanthone, and dibenzofuryl, etc.) and the like.

In the above formulas (c3) to (c6), the aryloxy group includes, for example, an aryloxy group having 6 to 10 carbon atoms (phenoxy, naphthyloxy, etc.).

In the above-mentioned formulas (c2) to (c6), the alkylsulfinyl group can be, for example, a straight chain or branched chain sulfinyl group (methylsulfinyl, ethyl sulfinyl, propylsulfinyl, isopropylsulfinyl, butylsulfinyl, isobutylsulfinyl, sec-butylsulfinyl, tert-butylsulfinyl Sulfonyl, pentylsulfinyl, isopentylsulfinyl, neopentylsulfinyl, tert-pentylsulfinyl, octylsulfinyl, and isostearylsulfinyl sulfonyl, etc.) etc.

Among the above-mentioned formulas (c3) to (c6), the arylsulfinyl group includes, for example, an arylsulfinyl group (phenylsulfinyl, tolylsulfinyl) having 6 to 10 carbon atoms. Acyl, and naphthylsulfinyl, etc.) etc.

In the above-mentioned formulas (c2) to (c6), the alkylsulfonyl group can be, for example, a straight chain or branched chain alkylsulfonyl group (methylsulfonyl, ethyl, etc.) with a carbon number of 1 to 18. Sulfonyl, propylsulfonyl, isopropylsulfonyl, butylsulfonyl, isobutylsulfonyl, sec-butylsulfonyl, tert-butylsulfonyl, pentylsulfonyl group, isopentylsulfonyl, neopentylsulfonyl, tert-pentylsulfonyl, octylsulfonyl, and octadecylsulfonyl, etc.) etc.

Among the above-mentioned formulas (c3) to (c6), the arylsulfonyl group can be enumerated, for example, an arylsulfonyl group (phenylsulfonyl, tolylsulfonyl (toluenesulfonyl) having a carbon number of 6 or more and 10 or less. sulfonyl), and naphthylsulfonyl, etc.) etc.

In the above formulas (c2)~(c6), the hydroxyl (poly) alkoxyl group can be exemplified, for example, HO(AO) _q- (wherein, AO independently represents ethoxyl and/or propoxyl; q represents a hydroxy (poly)alkyleneoxy group represented by an integer of 1 to 5).

In the above formulas (c2)~(c6), the amino group that can be substituted includes, for example, an amino group (-NH ₂ ) and a substituted amino group with a carbon number of 1 to 15 (methylamino, dimethyl Amine, ethylamino, methylethylamino, diethylamino, n-propylamino, methyl-n-propylamino, ethyl-n-propylamino, n-propylamino, isopropylamino, isopropylmethylamine group, isopropylethylamino group, diisopropylamino group, anilino group, diphenylamino group, methylanilino group, ethylanilino group, n-propylanilino group, and isopropylanilino group, etc.) etc.).

In the above formulas (c3) and (c4), the alkylene group includes, for example, straight or branched chain alkylene groups (methylene, 1,2-ethylene, 1,1-ethylene, propane-1,3-diyl, propane-1,2-diyl, propane-1,1-diyl, propane-2,2-diyl, butane-1,4 -diyl, butane-1,3-diyl, butane-1,2-diyl, butane-1,1-diyl, butane-2,2-diyl, butane-2,3 -diyl, pentane-1,5-diyl, pentane-1,4-diyl, hexane-1,6-diyl, heptane-1,7-diyl, octane-1,8 -diyl, 2-ethylhexane-1,6-diyl, nonane-1,9-diyl, decane-1,10-diyl, undecane-1,11-diyl, deca Diadecane-1,12-diyl, tridecane-1,13-diyl, tetradecane-1,14-diyl, pentadecane-1,15-diyl, and hexadecane-1, 16-dibase, etc.) etc.

Calcite salt (Q), for example, can be synthesized by the following method. Specifically, for example, in 1-fluoro-2-methyl-4-nitrobenzene represented by the following formula (c1-1), in the presence of a base such as potassium hydroxide, the following formula ( The compound represented by c1-2) is reacted to obtain the nitro compound represented by the following formula (c1-3), and then reduced in the presence of reduced iron to obtain the following formula (c1-4 ) The amine compound represented by ). The amine compound is reacted with a nitrite (for example, sodium nitrite) represented by MaNO ₂ (wherein, Ma is a metal atom, for example, an alkali metal atom such as a sodium atom) to obtain a diazo compound, and then , mix the cuprous halide represented by the diazo compound with CuX' (in the formula, X' represents a halogen atom such as a bromine atom, the same below) and the hydrogen halide represented by HX', and react to obtain the following formula: (c1-5) halides. The Grignard reagent is produced from the halide and magnesium, and then, in the presence of trimethylsilyl chloride, the Grignard reagent is reacted with a sulfinyl compound represented by the following formula (c1-6), On the other hand, a permeic salt represented by the following formula (c1-7) can be obtained. In addition, the permeium salt is combined with Mb ⁺ X" ^- (wherein, Mb ⁺ is a metal cation, for example, represents an alkali metal cation such as potassium ion, and X" ^-is a monovalent anion represented by ^X- (wherein, halogen The salt represented by the anion except)) is reacted, and as a result of base exchange, the permeic salt represented by the following formula (c1-8) can be obtained. In addition, in the following formulas (c1-2) to (c-8), R ^c1 to R ^c3 and A ^c1 have the same content as the above formula (c1).

<Method>

Specific examples of the cation portion of the cobaltium salt (Q) are the cations represented by the formula (c1), such as the following. Specific examples of the anion moiety of the cobaltium salt (Q) include those listed in the description of ^X- above, and conventionally known ones. The cation moiety (Q) containing the cation moiety represented by the above formula (c1) can be synthesized according to the above method, and if necessary, the cation moiety can be combined with the desired anion moiety through base exchange reaction, especially with R ^x1 _c BY _4-c ^- (In the formula, R ^x1 represents a phenyl group in which at least a part of the hydrogen atom is replaced by a halogen atom or an electron-withdrawing group, Y represents a halogen atom, and c represents an integer between 1 and 4) A combination of the anions indicated is preferred.

Among the above-mentioned group of preferable cation moieties, the cation moieties represented by the following formula are more preferable.

Other cationic polymerization initiators (B2) may contain other photocationic polymerization initiators other than the above-mentioned columium salt (Q) at the same time. In other cationic polymerization initiators (B2), the content of the cobalt salt (Q) is not particularly limited, and more typically, it is preferably more than 70% by mass, preferably more than 80% by mass, More than 90% by mass is particularly preferred, and 100% by mass is most preferred.

The photocationic polymerization initiator (B2-2) may further contain photocationic polymerization initiators other than the above-mentioned perzium salt (B1) and percite salt (Q) together with the above-mentioned perzium salt (Q). The photocationic polymerization initiators other than the above-mentioned percited salt (B1) and percited salt (Q) are not particularly limited and can be used as long as they are various cationic polymerization initiators conventionally used for cationic polymerization. The photocationic polymerization initiators other than the above-mentioned permeic salt (B1) and permeic salt (Q), as mentioned above, are preferably onium salts such as permeic salt or permeic salt, and other permeic acid salts other than permeic salt (Q) are preferred. Salt is preferred.

Hereinafter, the percited salts of photocationic polymerization initiators other than the above-mentioned percited salts (B1) and percited salts (Q) are also referred to as "concited salts (Q')". The content of the permeic salt (Q') can be the same as that of the permeic salt (Q), and the monovalent anion X ^- preferably contains the above-mentioned R ^x1 _c BY _4-c ^- .

A percited salt (Q') having a monovalent anion represented by R ^x1 _c BY _4-c ^- , for example, a percited salt represented by the following formula (c1').

(式中，R^c1 、R^c2 、R^c3 、A^c1 、R^x1 、Y及c，係如上所述)。

(In the formula, R ^c1 , R ^c2 , R ^c3 , A ^c1 , R ^x1 , Y and c are as described above).

Specific examples of the cation portion of the permeic acid salt (Q') represented by the above formula (c1') are as follows.

Typical examples of the cation part of the permeic acid salt (Q') are as follows.

The content of other cationic polymerization initiators (B2) in the curable composition is not particularly limited as long as the curable composition can be cured favorably. From the viewpoint of making the hardening composition easy to harden well, more typically, the content of other cationic polymerization initiators (B2) is the amount of (A) hardening properties relative to the total amount of (B) cationic polymerization initiators. 100 parts by mass of the compound, preferably 0 to 5 parts by mass, more preferably 0.01 to 3 parts by mass, particularly preferably 0.03 to 2 parts by mass. Also, the content of other cationic polymerization initiators (B2) is preferably not more than 90% by mass, more preferably not more than 70% by mass, and not more than 50% by mass relative to the total amount of the cationic polymerization initiator (B). More preferably, it is especially preferably 30% by mass or less. It is also preferable that the curable composition does not contain other cationic polymerization initiators (B2).

＜Anionic polymerization initiator＞ As the anionic polymerization initiator, an anionic polymerization initiator induced by light or an anionic polymerization initiator induced by heat may be used. For example, when the aforementioned epoxy compound is added to the curable composition together with the anionic polymerization initiator, an anion-curable curable composition can be obtained. Anionic polymerization initiators caused by light are not particularly limited, for example, photoactive carbamates such as triphenyl carbinol, benzyl carbamate and benzamide carbamate; O-amine Amides such as formyl hydroxyamide, O-aminoformyl oxime, aromatic amide, α-lactam and N-(2-allylethylidene)amide and other amides ; Oxime ester compounds, α-aminoacetophenone, cobalt complexes, etc. Among these, 2-nitrobenzylcyclohexylcarbamate, triphenylmethanol, o-aminoformyl hydroxyamide, o-carbamoyl oxime, [[(2,6- Dinitrobenzyl)oxy]carbonyl]cyclohexylamine, bis[[(2-nitrobenzyl)oxy]carbonyl]hexane 1,6-diamine, 4-(methylthiobenzoyl )-1-methyl-1-morpholinoethane, (4-morpholinobenzoyl)-1-benzyl-1-dimethylaminopropane, N-(2-nitrobenzyloxycarbonyl ) pyrrolidine, hexaamine cobalt (III) tris(trityl borate), 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone, etc. are preferred instantiate. Desirable examples other than the above include, for example, compounds decomposed by the action of light (and/or heat) to form imidazole compounds. The anionic polymerization initiator caused by heat is not particularly limited as long as it is a conventionally used compound, for example, 2-benzyl-2-dimethylamino-1-(4-morpholine Other than phenyl)-butan-1-one, another example is amine-epoxy adduct-based thermal anionic polymerization initiator, amine-isocyanate-based compound formed thermal base generator, or dicyanodiamides , hydrazines, or anionic polymeric hardeners such as aromatic diamines, or composite anionic polymeric hardeners formed by different types of hardeners. Amine-epoxy adduct-based thermal anionic polymerization initiators, for example, "Ajicure-PN-23", "Ajicure-PN-40", Ajicure-PN-50", "Ajicure-PN-H" (all Ajinomoto Fine-techno company's product name), "Hardener-X-3661S" (A･C･R company's product name), "Hardener-X-3670S" (A･C･R company's product name), "Novacure -HX-3742" (trade name of Asahi Kasei Co., Ltd.), "Novacure-HX-3721" (trade name of Asahi Kasei Co., Ltd.) and the like. Moreover, the thermal base generator which consists of an amine-isocyanate type compound, for example, "Fujicure-FXE-1000" (trade name of Fuji Chemical Co., Ltd.), "Fujicure-FXR-1030" (trade name of Fuji Chemical Co., Ltd.) and the like. Also, 2-benzyl-2-dimethylamino-1-(4-morpholinephenyl)-butan-1-one functions as an anionic polymerization initiator that can be initiated by the action of light.

The content of the anionic polymerization initiator in the curable composition is not particularly limited as long as it is within the range that does not hinder the object of the present invention. The content of the anionic polymerization initiator in the curable composition is preferably not less than 0.01 parts by mass and not more than 5 parts by mass, and preferably not less than 0.05 parts by mass and not more than 3 parts by mass relative to 100 parts by mass of the (A) curable compound. Preferably, 0.1 mass part or more and 2 mass parts or less are especially preferable.

<(C) Ionic liquids with a melting point of 140°C or less (hereinafter, also referred to simply as "(C) ionic liquids")> (C) The ionic liquid is preferably a salt that melts in a temperature range below 140°C and is a stable salt that is liquid at a temperature below 140°C. (C) The melting point of the ionic liquid is preferably 120°C or lower, more preferably 100°C or lower, and more preferably 80°C or lower from the viewpoint of achieving the effects of the present invention more reliably and from the viewpoint of coatability. When the curable composition contains (S) solvent, the viewpoint of achieving the effect of the present invention more reliably, and the viewpoint of suppressing coatability and foreign matter, etc. The solubility of the (S) solvent and (C) ionic liquid is preferably at least 70% by mass, more preferably at least 80% by mass, and most preferably at least 90% by mass.

In addition, the above-mentioned solubility means that 70 parts by mass, 80 parts by mass, or 90 parts by mass of the (C) ionic liquid is mixed with 100 parts by mass of the (S) solvent contained in the curable composition, and the mixture is mixed by a vibrating machine. When the treatment was performed for 5 minutes, the presence or absence of precipitation was confirmed by visual observation, but the quality at the time of precipitation was not observed. (C) When the ionic liquid is a salt, it can have excellent ion conductivity, and since it is a liquid at a melting point below 140° C., it can be uniformly diffused in the curable composition. In addition, the thermal decomposition temperature is also high. Therefore, in the curable composition, it has low dependence on cationic polymerization or anionic polymerization, and can promote uniform hardening reaction. properties), excellent heat resistance, and a hardened product that also has good adhesion to the substrate.

The above (C) ionic liquid is preferably composed of organic cations and anions. The above-mentioned organic cations constituting the (C) ionic liquid can more reliably achieve the effect of the present invention. From the viewpoint of alkyl chain quaternary ammonium cations, piperidinium cations, pyrimidinium cations, pyrrolidinium salt cations, imidazolium cations , pyridinium cations, pyrazolium cations, guanidinium cations, phosphonium cations, and perium cations are preferably at least one selected from the group consisting of alkyl chain quaternary ammonium cations, piperidinium cations, imidazolium cations or phosphonium A cation is preferred, and an imidazolium cation or a phosphonium cation is more preferred from the viewpoint of yellowing resistance.

Specific examples of the above-mentioned alkyl chain quaternary ammonium cations include, for example, quaternary ammonium cations represented by the following formula (L1), and specifically, tetramethylammonium, ethyltrimethylammonium, Diethyldimethylammonium, triethylmethylammonium, tetraethylammonium, octyltrimethylammonium, hexyltrimethylammonium, methyltrioctylammonium, etc. Specific examples of the above-mentioned piperidinium cations include, for example, piperidinium cations represented by the following formula (L2), and more specifically, 1-propylpiperidinium cations, 1-pentyl Piperidinium cation, 1,1-dimethylpiperidinium cation, 1-methyl-1-ethylpiperidinium cation, 1-methyl-1-propylpiperidinium cation, 1-methyl- 1-butylpiperidinium cation, 1-methyl-1-pentylpiperidinium cation, 1-methyl-1-hexylpiperidinium cation, 1-methyl-1-heptylpiperidinium cation, 1-Ethyl-1-propylpiperidinium cation, 1-ethyl-1-butylpiperidinium cation, 1-ethyl-1-pentylpiperidinium cation, 1-ethyl-1-hexyl Piperidinium cation, 1-ethyl-1-heptylpiperidinium cation, 1,1-dipropylpiperidinium cation, 1-propyl-1-butylpiperidinium cation, 1,1-di Butylpiperidinium cation, etc. Specific examples of the above-mentioned pyrimidinium cations include, for example, 1,3-dimethyl-1,4,5,6-tetrahydropyrimidinium cations, 1,2,3-trimethyl-1,4,5, 6-tetrahydropyrimidinium cation, 1,2,3,4-tetramethyl-1,4,5,6-tetrahydropyrimidinium cation, 1,2,3,5-tetramethyl-1,4, 5,6-tetrahydropyrimidinium cation, 1,3-dimethyl-1,4-dihydropyrimidinium cation, 1,3-dimethyl-1,6-dihydropyrimidinium cation, 1,2, 3-Trimethyl-1,4-dihydropyrimidinium cation, 1,2,3-trimethyl-1,6-dihydropyrimidinium cation, 1,2,3,4-tetramethyl-1, 4-dihydropyrimidinium cation, 1,2,3,4-tetramethyl-1,6-dihydropyrimidinium cation, and the like.

Specific examples of the above-mentioned pyrrolidinium salt cation include, for example, pyrrolidinium salt cations represented by the following formula (L3), and more specifically, 1,1-dimethylpyrrolidinium salt Cation, 1-ethyl-1-methylpyrrolidinium salt cation, 1-methyl-1-propylpyrrolidinium salt cation, 1-methyl-1-butylpyrrolidinium salt cation, 1-methyl Base-1-pentylpyrrolidinium salt cation, 1-methyl-1-hexylpyrrolidinium salt cation, 1-methyl-1-heptylpyrrolidinium salt cation, 1-ethyl-1-propyl Pyrrolidinium salt cation, 1-ethyl-1-butylpyrrolidinium salt cation, 1-ethyl-1-pentylpyrrolidinium salt cation, 1-ethyl-1-hexylpyrrolidinium salt cation, 1-Ethyl-1-heptylpyrrolidinium salt cation, 1,1-dipropylpyrrolidinium salt cation, 1-propyl-1-butylpyrrolidinium salt cation, 1,1-dibutyl Pyrrolidinium salt cation, etc. Specific examples of the above-mentioned imidazolium cations include, for example, imidazolium cations represented by the following formula (L5), and more specifically, 1,3-dimethylimidazolium cations, 1,3- Diethylimidazolium cation, 1-ethyl-3-methylimidazolium cation, 1-propyl-3-methylimidazolium salt ion, 1-butyl-3-methylimidazolium cation, 1-hexyl- 3-methylimidazolium cation, 1-octyl-3-methylimidazolium cation, 1-decyl-3-methylimidazolium cation, 1-dodecyl-3-methylimidazolium cation, 1 -tetradecane-3-methylimidazolium cation, 1,2-dimethyl-3-propylimidazolium cation, 1-ethyl-2,3-dimethylimidazolium cation, 1-butyl- 2,3-dimethylimidazolium cation, 1-hexyl-2,3-dimethylimidazolium cation, and the like. Specific examples of the above-mentioned pyridinium cations include, for example, pyridinium cations represented by the following formula (L6), and more specifically, 1-ethylpyridinium cations, 1-butylpyridinium cations, etc. , 1-hexylpyridinium cation, 1-butyl-3-methylpyridinium cation, 1-butyl-4-methylpyridinium cation, 1-hexyl-3-methylpyridinium cation, 1-butyl -3,4-Dimethylpyridinium cation, etc.

Specific examples of the aforementioned pyrazolium cation include, for example, 1,3-dimethyl-1,4,5,6-tetrahydropyrazolium cation, 1,2,3-trimethyl-1,4, 5,6-tetrahydropyrazolium cation, 1,2,3,4-tetramethyl-1,4,5,6-tetrahydropyrazolium cation, 1,2,3,5-tetramethyl- 1,4,5,6-tetrahydropyrazolium cation, 1,3-dimethyl-1,4-dihydropyrazolium cation, 1,3-dimethyl-1,6-dihydropyrazolium Onium cation, 1,2,3-trimethyl-1,4-dihydropyrazolium cation, 1,2,3-trimethyl-1,6-dihydropyrazolium cation, 1,2,3 , 4-tetramethyl-1,4-dihydropyrazolium cation, 1,2,3,4-tetramethyl-1,6-dihydropyrazolium cation, etc.

Specific examples of the above-mentioned phosphonium cations include, for example, phosphonium cations represented by the following formula (L4), tetraalkylphosphonium cations (for example, tetrabutylphosphonium ions, tributylhexylphosphonium ions, etc.), and the above-mentioned phosphonium cations Specific examples, for example, triacetoium ion, dimethylacetoium ion, triacetoium ion, ethylmethylcerium ion, butyldimethylacetoium ion, 1-methyltetrahydrothiophenium ion, 1-ethyl Tetrahydrothiophenium ion, 1-propyltetrahydrothiophenium ion, 1-butyltetrahydrothiophenium ion, or 1-methyl-[1,4]-sulfurium ion, etc. Among them, the above-mentioned percited cations are preferably tetrahydrothiophenium-based or hexahydrothiopyrylium-based percited cations having a ring structure such as a 5-membered ring or a 6-membered ring. In the ring structure, there may also be Heteroatoms such as oxygen atoms.

上述式(L1)~(L4)中，R^L1 ~R^L4 各自獨立為，碳原子數為1以上、20以下之烷基或R^L7 -O-(CH₂ )_Ln -所表示的烷氧烷基(R^L7 表示甲基或乙基；Ln表示1以上、4以下之整數)。上述式(L5)中，R^L1 ~R^L4 各自獨立為碳原子數為1以上、20以下之烷基或R^L7 -O-(CH₂ )_Ln -所表示的烷氧烷基(R^L7 表示甲基或乙基；Ln表示1以上、4以下之整數)或氫原子。通式(L6)中，R^L1 ~R^L6 各自獨立為碳原子數為1~20之烷基或 R^L7 -O-(CH₂ )_Ln -所表示的烷氧烷基(R^L7 表示甲基或乙基；Ln表示1~4之整數)或氫原子。

In the above formulas (L1) to (L4), R ^L1 to R ^L4 are each independently an alkyl group having 1 to 20 carbon atoms or an alkoxane represented by R ^L7 -O-(CH ₂ ) _Ln - group (R ^L7 represents a methyl group or an ethyl group; Ln represents an integer of 1 to 4). In the above formula (L5), R ^L1 to R ^L4 are each independently an alkyl group with 1 to 20 carbon atoms or an alkoxyalkyl group represented by R ^L7 -O-(CH ₂ ) _Ln - (R ^L7 represents Methyl or ethyl; Ln represents an integer of 1 to 4) or a hydrogen atom. In the general formula (L6), R ^L1 ~ R ^L6 are each independently an alkyl group with 1 to 20 carbon atoms or an alkoxyalkyl group represented by R ^L7 -O-(CH ₂ ) _Ln - (R ^L7 represents methyl or ethyl; Ln represents an integer of 1 to 4) or a hydrogen atom.

The above-mentioned anions constituting the (C) ionic liquid include, for example, organic anions, inorganic anions, etc., and organic anions are preferable in terms of achieving the effect of the present invention. Among the above-mentioned organic anions, from the viewpoint of achieving the effect of the present invention, the anions of carboxylic acid series, N-amido acid ion, acidic amino acid anion, neutral amino acid anion, alkylsulfuric acid series anion, fluorine-containing compound series At least one selected from the group consisting of anion and phenolic anion is preferred, and carboxylic acid anion or N-amido acid ion is more preferred.

Specific examples of the above-mentioned carboxylic acid-based anions include, for example, acetate ion, capric acid ion, 2-pyrrolidone-5-carboxylic acid ion, formic acid ion, α-lipoic acid ion, lactate ion, tartrate ion, hippurate ion, N -Methylhippuric acid ion, etc. Among them, acetate ion, 2-pyrrolidone-5-carboxylic acid ion, formic acid ion, lactate ion, tartrate ion, hippuric acid ion, N-methyl hippuric acid ion are preferred, Acetate ion, N-methylhippurate ion and formate ion are preferred. Specific examples of the above-mentioned N-amide ion, for example, N-benzoylalanine ion, N-acetylphenylalanine ion, aspartic acid ion, glycine ion, N-acetylglycine ion Acid ions, etc. Among them, N-benzoylalanine ion, N-acetylphenylalanine ion, N-acetylglycine ion are preferred, and N-acetylglycine ion is better.

Specific examples of the above-mentioned acidic amino acid anions include, for example, aspartic acid ion, glutamic acid ion, etc. Specific examples of the above-mentioned neutral amino acid anions include, for example, glycine ion, alanine ion, phenylalanine ion, etc. . Specific examples of the above-mentioned alkylsulfate-based anions include, for example, methanesulfonate ions, etc. Specific examples of the above-mentioned fluorine-containing compound-based anions include, for example, trifluoromethanesulfonate ions, hexafluorophosphonate ions, trifluorotris(pentafluoroethyl base) phosphonic acid ion, bis(trifluoromethanesulfonyl)imide ion, trifluoroacetic acid ion, tetrafluoroborate ion, etc., specific examples of the above-mentioned phenolic anions, for example, phenolic ion, 2-methoxyphenolic ion , 2,6-di-tert-butylphenol ion, etc.

Among the above-mentioned inorganic anions, the viewpoint that the effect of the present invention can be reliably achieved is formed by the group consisting of F ^- , Cl ^- , Br ^- , I ^- , BF ₄ ^- , PF ₆ ^- and N(SO ₂ F) ₂ ^- At least one selected is preferred, BF ₄ ^- , PF ₆ ^- or N(SO ₂ F) ₂ ^- is preferred, BF ₄ ^- or PF ₆ ^- is preferred.

The above-mentioned (C) ionic liquid can be prepared, for example, according to the method disclosed in paragraph 0045 of International Publication No. 2014/178254. The above (C) ionic liquids may be used alone or in combination of two or more. The content of the above-mentioned (C) ionic liquid is not particularly limited as long as the effect of the present invention can be achieved. Generally, relative to 100 parts by mass of the hardening compound, it is preferably 0.0001 mass part or more and 1 mass part or less, and 0.001 mass part It is preferably not less than 1 part by mass, more preferably not less than 0.002 part by mass and not more than 0.1 part by mass, and particularly preferably not less than 0.003 part by mass and not more than 0.07 part by mass.

＜(D) Hardening Accelerator＞ The curable composition may contain (D) a curing accelerator. When the curable composition contains (D) a hardening accelerator, in addition to having both refractive index and yellowing resistance, it can also improve the curability of the curable composition, and form a particularly good heat resistance (heat resistance Decomposability), hardened product with adhesion to the substrate.

(D) Hardening accelerators, for example, urea compounds, tertiary amines and their salts, imidazoles and their salts, phosphine compounds and their derivatives, carboxylic acid metal salts or Lewis acids, Brønsted ) acids and their salts, tetraphenyl boron salts, etc.

(D) Preferred specific examples of hardening accelerators include, for example, 1,8-diazabicyclo(5,4,0)undecene-7, triethylenediamine, benzyldimethylamine, triethylenediamine, Ethanolamine, dimethylaminoethanol, and tertiary amines such as tris(dimethylaminomethyl)phenol; 2-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, and 2 - imidazoles such as heptadecyl imidazole; tributylphosphine, methyldiphenylphosphine, triphenylphosphine, diphenylphosphine, and phenylphosphinate and other phosphine compounds; four Phenylphosphonium tetraphenyl borate, triphenylphosphine tetraphenyl borate, 2-ethyl-4-methylimidazolium tetraphenyl borate, and N-methylmorpholine tetraphenyl borate Phenyl boron salt, etc.

Among the (D) hardening accelerators described above, phosphine compounds and their derivatives, and tetraphenyl boron salts are also preferable. Among the above specific examples, triphenylphosphine and triphenylphosphine triphenylborane are preferred.

(D) The usage-amount of a hardening accelerator is not specifically limited as long as it is the range which does not hinder the object of this invention. Generally, the usage amount of (D) hardening accelerator is preferably 0.01 mass parts to 5 mass parts, more preferably 0.05 mass parts to 3 mass parts with respect to 100 mass parts of (A) hardening compound, It is particularly preferably at least 0.1 parts by mass and at most 2 parts by mass.

＜(E) Inorganic filler＞ The curable composition may or may not contain the (E) inorganic filler, and may contain the (E) inorganic filler from the viewpoint of adjusting the refractive index. When the content of (A) curable compound in the curable composition is small, or when the curable composition does not contain (A) curable compound, when the curable composition contains (E) inorganic filler, the refractive index can reach 1.60 or more and 2.20 or less range. (E) Inorganic fillers are preferably metal oxide particles. The metal oxide particles include, for example, metal oxides of at least one selected from aluminum, zirconium, titanate, zinc, indium, tin, antimony, lanthanum, cerium, neodymium, gadolinium, lutetium, hafnium, and tantalum. particles etc. Zirconium, titanate, or cerium oxides are preferred, and titanate oxides or cerium oxides are particularly preferred from the viewpoint of achieving a high refractive index. The shape of these metal oxide particles is not particularly limited, and the average particle diameter is, for example, 200 nm or less, preferably 50 nm or less, more preferably 20 nm or less when measured by dynamic scattering method. The lower limit is not particularly limited, and may be, for example, 0.1 nm or more, or 2 nm or more. (E) The content of the inorganic filler is, for example, not less than 1% by mass and not more than 120% by mass, preferably not less than 3% by mass and not more than 110% by mass, and preferably not more than 5% by mass, in the component after removing the solvent of the curable composition. % or more and 100% by mass or less is preferable.

(phenothiazine)、N-甲基啡噻

、N-乙基啡噻

，及N-苯基啡噻

等的啡噻

化合物；噻噸酮；1-萘酚、2-萘酚、1-甲氧基萘、2-甲氧基萘、1,4-二羥基萘，及4-甲氧基-1-萘酚等的萘化合物；二甲氧基苯乙酮、二乙氧基苯乙酮、2-羥基-2-甲基-1-苯基丙烷-1-酮、4’-異丙基-2-羥基-2-甲基丙醯苯，及4-苯甲醯基-4’-甲基二苯基硫醚等的酮；N-苯基咔唑、N-乙基咔唑、聚-N-乙烯咔唑，及N-縮水甘油咔唑等的咔唑化合物；1,4-二甲氧基1,2-苯併菲及1,4-二-α-甲基苄氧基1,2-苯併菲等的1,2-苯併菲化合物；9-羥基菲、9-甲氧基菲、9-羥基-10-甲氧基菲，及9-羥基-10-乙氧基菲等的菲化合物等。 該些的增感劑，亦可將2種以上組合使用。<(F) sensitizer> The curable composition may contain (F) sensitizer. In the curable composition, when the (B) cationic polymerization initiator contains perium cation and/or odonium cation, the curable composition preferably contains (F) sensitizer. The sensitizer can be used without particular limitation as long as it is a conventionally known sensitizer used in combination with various cationic polymerization initiators. Specific examples of sensitizers, for example, anthracene, 9,10-dibutoxyanthracene, 9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 2-ethyl-9,10- Anthracene compounds such as dimethoxyanthracene and 9,10-dipropoxyanthracene; pyrene; 1,2-benzanthracene; perylene; naphthacene; coronene; thioxanthone, 2-methyl Thioxanthone compounds such as thioxanthone, 2-ethylthioxanthone, 2-chlorothioxanthone, 2-isopropylthioxanthone and 2,4-diethylthioxanthone;

(phenothiazine), N-methylphenothiazine

, N-Ethyl phenanthrene

, and N-phenylphenanthidine

phenanthrene

Compounds; thioxanthone; 1-naphthol, 2-naphthol, 1-methoxynaphthalene, 2-methoxynaphthalene, 1,4-dihydroxynaphthalene, and 4-methoxy-1-naphthol, etc. Naphthalene compounds; dimethoxyacetophenone, diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 4'-isopropyl-2-hydroxy- 2-methylacrylbenzene, and ketones such as 4-benzoyl-4'-methyldiphenylsulfide; N-phenylcarbazole, N-ethylcarbazole, poly-N-vinylcarbazole azoles, and carbazole compounds such as N-glycidyl carbazole; 1,4-dimethoxy 1,2-triphenylene and 1,4-di-α-methylbenzyloxy 1,2-benzo 1,2-triphenylene compounds such as phenanthrene; wait. These sensitizers may be used in combination of two or more.

(F) The usage amount of the sensitizer is not particularly limited. Generally, relative to the mass of (B) cationic polymerization initiator, it is preferably at least 1% by mass and not more than 300% by mass, and it is preferably at least 5% by mass and at least 300% by mass. It is preferably 200% by mass or less. When the (F) sensitizer is used in an amount within this range, desired sensitization can be easily achieved.

＜(G)Antioxidant＞ The curable composition may or may not contain (G) antioxidant, but it is preferable to contain (G) antioxidant from the viewpoint of anti-yellowing property. (G) Antioxidants, such as phenolic compounds, phosphite compounds, thioether compounds, etc., preferably phenolic compounds with a molecular weight of 500 or more, phosphite compounds with a molecular weight of 500 or more, or sulfide compounds with a molecular weight of 500 or more . Also, (G) antioxidant is preferably a phenolic compound, preferably a phenolic compound with a molecular weight of 500 or more.

As the phenolic compound, any phenolic compound known to be used as a phenolic anti-staining agent can be used. Preferable phenol compounds include, for example, hindered phenol compounds and the like. In particular, a compound having a substituent at the position adjacent to the phenolic hydroxyl group (ortho position) is preferable. The aforementioned substituents, for example, are preferably substituted or unsubstituted alkyl groups with 1 to 22 carbon atoms, such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, t-butyl , pentyl, isopentyl, t-pentyl, hexyl, octyl, isooctyl, and 2-ethylhexyl are preferred. Also, a compound having a phenol group and a phosphite group in the same molecule is also preferable.

Phosphite compounds, for example, from tris[2-[[2,4,8,10-tetrakis(1,1-dimethylethyl)dibenzo[d,f][1,3,2]di Dioxaphosphepin-6-yl]oxy]ethyl]amine, tris[2-[(4,6,9,11-tetra-tert-butyldibenzo[d,f] [1,3,2]dioxaphosphoheptan-2-yl)oxy]ethyl]amine, and ethyl phosphite bis(2,4-ditert-butyl-6-methylphenyl) At least one compound selected from the group, etc.

(G) Antioxidant, which can be easily obtained from commercially available products, for example, AdekaSTUB AO-20, AdekaSTUB AO-30, AdekaSTUB AO-40, AdekaSTUB AO-50, AdekaSTUB AO-50F, AdekaSTUB AO-60, AdekaSTUB AO-60G , AdekaSTUB AO-80, AdekaSTUB AO-330, AdekaSTUB PEP-36A, AdekaSTUB AO-412S ((stock) Adeka), etc.

(G) The content of the antioxidant is preferably at least 0.01% by mass and not more than 20% by mass, more preferably at least 0.3% by mass and not more than 15% by mass, in the curable composition after removing the solvent. As the anti-staining agent, only one type may be used, or two or more types may be used. When there are two or more types, the total amount is preferably within the above-mentioned range.

＜Other ingredients＞ The curable composition may contain surfactants, thermal polymerization inhibitors, defoamers, silane coupling agents, colorants (pigments, dyes), resins (thermoplastic resins, alkali-soluble resins, etc.), organic fillers, etc., if necessary additives. Any of the additives can use conventionally known components. Surfactant, for example, anionic, cationic, nonionic compounds, etc., thermal polymerization inhibitor, for example, hydroquinone, hydroquinone monoethyl ether, etc., antifoaming agent, for example, polysiloxane Oxygen-based, fluorine-based compounds, etc.

The curable composition containing essential or optional components described above can form a cured product with excellent refractive index and yellowing resistance, and also has good heat resistance (resistance to thermal decomposition) and adhesion to the substrate, and Suitable for various purposes. The curable composition is particularly suitably used to form a transparent film covering metal wiring or the like in a display element such as a touch panel. Also, when the aforementioned curable composition is used, it is easy to form a cured film that is less likely to be penetrated by gases such as water vapor and less likely to cause yellowing due to long-term exposure. Therefore, the above-mentioned curable composition is also suitable for use as a film formed for the purpose of protection, insulation, etc. in devices equipped with OLEDs, especially in OLED lighting.

＜(S)Solvent＞ The curable composition preferably contains (S) solvent for the purpose of adjusting coatability or viscosity. (S) As a solvent, more typically, an organic solvent is used. The type of organic solvent is not particularly limited as long as it can uniformly dissolve or disperse the components contained in the curable composition.

Preferred examples of organic solvents used as the (S) solvent include, for example, 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 mono Ethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether, propylene glycol mono-n-butyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol mono-n-propyl ether, dipropylene glycol mono -(poly)glycol monoalkyl ethers such as n-butyl ether, tripropylene glycol monomethyl ether, tripropylene glycol monoethyl ether; ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol (poly)glycol monoalkyl ether acetates such as alcohol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate; diethylene glycol Other ethers such as dimethyl ether, diethylene glycol methyl ether, diethylene glycol diethyl ether, tetrahydrofuran, etc.; ketones such as methyl ethyl ketone, cyclohexanone, 2-heptanone, 3-heptanone, etc.; 2-hydroxy Lactate alkyl esters such as methyl propionate and ethyl 2-hydroxypropionate; ethyl 2-hydroxy-2-methylpropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate Ester, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl ethoxyacetate, ethyl glycolate, methyl 2-hydroxy-3-methyl carbonate, 3-methyl Base-3-methoxybutyl acetate, 3-methyl-3-methoxybutyl propionate, ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, Isobutyl acetate, n-pentyl formate, isoamyl acetate, n-butyl propionate, ethyl butyrate, n-propyl butyrate, isopropyl butyrate, n-butyl butyrate, pyruvic acid Other esters such as methyl ester, ethyl pyruvate, n-propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, and ethyl 2-oxabutyrate; aromatics such as toluene and xylene Hydrocarbons; Amides such as N-methylpyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide, etc. These organic solvents may be used alone or in combination of two or more.

In the curable composition, the amount of (S) solvent used is not particularly limited. From the viewpoint of the coatability of the curable composition, etc., the amount of the (S) solvent used is, for example, 30 mass % or more and 99.9 mass % or less, preferably 50 mass % or more and 98 mass % with respect to the entire curable composition. %the following.

＜Cured film＞ The cured film formed from the cured product of the curable composition described above has excellent refractive index and yellowing resistance, and also has excellent heat resistance and adhesion to the substrate. The thickness of the cured film is not particularly limited. Generally, it is better to be above 10nm and below 50μm; good. The cured film is, for example, very suitable for use in sealing materials for OLED display elements, OLED lighting, hard coating, insulating films, antireflection films, interlayer insulating films, carbon hard masks, display panel materials (planarizing films, color filters, etc.) Pixels of devices, partitions for organic EL, spacers), optical components (lenses, microscopes, wafer-level lenses, optical fibers, optical waveguides, thin films, full-phase diagrams, high-refractive films, retro-reflective films), etc. Various uses. Moreover, the cured film has excellent flexibility and is not easy to crack, so it is suitable for use in flexible display panels or flexible lighting. Moreover, a cured film is used especially suitably as a transparent coating film which covers metal wiring etc. in display elements, such as a touch panel.

≪Manufacturing method of curable composition≫ The curable composition can be prepared by uniformly mixing the ingredients described above in a specific ratio. As a mixing device used for producing the curable composition, for example, a Nihon roll or a Sanhon roll, etc. are mentioned. When the viscosity of the hardening composition is extremely low, if necessary, for the purpose of removing insoluble foreign matter, etc., the hardening composition can also be filtered using a filter having openings of a desired size.

≪Manufacturing method of hardened product≫ The method for producing the cured product is not particularly limited as long as it can cure and mold the curable composition into a desired shape. The curing method is not particularly limited as long as it is a method capable of curing the curable composition, and includes, for example, exposure and/or heating, preferably including exposure.

The shape of the molded body is not particularly limited, and it is generally possible to uniformly apply heat to the molded body, or to uniformly irradiate the molded body with exposure light, and a film (thin film) is preferred.

A typical example of the method of producing a cured film from a cured product will be described below. First, a curable composition is applied on a substrate such as a glass substrate to form a coating film. Coating method, for example, a contact transfer type coating device such as a roll coating, a reverse coater (reverse coater), a rod coater, or a spin coater (rotary coating device), Methods such as non-contact coating devices such as slot coaters and curtain coaters. Also, after adjusting the viscosity of the curable composition to an appropriate range, the curable composition can be applied by printing methods such as inkjet method and screen printing method, and then patterned according to the desired shape ( Patterning) obtained coating film.

Next, if necessary, volatile components such as the (S) solvent may be removed, and the coating film may be dried. The drying method is not particularly limited. For example, a vacuum drying device (VCD) can be used to dry under reduced pressure at room temperature, and then, using a heating plate, the temperature is above 80°C and below 120°C, preferably above 90°C. , The method of drying at a temperature of 100°C or less within a time range of 60 seconds or more and 120 seconds or less, etc. After the coating film is formed in this way, at least one of exposure and heating is applied to the coating film. Exposure is to irradiate active energy rays such as excimer laser light. The amount of energy ray to be irradiated varies depending on the composition of the curable composition. Generally, for example, it is better to be above 30mJ/cm ² and below 2000mJ/cm ² , and to be above 50mJ/cm ² and below 500mJ/cm ² . good. The heating temperature is not particularly limited, but it is preferably 180°C to 280°C, more preferably 200°C to 260°C, and particularly preferably 220°C to 250°C. More typically, the heating time is preferably from 1 minute to 60 minutes, preferably from 10 minutes to 50 minutes, and particularly preferably from 20 minutes to 40 minutes.

The cured product formed in the above manner, especially the cured film, is suitable for the various purposes mentioned above.

[Example]

Hereinafter, the present invention will be specifically described using examples, but the scope of the present invention is not limited by these examples.

EXAMPLES 1-17 AND COMPARATIVE EXAMPLES 1-3 In an Example and a comparative example, (A) curable compound ((A) component) used the compound A1-A3 represented by the following formula.

In Examples and Comparative Examples, compounds B1 and B2 represented by the following formulas were used as (B) cationic polymerization initiator ((B) component).

In the examples, (C) ionic liquid ((C) component) used the following C1-C5. C1: N-butyl-N-methylpiperidinium tetrafluoroborate C2: N-methyl-N-propylpiperidinium tetrafluoroborate C3: 1-ethyl-3-methylimidazolium tetrafluoroborate C4: N-acetylglycine tetrabutylphosphonium salt C5: 1-ethyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide

In the examples, (D) the curing accelerator ((D) component) used triphenylphosphinetriphenylborane.

Dissolve (A) and (B) components of the type and amount described in Table 1, and (C) and (D) components of the amount described in Table 1 in propylene glycol so that the solid content concentration is 22% by mass. Monomethyl ether acetate was used to prepare the curable compositions of the Examples and Comparative Examples.

Using the obtained curable composition, evaluate the refractive index, yellowing resistance, adhesion and heat resistance of the cured film according to the following methods. These evaluation results are described in Table 1.

<Evaluation of Refractive Index> Each curable composition was coated on a glass substrate using a spin coater, prebaked at 100°C for 120 seconds, and exposed with an exposure dose of 100mJ/ ^cm2 using a UV curing machine (broadband ) and post-exposure baking at 230° C. for 20 minutes to obtain a cured film with a film thickness of about 1 μm. For each cured film, the refractive index at a wavelength of 550 nm was measured, and evaluated according to the following criteria. ◎: Refractive index is 1.65 or more ○: Refractive index is less than 1.65 and is 1.60 or more ×: Refractive index is less than 1.60

＜Evaluation of yellowing resistance＞ According to the same method as the evaluation of the refractive index, after sintering the cured film formed on the substrate at 250°C for 3 hours, measure the transmittance at a wavelength of 380nm with a UV-visible spectrophotometer, and evaluate according to the following criteria. ◎: Penetration rate above 90% 〇: Penetration rate is less than 90% and more than 85% ×: The penetration rate is less than 85%

＜Adhesion evaluation＞ According to the same method as the evaluation of the refractive index, the cured film formed on the substrate is cross-cut (cut into a grid shape with a width of 1 mm), and the adhesive tape test specified in JIS Z 1522 is used to confirm whether the cured film is peeled off. . When no peeling phenomenon occurred at all, it was rated as "◎", when the number of peeled holes was less than 5%, it was rated as "○", and when the number of peeled holes exceeded 5%, it was rated as "×".

＜Heat Resistance Evaluation＞ A cured film was formed on the substrate in the same manner as for the evaluation of the refractive index. A part of the formed cured film was peeled off from the board|substrate, and it was set as a sample. Thermogravimetric analysis (TGDTA) in air was performed using the obtained sample, and the heat resistance was evaluated. For thermogravimetric analysis, heating was performed at a rate of 10°C/min from room temperature (20°C). Based on the weight at the beginning of the analysis, the temperature at which the weight decreases by 5% is measured (Td5%: temperature at which the weight decreases by 5%). When Td5% is 430°C or higher, it is rated as "◎", when Td5% is 400°C or higher but less than 430°C, it is rated as "○", and when Td5% is less than 400°C, it is rated as "×".

From the results shown in Table 1, it was confirmed that the curable compositions of Examples 1 to 17 containing ionic liquids can form cured films having both refractive index and yellowing resistance. In addition, among the cured films after the above yellowing resistance evaluation, the cured films obtained from the curable compositions of Examples 1-17 were colorless and transparent in appearance, which were weaker than the cured films of Comparative Examples 1-3. yellow tint. Moreover, both the adhesiveness to a board|substrate and heat resistance (pyrolysis resistance) were favorable. In particular, Examples 4, 5, and 7 to 17 in which imidazolium salt or N-acetylglycinate phosphonium salt was used as the ionic liquid tended to have particularly excellent yellowing resistance.

On the other hand, in the curable compositions of Comparative Examples 1 to 3, it was confirmed that the effects of both refractive index and yellowing resistance (especially yellowing resistance) could not be achieved. Also, from the comparison of Example 2 and Comparative Example 1, it can be known that the inclusion of ionic liquid can indeed improve the yellowing resistance.

Claims (12)

A curable composition, which is a cation-curable or anion-curable curable composition, characterized by containing: a functional group containing at least one element selected from the group consisting of N, O, S and Si (A) hardening compound, and (C) an ionic liquid with a melting point of 140°C or less, and the aforementioned (A) hardening compound contains an aromatic group, three

At least one selected from the group consisting of a ring structure, an isocyanuric acid ring structure, and a cyclic siloxane structure. has three

At least one member of the group consisting of a polymer having a ring structure, a compound represented by the following formula (a1-I), and a silicone epoxy compound represented by the following formula (a1-III); constituting the aforementioned (C) ionic liquid The combination of organic cations and anions is piperidinium cations and fluorine-containing compound anions, or imidazolium cations and fluorine-containing compound anions, and the aforementioned piperidinium cations are selected from 1-propylpiperidinium cations, 1- Pentylpiperidinium cation, 1,1-dimethylpiperidinium cation, 1-methyl-1-ethylpiperidinium cation, 1-methyl-1-butylpiperidinium cation, 1-methylpiperidinium cation Base-1-pentylpiperidinium cation, 1-methyl-1-hexylpiperidinium cation, 1-methyl-1-heptylpiperidinium cation, 1-ethyl-1-propylpiperidinium Cation, 1-ethyl-1-butylpiperidinium cation, 1-ethyl-1-pentylpiperidinium cation, 1-ethyl-1-hexylpiperidinium cation, 1-ethyl-1- At least 1. The aforementioned imidazolium cation is selected from 1,3-dimethylimidazolium cation, 1,3-diethylimidazolium cation, 1-ethyl-3-methylimidazolium cation, 1-propyl- 3-methylimidazolium ion, 1-hexyl-3-methylimidazolium cation, 1-octyl-3-methylimidazolium cation, 1-decyl-3-methylimidazolium cation, 1-dodecyl Alkyl-3-methylimidazolium cation, 1-tetradecyl-3-methylimidazolium cation, 1,2-dimethyl-3-propylimidazolium cation, 1-ethyl-2,3 -at least one group of dimethylimidazolium cation, 1-butyl-2,3-dimethylimidazolium cation, and 1-hexyl-2,3-dimethylimidazolium cation,

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

In the formula (a2), the ring Z represents an aromatic hydrocarbon ring; X represents a single bond or a group represented by -S-; R ⁰¹ represents a single bond, an alkylene group with a carbon number of 1 or more and 4 or less, or a carbon atom An alkoxyl group whose number is more than 1 and less than 4; when R ⁰¹ is an alkoxyl group, the oxygen atom in the alkoxyl group is bonded to the ring Z; R ⁰² represents a monovalent hydrocarbon group, a hydroxyl group, or -OR ^4a The group shown, the group shown by -SR ^4b , the acyl group, the alkoxycarbonyl group, the halogen atom, the nitro group, the cyano group, the mercapto group, the carboxyl group, the amino group, the carbamoyl group, the group shown by -NHR ^4c , A group represented by -N(R ^4d ) ₂ , a sulfonic acid group; or a monovalent hydrocarbon group, a group represented by -OR ^4a , a group represented by -SR ^4b , an acyl group, an alkoxycarbonyl group, or -NHR ^4c or at least a part of the hydrogen atoms bonded to the carbon atoms contained in the group represented ^by -N(R ^4d ) 2 is monovalent hydrocarbon group, hydroxyl, the group represented by -OR _4a , -SR ^4b The group shown, acyl group, alkoxycarbonyl group, halogen atom, nitro group, cyano group, mercapto group, carboxyl group, amino group, carbamoyl group, the group shown in -NHR ^4c , -N(R ^4d ) ₂ The base shown, methanesulfonyloxy group, or a base substituted by a sulfonic acid group; R ^4a ~ R ^4d independently represent a monovalent hydrocarbon group; m represents an integer of 0 or more; R ⁰³ is a hydrogen atom, vinyl, thiopyran ( thiirane)-2-methyl, or glycidyl, does not have the situation that R ⁰³ of both W ¹ and W ² is a hydrogen atom; ring Y ¹ and ring Y ² represent the same or different aromatic hydrocarbon rings; R represents A single bond, a methylene group that may have a substituent, an ethylylene group that may have a substituent and may contain a heteroatom between two carbon atoms, a group represented by -O-, a group represented by -NH-, or - The group represented by S-; R ^3a and R ^3b independently represent a cyano group, a halogen atom, or a monovalent hydrocarbon group; n1 and n2 independently represent an integer of 0 or more and 4 or less)

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

(In the formula (a1-III), R ^a24 and R ^a25 represent a monovalent base or an alkyl group containing an epoxy group; but, in the compound represented by the formula (a1-III), x1 R ^a24 and x1 R In ^a25 , at least two are monovalent groups containing epoxy groups; and x1 in formula (a1-III) represents an integer of 3 or more; in the compound represented by formula (a1-III), R ^a24 , R ^a25 may be the same or different, plural R ^a24 may be the same or different, and plural R ^a25 may be the same or different). The curable composition according to claim 1, wherein the content of the (C) ionic liquid is not less than 0.001 part by mass and not more than 1 part by mass relative to 100 parts by mass of the curable compound. The curable composition according to claim 1 or 2, wherein the curable composition can provide a cured film having a refractive index of 1.60 to 2.20 with respect to light having a wavelength of 550 nm. The curable composition according to claim 1, which further contains (B) a cationic polymerization initiator. The curable composition according to claim 4, wherein the cationic polymerization initiator (B) is a percited salt composed of a cationic part and an anionic part, and the anionic part is an anion represented by the following formula (b1) (B1);

(In formula (b1), R ^b1 , R ^b2 , R ^b3 , and R ^b4 are each independently a hydrocarbon group or a heterocyclic group that may have a substituent, and at least one of R ^b1 , R ^b2 , R ^b3 , and R ^b4 may be Aromatic hydrocarbon groups with substituents). The curable composition according to claim 4, wherein the cationic polymerization initiator (B) contains another cationic polymerization initiator (B2) different from the permalium salt (B1). The curable composition according to claim 5 or 6, wherein the above-mentioned cobaltium salt (B1), and/or the above-mentioned other cationic polymerization initiator (B2) is composed of a cationic part and an anionic part, and the aforementioned cationic Part is a cation salt represented by the following formula (c1);

(In formula (c1), R ^c1 and R ^c2 independently represent an alkyl group that may be substituted by a halogen atom or a group represented by the following formula (c2); R ^c1 and R ^c2 may be bonded to each other and with the sulfur atom in the formula Together form a ring; R ^c3 represents the group represented by the following formula (c3) or the group represented by the following formula (c4); A ^c1 represents S, O, or Se; wherein, R ^c1 and R ^c2 are not optional Alkyl group substituted by halogen atom)

(In the formula (c2), the ring Z ^c1 represents an aromatic hydrocarbon ring; R ^c4 represents an alkyl, hydroxyl, alkoxy, alkylcarbonyl, alkoxycarbonyl, acyloxy, alkylthio, thiophene group that can be substituted by a halogen atom group, thiophenecarbonyl, furyl, furancarbonyl, selenophene, selenophene carbonyl, heterocyclic aliphatic hydrocarbon group, alkylsulfinyl, alkylsulfonyl, hydroxyl (poly) alkyleneoxy, can be Substituted amino group, cyano group, nitro group, or halogen atom; m1 represents an integer of 0 or more)

(In the formula (c3), R ^C5 represents hydroxyl, alkoxy, alkylcarbonyl, arylcarbonyl, alkoxycarbonyl, aryloxycarbonyl, arylthiocarbonyl, acyloxy, arylthio, alkylthio, aryl, Heterocyclic hydrocarbon group, aryloxy group, alkylsulfinyl group, arylsulfinyl group, alkylsulfonyl group, arylsulfonyl group, hydroxy(poly)alkyleneoxy group, amino group which may be substituted , cyano, nitro, or an alkylene group which may be substituted by a halogen atom or a group represented by the following formula ( ^c5 ); Carbonyl, arylthiocarbonyl, acyloxy, arylthio, alkylthio, aryl, heterocyclic hydrocarbon, aryloxy, alkylsulfinyl, arylsulfinyl, alkylsulfonyl , arylsulfonyl group, hydroxy (poly) alkoxyl group, amino group that may be substituted, cyano group, nitro group or alkyl group that may be substituted by halogen atom, or a group represented by the following formula (c6); A ^c2 represents a single bond, S, O, sulfinyl, or carbonyl; m2 represents 0 or 1)

(In formula (c4), R ^c7 and R ^c8 independently represent hydroxyl, alkoxyl, alkylcarbonyl, arylcarbonyl, alkoxycarbonyl, aryloxycarbonyl, arylthiocarbonyl, acyloxy, arylthio, alkylthio , aryl, heterocyclic hydrocarbon group, aryloxy group, alkylsulfinyl group, arylsulfinyl group, alkylsulfonyl group, arylsulfonyl group, hydroxyl (poly) alkoxyl group, can be Substituted amino, cyano, nitro or alkylene groups that may be substituted by halogen atoms, or groups represented by the following formula (c5); R ^c9 and R ^c10 independently represent alkyl groups that may be substituted by halogen atoms, or The base represented by the above formula (c2); R ^c9 and R ^c10 can be bonded to each other and form a ring with the sulfur atom in the formula; A ^c3 represents a single bond, S, O, sulfinyl, or carbonyl; m3 represents 0 or 1; wherein, R ^c9 and R ^c10 are not simultaneously alkyl groups that may be substituted by halogen atoms)

(In the formula (c5), the ring Z ^c2 represents an aromatic hydrocarbon ring; R ^c11 represents an alkyl group, a hydroxyl group, an alkoxyl group, an alkylcarbonyl group, an aryl carbonyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an aryl group which may be substituted by a halogen atom Thiocarbonyl, acyloxy, arylthio, alkylthio, aryl, heterocyclic hydrocarbon, aryloxy, alkylsulfinyl, arylsulfinyl, alkylsulfonyl, arylsulfonyl Acyl group, hydroxy (poly) alkoxyl group, amino group, cyano group, nitro group, or halogen atom that can be substituted; m4 represents an integer of 0 or more)

(In the formula (c6), the ring Z ^c3 represents an aromatic hydrocarbon ring; R ^c12 represents an alkyl, hydroxyl, alkoxy, alkylcarbonyl, arylcarbonyl, alkoxycarbonyl, aryloxycarbonyl, aryl that can be substituted by a halogen atom Thiocarbonyl, acyloxy, arylthio, alkylthio, thiophenecarbonyl, furancarbonyl, selenophenecarbonyl, aryl, heterocyclic hydrocarbon group, aryloxy, alkylsulfinyl, arylsulfinyl , alkylsulfonyl group, arylsulfonyl group, hydroxyl (poly)alkoxyl group, amino group that may be substituted, cyano group, nitro group, or a halogen atom; m5 represents an integer of 0 or more). The curable composition according to claim 7, wherein the aforementioned R ^c1 and the aforementioned R ^c2 in the aforementioned formula (c1) are both phenyl groups. The curable composition according to claim 7, wherein the aforementioned A ^c1 in the aforementioned formula (c1) is S. A cured film characterized by being formed of a cured product of the curable composition according to any one of claims 1 to 9. A method for producing a cured product, characterized by comprising: a step of molding the curable composition according to any one of claims 1 to 9 into a specific shape, heating and exposing the curable composition after molding, Or the steps of exposure and heating. The method for producing a cured product according to claim 11, wherein the curable composition is molded to form a coating film, and at least one of exposure and heating is performed on the coating film.