KR102376062B1 - Curable Compositions Comprising Vinyl Group-Containing Compound - Google Patents

Abstract

The present invention provides a curable composition containing a compound containing a vinyl group in the form of a vinyloxy group or the like, and imparting a cured film excellent in solvent resistance and heat resistance by curing.
The curable composition which concerns on this invention contains the vinyl group containing compound represented by following formula (1), and an electron pair donating compound. In formula (1), W ¹ and W ² are a group represented by the following formula (2), a hydroxyl group or a (meth)acryloyloxy group, ring Y ¹ and ring Y ² are an aromatic hydrocarbon ring, R is a single bond or a specific A divalent group, R ^3a and R ^3b independently represent a cyano group, a halogen atom or a monovalent hydrocarbon group, and n1 and n2 represent an integer of 0-4. In the formula (2), ring Z is an aromatic hydrocarbon ring, X is a single bond or a group represented by -S-, R ¹ is a single bond or an alkylene group having 1 to 4 carbon atoms, R ² is a monovalent hydrocarbon group A substituent and m represent an integer of 0 or more.

Description

Curable composition containing a vinyl group-containing compound {Curable Compositions Comprising Vinyl Group-Containing Compound}

The present invention relates to a curable composition containing a vinyl group-containing compound, and a cured film made of a cured product thereof.

Condensed polycyclic compounds have various excellent functions and are used for various purposes. For example, a compound having a fluorene skeleton (9,9-bisphenylfluorene skeleton, etc.), which is a condensed polycyclic aromatic compound, has an excellent function in optical properties such as light transmittance and refractive index, and thermal properties such as heat resistance. is known Therefore, compounds having a fluorene skeleton are used as raw materials for optical members such as lenses, prisms, filters, image display materials, substrates for optical disks, optical fibers, optical waveguides, packaging materials, films, and coating materials. As a compound which has such a fluorene skeleton, what is disclosed by patent document 1 is mentioned, for example.

In the condensed polycyclic compound, in particular, a compound containing a vinyl group in the form of a vinyloxy group or the like is conventionally used as a component of a curable composition together with an alicyclic ether group-containing compound. For example, in patent document 2, the curable composition containing cationically polymerizable unsaturated vinyl compounds, such as a divinyl ether compound, and an epoxy compound is described.

However, the cured film obtained from the curable composition containing the conventional vinyl group containing compound described in patent document 2 was inferior in solvent resistance and heat resistance.

Japanese Patent Laid-Open No. 2011-201791 Japanese Patent Application Laid-Open No. 6-298912

The present invention has been made in view of the above-described problems, and a curable composition containing a compound containing a vinyl group in the form of a vinyloxy group or the like and imparting a cured film excellent in solvent resistance and heat resistance by curing, and a cured product thereof An object of the present invention is to provide a cured film comprising

MEANS TO SOLVE THE PROBLEM In order to solve the subject mentioned above, the present inventors repeated earnest examination. As a result, it was discovered that a cured film excellent in solvent resistance and heat resistance was obtained by using a composition containing a novel vinyl group-containing condensed polycyclic compound and an electron pair donating compound, and the present invention was completed. Specifically, the present invention provides the following.

A first aspect of the present invention is a curable composition containing a vinyl group-containing compound represented by the following general formula (1) and an electron pair donating compound.

(Wherein, W ¹ and W ² independently represent a group represented by the following general formula (2), a hydroxyl group, or a (meth)acryloyloxy group, provided that W ¹ and W ² are not simultaneously a hydroxyl group, and the ring Y ¹ and ring Y ² represents the same or different aromatic hydrocarbon ring, R represents a single bond, a methylene group which may have a substituent, an ethylene group which may have a substituent and may contain a hetero atom between two carbon atoms, -O represents a group represented by -, 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 are independently 0 to Represents an integer of 4.)

(Wherein, ring Z represents an aromatic hydrocarbon ring, X represents a single bond or a group represented by -S-, R ¹ represents a single bond or an alkylene group having 1 to 4 carbon atoms, R ² 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, a group represented by -NHR ^4c , - A group represented by N(R ^4d ) ₂ , a (meth)acryloyloxy group, a sulfo group or a monovalent hydrocarbon group, a group represented by -OR ^4a , a group represented by -SR ^4b , an acyl group, an alkoxycarbonyl group, or -NHR ^4c At least a part of hydrogen atoms bonded to carbon atoms contained in the group represented by the group represented by -N(R ^4d ) ₂ is a monovalent hydrocarbon group, a hydroxyl group, a group represented by -OR ^4a , a group represented by -SR ^4b , an acyl group, Alkoxycarbonyl group, halogen atom, nitro group, cyano group, mercapto group, carboxyl group, amino group, carbamoyl group, group represented by -NHR ^4c , group represented by -N(R ^4d ) ₂ , (meth)acryloyloxy group, mesyl group represents a group substituted with an oxy group or a sulfo group, R ^4a to R ^4d independently represent a monovalent hydrocarbon group, and m represents an integer of 0 or more.)

A 2nd aspect of this invention is a cured film which consists of hardened|cured material of the above-mentioned curable composition.

ADVANTAGE OF THE INVENTION According to this invention, while containing the compound containing a vinyl group in the form of a vinyloxy group etc., the curable composition which provides the cured film excellent in solvent resistance and heat resistance by hardening, and the cured film which consists of the cured film can be provided.

EMBODIMENT OF THE INVENTION Hereinafter, specific embodiment of this invention is described. In addition, this invention is not limited to the following embodiment, Various changes are possible in the range which does not change the summary of this invention.

≪1. Curable composition≫

The curable composition which concerns on this invention is a curable composition containing the vinyl group containing compound represented by following General formula (1), and an electron pair donating compound.

According to the curable composition containing such a vinyl group containing compound and an electron pair donating compound, the cured film which consists of a hardened|cured material obtained using this will have the outstanding heat resistance and solvent resistance. Hereinafter, each component of the curable composition which concerns on this invention is demonstrated in detail.

<Vinyl group-containing compound>

[About the vinyl group-containing compound represented by the general formula (1)]

As mentioned above, the curable composition which concerns on this invention contains the vinyl group containing compound represented by the said General formula (1). These vinyl group-containing compounds can be used individually by 1 type or in combination of 2 or more type.

With respect to this vinyl group-containing compound, W ¹ and W ² in the general formula (1) independently represent a group represented by the following general formula (2), a hydroxyl group, or a (meth)acryloyloxy group. However, W ¹ and W ² are not hydroxyl groups at the same time. It is preferable that at least one of W ¹ and W ² is a group represented by the following general formula (2), and it is more preferable that both W ¹ and W ² are groups represented by the following general formula (2). In addition, in this specification, "(meth)acryloyloxy group" means both an acryloyloxy group and a methacryloyloxy group.

Here, the ring Z of the said General formula (2) represents an aromatic hydrocarbon ring. Specifically, as ring Z, 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, preferably is a C _10-16 condensed bicyclic hydrocarbon ring) and a condensed bicyclic aromatic hydrocarbon ring such as a condensed tricyclic aromatic hydrocarbon ring (eg, anthracene ring, phenanthrene ring, etc.)] and the like. Moreover, it is preferable that ring Z is a benzene ring or a naphthalene ring.

In addition, when both W ¹ and W ² in the general formula (1) are groups represented by the general formula (2), the ring Z contained in W ¹ and the ring Z contained in W ² may be the same or different. , for example, one ring may be a benzene ring, and the other ring may be a naphthalene ring. Moreover, the substitution position of the ring Z couple|bonded through X to the carbon atom which both W< ¹ > and W< ² > is directly connected with is not specifically limited. For example, when ring Z is a naphthalene ring, the group corresponding to the ring Z bonded to the carbon atom may be a 1-naphthyl group, a 2-naphthyl group, or the like.

In the general formula (2), X independently represents a single bond or a group represented by -S-, and is typically a single bond.

In the general formula (2), R ¹ represents a single bond or an alkylene group having 1 to 4 carbon atoms. Specifically, R ¹ is a single bond; and C1-C4 alkylene groups, such as a methylene group, an ethylene group, a trimethylene group, a propylene group, and a butane-1,2-diyl group. Among them, single bonds; A C _2-4 alkylene group (especially, a C _2-3 alkylene group such as an ethylene group or a propylene group) is preferable, and a single bond is more preferable.

Further, when both W ¹ and W ² in the general formula (1) are groups represented by the general formula (2), R ¹ contained in W ^{1 and R 1 contained} in W ² may be the same as or different from each other. You can do it.

In the general formula (2), R ² is 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, a group represented by -NHR ^4c , a group represented by -N(R ^4d ) ₂ , a (meth)acryloyloxy group, a sulfo group or a monovalent hydrocarbon group, a group represented by -OR ^4a , - At least a part of hydrogen atoms bonded to carbon atoms included in the group represented by SR ^4b , acyl group, alkoxycarbonyl group, -NHR ^4c , or group represented by -N(R ^4d ) ₂ is 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, a group represented by -NHR ^4c , -N(R ^4d ) represents a group represented by ₂ , a (meth)acryloyloxy group, a mesyloxy group, or a group substituted with a sulfo group, and R ^4a to R ^4d independently represent a monovalent hydrocarbon group. Moreover, m represents the integer of 0 or more.

Specifically, as R ² , for example, an alkyl group (for example, a C _1-12 alkyl group such as a methyl group, an ethyl group, a propyl group, an isopropyl group, or a butyl group, preferably a C _1-8 alkyl group, more preferably C _1-6 alkyl group, etc.), cycloalkyl group (C _5-10 cycloalkyl group such as cyclohexyl group, preferably C _5-8 cycloalkyl group, more preferably C _5-6 cycloalkyl group, etc.), aryl group (eg For example, a C _6-14 aryl group such as a phenyl group, a tolyl group, a xylyl group, or a naphthyl group, preferably a C _6-10 aryl group, more preferably a C _6-8 aryl group, etc.), an aralkyl group (benzyl group, etc.) monovalent hydrocarbon groups such as C _6-10 aryl-C _1-4 alkyl groups such as group and phenethyl group); hydroxyl group; Alkoxy group (C _1-12 alkoxy group such as methoxy group, ethoxy group, propoxy group, butoxy group, preferably C _1-8 alkoxy group, more preferably C _1-6 alkoxy group, etc.), cycloalkoxy group (C _5-10 cycloalkoxy group such as cyclohexyloxy group), aryloxy group (C _6-10 aryloxy group such as phenoxy group), aralkyloxy group (eg, C _6- such as benzyloxy group) a group represented by -OR ^4a such as ₁₀ aryl-C _1-4 alkyloxy group) [wherein R ^4a represents a monovalent hydrocarbon group (such as the monovalent hydrocarbon group exemplified above)]; An alkylthio group (a C _1-12 alkylthio group such as a methylthio group, an ethylthio group, a propylthio group, or a butylthio group, preferably a C _1-8 alkylthio group, more preferably a C _1-6 alkylthio group group), a cycloalkylthio group (such as a C _5-10 cycloalkylthio group such as a cyclohexylthio group), an arylthio group (such as a C _6-10 arylthio group such as a phenylthio group), an aralkylthio group (eg For example, a group represented by -SR ^4b such as a C _6-10 aryl-C _1-4 alkylthio group such as a benzylthio group [wherein R ^4b is a monovalent hydrocarbon group (monovalent hydrocarbon group etc. exemplified above) indicates.]; acyl groups (such as C _1-6 acyl groups such as acetyl groups); an alkoxycarbonyl group (such as a C _1-4 alkoxycarbonyl group such as a methoxycarbonyl group); halogen atom (fluorine atom, chlorine atom, bromine atom, iodine atom, etc.); nitro group; cyano group; mercapto group; carboxyl group; amino group; carbamoyl group; An alkylamino group (a C _1-12 alkylamino group such as a methylamino group, an ethylamino group, a propylamino group, or a butylamino group, preferably a C _1-8 alkylamino group, more preferably a C _1-6 alkylamino group, etc.), a cycloalkylamino group ( C _5-10 cycloalkylamino group such as cyclohexylamino group), arylamino group (C _6-10 arylamino group such as phenylamino group), aralkylamino group (eg, C _6-10 aryl-C ₁ such as benzylamino group) a group represented by -NHR ^4c such as _-4 alkylamino group) [wherein R ^4c represents a monovalent hydrocarbon group (such as the monovalent hydrocarbon group exemplified above)]; A di(C _1-12 alkyl)amino group such as a dialkylamino group (dimethylamino group, diethylamino group, dipropylamino group, and dibutylamino group), preferably a di(C _1-8 alkyl)amino group, more preferably a di(C _1-6 alkyl)amino group), dicycloalkylamino group (di(C _5-10 cycloalkyl)amino group such as dicyclohexylamino group), diarylamino group (di(C _6-10 aryl such as diphenylamino group) A group represented by -N(R ^4d ) ₂ such as an amino group), a diaralkylamino group (eg, a di(C _6-10 aryl-C _1-4 alkyl)amino group such as a dibenzylamino group) [wherein R ^4d independently represents a monovalent hydrocarbon group (such as the monovalent hydrocarbon group exemplified above)]; (meth)acryloyloxy group; sulfo group; bonded to a carbon atom contained in the monovalent hydrocarbon group, the group represented by -OR ^4a , the group represented by -SR ^4b , an acyl group, an alkoxycarbonyl group, a group represented by -NHR ^4c , or a group represented by -N(R ^4d ) ₂ At least a part of the hydrogen atoms is 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 group substituted with a carbamoyl group, a group represented by -NHR ^4c , a group represented by -N(R ^4d ) ₂ , a (meth)acryloyloxy group, a mesyloxy group, or a sulfo group [for example, an alkoxyaryl group ( For example, a C _1-4 alkoxy C _6-10 aryl group such as a methoxyphenyl group), an alkoxycarbonylaryl group (eg, a C _1-4 alkoxy group such as a methoxycarbonylphenyl group and an ethoxycarbonylphenyl group) carbonyl C _6-10 aryl group, etc.)] and the like.

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

In addition, preferred R ² is a monovalent hydrocarbon group [eg, an alkyl group (eg, C _1-6 alkyl group), a cycloalkyl group (eg, C _5-8 cycloalkyl group), an aryl group (eg, , C _6-10 aryl group), aralkyl group (eg, C _6-8 aryl-C _1-2 alkyl group)], alkoxy group (C _1-4 alkoxy group, etc.). In particular, R ^2a and R ^2b are _{monovalent hydrocarbon} groups (especially, alkyl group).

In addition, when m is an integer of 2 or more, R< ² > may mutually differ and may be same. In addition, when both W ¹ and W ² in the general formula (1) are groups represented by the general formula (2), R ² contained in W ¹ and R ² contained in W ² may be the same as or different from each other. You can do it.

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

In the general formula (1), ring Y ¹ and ring Y ² represent the same or different aromatic hydrocarbon rings. Specifically, as ring Y ¹ and ring Y ² , for example, a benzene ring, a condensed polycyclic aromatic hydrocarbon ring [for example, a condensed bicyclic hydrocarbon ring (eg, C _8-20 condensed 2 such as a naphthalene ring Condensed 2 to 4 cyclic aromatic hydrocarbon rings such as a cyclic hydrocarbon ring, preferably a C _10-16 condensed bicyclic hydrocarbon ring), a condensed tricyclic aromatic hydrocarbon ring (eg, anthracene ring, phenanthrene ring, etc.) can be heard Especially, it is preferable that ring Y1 and ring Y2 are ^a benzene ring or ^a naphthalene ring. ^In addition, ring Y1 and ring Y2 may be same or different, for example, ^a benzene ring may be sufficient as one ring, and a naphthalene ring etc. may be sufficient as the other ring.

In the general formula (1), R is a single bond, a methylene group which may have a substituent, an ethylene group which may have a substituent and may contain a hetero atom between two carbon atoms, a group represented by -O-, - A group represented by NH- or a group represented by -S- is represented. Among them, R is preferably a single bond. Here, as the substituent, for example, a cyano group, a halogen atom (fluorine atom, chlorine atom, bromine atom, etc.), a monovalent hydrocarbon group [for example, an alkyl group (methyl group, ethyl group, propyl group, isopropyl group, butyl group, C _1-6 alkyl group such as t-butyl group), aryl group (C _6-10 aryl group such as phenyl group), etc.], and the hetero atom includes, for example, an oxygen atom, a nitrogen atom, a sulfur atom, A silicon atom etc. are mentioned.

In the general formula (1), R ^3a and R ^3b independently represent a cyano group, a halogen atom, or a monovalent hydrocarbon group, and n1 and n2 independently represent an integer of 0-4. Specifically, R ^3a and R ^3b are usually non-reactive substituents, such as cyano group, halogen atom (fluorine atom, chlorine atom, bromine atom, etc.), monovalent hydrocarbon group [eg, alkyl group, aryl group (phenyl group) C _6-10 aryl groups such as ) etc.], etc. are mentioned, It is preferable that it is a cyano group or an alkyl group, and it is especially preferable that it is an alkyl group. Examples of the alkyl group include C _1-6 alkyl groups such as methyl group, ethyl group, propyl group, isopropyl group, butyl group and t-butyl group (eg, C _1-4 alkyl group, particularly methyl group). In addition, when n1 is an integer of 2 or more, R ^3a may mutually differ and may be same. Moreover, when n2 is an integer of 2 or more, R ^3b may mutually differ and may be same. In addition, R ^3a and R ^3b may be the same or different. Moreover, the bonding position (substitution position) of R ^3a and R ^3b with respect to ring Y ¹ and ring Y ² is not specifically limited. Preferred substitution numbers n1 and n2 are 0 or 1, particularly 0. In addition, n1 and n2 may mutually be same or different.

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

The compound represented by the general formula (1) is a novel vinyl group-containing condensed polycyclic compound, and has high reactivity because it has a vinyloxy group and/or (meth)acryloyloxy group while maintaining excellent optical and thermal properties. . In particular, when ring Y ¹ and ring Y ² are a benzene ring, and R is a single bond, the compound represented by the general formula (1) has a fluorene skeleton and has further excellent optical and thermal properties. Since the compound represented by such general formula (1) can superpose|polymerize, it functions as a polymerizable monomer. In particular, when both W ¹ and W ² are groups represented by the general formula (2), the compound represented by the general formula (1) can be cationic polymerized, and thus functions as a cationically polymerizable monomer. On the other hand, when W< ¹ > and W< ² > are both (meth)acryloyloxy group, since the compound represented by the said General formula (1) can radically polymerize, it functions as a radically polymerizable monomer. Moreover, as for the compound represented by the said General formula (1), when W< ¹ > and W< ² > are the group or (meth)acryloyloxy group independently represented by the said General formula (2), a vinyloxy group and/or (meth)acryl Since two vinyl groups contained in the form of a royloxy group can react with other molecules, they can be suitably used as a crosslinking agent. Moreover, the compound represented by the said General formula (1) provides the hardened|cured material which has high hardness, and is preferable as a base material component in a composition.

The compound represented by the said General formula (1) can be used for various uses. For example, alignment film and planarization film (For example, alignment film and planarization film used for a liquid crystal display display, an organic electroluminescent display, etc.); resist underlayer films, such as an antireflection film, an interlayer insulating film, and a carbon hard mask; Spacers and partitions, such as a liquid crystal display display and an organic electroluminescent display; a pixel or a black matrix of a color filter of a liquid crystal display; Display devices, such as a liquid crystal display display and an organic electroluminescent display; optical members such as lenses (eg, microlenses), optical fibers, optical waveguides, prism sheets, holograms, high refractive films, and retroreflective films; low moisture permeability membrane (for example, low moisture permeability membrane used as a water vapor barrier layer); optical materials; It can be used for the material for semiconductors.

As described above, when ring Y ¹ and ring Y ² are a benzene ring, and R is a single bond, the compound represented by the general formula (1) has a fluorene skeleton, and optical properties such as light transmittance and refractive index and thermal It is preferable because it is more excellent in a characteristic. Further, in the compound represented by the general formula (1), when both W ¹ and W ² are groups represented by the general formula (2), X is a single bond, and R ¹ is a single bond, light transmittance, refractive index, etc. The optical properties of , tend to be superior. In particular, when R ¹ is a single bond, optical properties and thermal properties tend to be remarkably improved, which is preferable.

Among the compounds represented by the general formula (1), a compound represented by the following formula is exemplified as a preferable specific example.

Although it does not specifically limit as content of the vinyl group containing compound represented by said Formula (1), It is preferable that it is 1-95 weight% with respect to solid content in a composition, It is more preferable that it is 3-80 weight%, It is 5-50 weight. % is particularly preferred. By making content of a vinyl group containing compound into the above-mentioned range, coating-film formation ability etc. improve.

[About the manufacturing method of the vinyl group containing compound represented by General formula (1)]

Next, the manufacturing method of the vinyl group containing compound represented by the said General formula (1) is demonstrated. The vinyl group-containing compound represented by the general formula (1) can be synthesized, for example, from any one of the following production methods 1-3.

(Manufacturing method 1)

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

R ₆ -CO-O-CH=CH ₂ (13)

(In the formula, R ⁶ represents a hydrogen atom or an organic group.)

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

(Wherein, rings Z, X, R ¹ , R ² and m are the same as above.)

The compound represented by the general formula (3) includes, for example, a compound represented by the following general formula (14) and/or a compound represented by the following general formula (15) in the presence of an acid catalyst, and a compound represented by the following general formula (16) ) can be synthesized by reacting the compound represented by Further, the desired hydroxyl group-containing compound represented by the general formula (3) can be obtained by appropriately adjusting the method of combining the compound represented by the following general formula (14) and the compound represented by the following general formula (15), the addition amount, and the like. Moreover, after reaction, you may isolate|separate the target hydroxyl-containing compound by well-known separation methods, such as silica gel column chromatography, for example.

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

As an acid catalyst, reaction conditions, etc. used for the synthesis|combination of the compound represented by the said General formula (3), fluorene as described in the Claim in Unexamined-Japanese-Patent No. 2011-201791 or 2002-255929, for example. What is described as being usable as a method for producing a system compound is exemplified.

(Manufacturing method 2)

The vinyl group-containing compound represented by the general formula (1) is, for example, from the hydroxyl group-containing compound represented by the formula (3) via the leaving group-containing compound represented by the following general formula (5) to the formula (1) It can also be synthesized by a manufacturing method comprising the step of obtaining a vinyl group-containing compound represented by ).

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

(Where E is a chlorine atom, a bromine atom, an iodine atom, a methanesulfonyloxy group, a trifluoromethanesulfonyloxy group, a paratoluenesulfonyloxy group, or an alkyloxy group having 1 to 4 carbon atoms substituted with a benzenesulfonyloxy group. represents, and rings Z, X, R ¹ , R ² and m are the same as above.)

The leaving group-containing compound represented by the formula (5) can be synthesized, for example, by reacting the hydroxyl group-containing compound represented by the formula (3) with the leaving group-containing compound. Examples of the leaving group-containing compound include thionyl chloride and a compound represented by the following formula. Moreover, as reaction temperature, it can be set as about -20-150 degreeC, for example, It is more preferable to set it as about -10-140 degreeC, It is especially preferable to set it as about 30-130 degreeC.

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

(Manufacturing method 3)

The compound represented by the general formula (1) is, for example, from a hydroxyalkyloxy group-containing compound represented by the following general formula (7) via a leaving group-containing compound represented by the general formula (5) to the above general formula ( It can also synthesize|combine by the manufacturing method which includes the step of obtaining the vinyl group containing compound represented by 1).

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

(Wherein, l is an integer of 1 to 4, and rings Z, X, R ¹ , R ² and m are the same as above.)

The hydroxyalkyloxy group-containing compound represented by the general formula (7) includes, for example, a compound represented by the following general formula (17) and/or a compound represented by the following general formula (18) in the presence of an acid catalyst; It can synthesize|combine by making the compound represented by General formula (16) react. Further, the desired hydroxyalkyloxy group-containing compound represented by the general formula (7) can be obtained by appropriately adjusting the method of combining the compound represented by the following general formula (17) and the compound represented by the following general formula (18), the amount of addition, etc. can Moreover, you may isolate|separate the target hydroxyalkyloxy group containing compound after reaction, for example by well-known separation methods, such as silica gel column chromatography. Examples of the acid catalyst and reaction conditions used in the synthesis of the compound represented by the general formula (7) include those exemplified in the description of the method for synthesizing the compound represented by the general formula (3).

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

The leaving group-containing compound represented by the formula (5) can be synthesized, for example, by reacting the hydroxyalkyloxy group-containing compound represented by the formula (7) with the leaving group-containing compound. Examples of the leaving group-containing compound and the reaction temperature include those exemplified in Production Method 2 described above.

The vinyl group-containing compound represented by the general formula (1) can be synthesized, for example, by reacting the leaving group-containing compound represented by the general formula (5) with a vinylating agent. Examples of the vinylating agent and the reaction temperature include those exemplified in the above-mentioned production method 2 .

<Electron pair donor compound>

The curable composition according to the present invention contains an electron pair donating compound. Although the detailed process is not clear, the presence of this electron pair donating compound causes the vinyl group-containing compound represented by the general formula (1) contained in the composition to react, thereby facilitating the curing of the curable composition, and the The heat resistance and solvent resistance of the hardened|cured material obtained by hardening can be improved.

An electron pair donating compound can be used individually by 1 type or in combination of 2 or more type. Specific examples of the electron pair donating compound include compounds capable of donating an electron pair to the vinyl group-containing compound represented by the above general formula (1), and are not limited thereto, but compared to the vinyl group-containing compound, Compounds that can act as weak Lewis bases are preferred. For example, as an electron pair donating compound, a nitrogen-containing compound and an oxygen-containing compound are mentioned.

Examples of the nitrogen-containing compound include a nitrogen-containing compound represented by the following general formula (p-1), a nitrogen-containing compound represented by the following general formula (p-2), a nitrogen-containing compound represented by the following general formula (p-3), etc. can be heard

Here, in the said general formula (p-1), R ^p1 represents the C1-C5 alkylene group which may have a substituent. Specifically, examples of the alkylene group represented by R ^p1 include a linear alkylene group such as a methylene group, n-ethylene group, n-propylene group, n-butylene group and n-pentylene group, 1-methylethylene group, and 1-methylpropylene group. and branched alkylene groups such as group and 2-methylpropylene group. Especially, it is preferable that it is a C2-C4 alkylene group, and it is more preferable that it is a C2-C3 alkylene group, such as an ethylene group and a propylene group.

In the general formula (p-1), R ^p2 represents an alkyl group having 1 to 3 carbon atoms. Specifically, the alkyl group represented by R ^p2 may be either linear or branched, and examples thereof include a methyl group, an ethyl group, a propyl group, and an isopropyl group.

In addition, in the said general formula (p-1), j represents the integer of 1-5, and k represents the integer of 0-4. However, j+k is an integer of 1-5, and when j is an integer of 2 or more, R ^p1 may be the same or different. Moreover, when k is 2 or more, R ^p2 may be the same or different, and at least two of R ^p2 may mutually couple|bond together, and may form the ring.

More specifically, as a nitrogen-containing compound represented by the said general formula (p-1), the following compound can be illustrated.

Moreover, as a nitrogen-containing compound which is an electron pair donating compound, the compound represented by the following general formula (p-2) can also be used.

Here, in the said general formula (p-2), R ^p3 and R ^p4 represent an alkyl group, Preferably a C1-C10 alkyl group is represented. Specifically, the alkyl group represented by R ^p3 and R ^p4 may be either linear or branched, and specifically, a methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec -butyl group, tert-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group etc. are mentioned.

In the general formula (p-2), R ^p5 represents any group selected from the group consisting of a hydrogen atom, an organic group, an amino group, a hydroxy group, a sulfanyl group and a sulfo group. Examples of the organic group represented by R ^p5 include an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a heteroaryl group, a hydroxyalkyl group, a hydroxyalkenyl group, a hydroxyalkynyl group, an alkoxyalkyl group, an alkoxyalkenyl group, an alkoxyalkynyl group. , arylalkyl group, arylalkenyl group, arylalkynyl group, heteroarylalkyl group, heteroarylalkenyl group, heteroarylalkynyl group, alkylaryl group, alkylheteroaryl group, alkoxyaryl group, alkoxyheteroaryl group, carboxyl group, carboxyalkyl group, alkoxy Carbonyl group, acyloxy group, acyl group, carbamoyl group, alkylcarbamoyl group, dialkylcarbamoyl group, alkylamino group, dialkylamino group, alkylsulfanyl group, alkylsulfonyl group, arylsulfonyl group, aminoaryloxy group, alkylamino An aryloxy group, a dialkylamino aryloxy group, etc. are mentioned. Especially, it is preferable that R ^p5 is an organic group, and a carboxyl group or an alkoxycarbonyl group (Here, the C1-C10 alkoxy group which may be linear or branched is mentioned as an alkoxy group.) is more preferable.

More specifically, as a nitrogen-containing compound represented by the said general formula (p-2), the following compound can be illustrated.

Moreover, as a nitrogen-containing compound as an electron pair donating compound, the compound represented by the following general formula (p-3) can also be used.

R ^p6 -NH-C(O)-V ¹ -R ^p7 -V ² (p-3)

Here, in general formula (p-3), R ^p6 is an alkyl group which may have a substituent. The alkyl group preferably has 1 to 12 carbon atoms, more preferably 1 to 3 carbon atoms, and may be any of linear, branched, and cyclic. As a linear or branched alkyl group, a C1-C5 thing is preferable. Specific examples of the alkyl group include a methyl group, an ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, n-hexyl group, n-hep group tyl group, n-octyl group, n-nonyl group, n-decyl group, n-undecyl group and n-dodecyl group are mentioned. Moreover, as a substituent which R ^p6 which is an alkyl group may have, Halogen atoms, such as alkoxy groups, such as a methoxy group, an ethoxy group, a propoxy group, and a butoxy group, fluorine, chlorine, iodine, and a bromine; hydroxyl group; Alkoxyalkyloxy groups such as ethoxymethyloxy group, trialkoxysilyl groups such as triethoxysilyl group, alkyldialkoxysilyl groups such as methyldiethoxysilyl group, alkoxydialkylsilyl groups such as ethoxydimethylsilyl group, etc. can be heard

In general formula (p-3), V ¹ is -NH-, -O-, or -S-, and it is preferable that it is -NH-. In V ¹ , the bond represented by -CO-NH- is less susceptible to hydrolysis than the bond represented by -CO-O- or -CO-S-, and it is preferable.

In general formula (p-3), R ^p7 is a single bond or an alkylene group, Preferably it is a single bond. When R ^p7 is an alkylene group, it preferably has 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, and either linear or branched may be sufficient. Specific examples of the alkylene group include a methylene group, 1,2-ethylene group, 1,1-ethylene group, propane-1,3-diyl group, propane-1,2-diyl group, propane-1,1-diyl group, Propane-2,2-diyl group, butane-1,4-diyl group, butane-1,3-diyl group, butane-1,2-diyl group, butane-1,1-diyl group, butane-2,2 -diyl group, butane-2,3-diyl group, pentane-1,5-diyl group, pentane-1,4-diyl group, and hexane-1,6-diyl group, heptane-1,7-diyl group, octane-1,8-diyl group, nonane-1,9-diyl group, decane-1,10-diyl group, undecane-1,11-diyl group, and dodecane-1,12-diyl group. there is.

In the general formula (p-3), V ² is a nitrogen-containing heteroaryl group which may have a substituent or may be monocyclic or polycyclic, and the ring bonded to -V ¹ -R ^p7 - in V ² is a nitrogen-containing 6-membered aromatic ring. , -V ¹ -R ^p7 - bonds to a carbon atom in the nitrogen-containing 6-membered aromatic ring.

When V ² is a polycyclic heteroaryl group, the heteroaryl group may be a contribution obtained by condensing a plurality of monocyclic rings or may be a contribution obtained by bonding a plurality of monocyclic rings through a single bond. Moreover, when V ² is a polycyclic heteroaryl group, the number of rings contained in the polycyclic heteroaryl group is preferably 1-3. Further, when V ² is a polycyclic heteroaryl group, the ring condensed or bonded to the nitrogen-containing 6-membered aromatic ring in V ² may or may not contain a hetero atom, and may or may not be an aromatic ring.

As a substituent which ^V2 which is a nitrogen-containing heteroaryl group may have, a C1-C6 alkyl group, a C1-C6 alkoxy group, a C2-C6 alkenyl group, a C2-C6 alkenyloxy group, a C2-6 aliphatic acyl group, benzoyl group, nitro group, nitroso group, amino group, hydroxyl group, mercapto group, cyano group, sulfonic acid group, carboxyl group, and halogen atom. Although the number of substituents which X has is not specifically limited, 5 or less are preferable and 3 or less are more preferable. When V ² has a plurality of substituents, the plurality of substituents may be the same or different.

As an especially preferable example of ^V2 , group of a following formula is mentioned.

More specifically, as a nitrogen-containing compound represented by the said general formula (p-3), the following compound can be illustrated.

Examples of the oxygen-containing compound include an ester compound, a β-diketone compound, and an ether compound. Specific examples of the ester compound include a chain alkyl ester compound, a cyclic alkyl ester compound, and a β-keto ester compound, and examples of the chain alkyl ester compound include methyl formate, ethyl formate, propyl formate, butyl formate, methyl acetate, Ethyl acetate, propyl acetate, butyl acetate, methyl chloroacetate, ethyl chloroacetate, propyl chloroacetate, methyl dichloroacetate, ethyl dichloroacetate, propyl dichloroacetate, methyl propionate, ethyl propionate, methyl butanoate, ethyl butanoate, methyl pentanoate , ethyl pentanoate, methyl hexanoate, ethyl hexanoate, methyl heptanoate, ethyl heptanoate, etc.; Examples of the cyclic alkyl ester compound include cyclohexyl acetate, cyclopentyl acetate, cyclooctyl acetate, methylcyclohexyl acetate, ethylcyclohexyl acetate, propylcyclohexyl acetate, i-propylcyclohexyl acetate, butylcyclohexyl acetate, and i-butylcyclohexyl. acetate, s-butylcyclohexylacetate, t-butylcyclohexylacetate, pentylcyclohexylacetate, etc.; Examples of the β-ketoester compound include methyl acetoacetate, ethyl acetoacetate, acetoacetate-n-propyl, acetoacetate isopropyl, acetoacetate-n-butyl, α-acetyl-γ-butyrolactone, and the like. . Moreover, acetylacetone, 2, 4- hexanedione, 2, 4- heptanedione, etc. can be illustrated as (beta)-diketone compound. Examples of the ether compound include dimethyl ether, ethyl methyl ether, diethyl ether, dipropyl ether, diisopropyl ether, dibutyl ether, 1,2-dimethoxyethane, anisole, 1,4-dioxane, tetrahydro Furan etc. can be illustrated.

Although it does not specifically limit as content of the electron pair donating compound in the curable composition which concerns on this invention, It is preferable that it is 0.5-50 weight part with respect to 100 weight part of vinyl group containing compounds represented by the said General formula (1), and 1-30 It is more preferable that it is a weight part, and it is especially preferable that it is 1-20 weight part. When content of an electron pair donating compound shall be 0.5-50 weight part with respect to 100 weight part of vinyl group containing compounds, the heat resistance and heat resistance of the cured film which consists of a hardened|cured material obtained by hardening of this curable composition will improve more easily.

When an electron-pair-donating compound solubilizes the vinyl group containing compound represented by the said General formula (1), you may use an electron-pair-donating compound as a solvent component. In this case, it is preferable that the solid content concentration of the said General formula (1) is 0.5 to 50 weight%, and it is more preferable that it is 1 to 40 weight%. Moreover, you may adjust the quantity of an electron pair donating compound so that solid content concentration of the whole curable composition may be set to 0.5 to 50 weight%, More preferably, it is a case where solid content concentration is 1 to 40 weight%.

<Polymerization Initiator>

The curable composition which concerns on this invention may contain a polymerization initiator further. The polymerization initiator is, for example, a compound that generates a cation by being irradiated with an active energy ray such as ultraviolet rays, far ultraviolet rays, excimer laser light such as KrF or ArF, X-rays, or electron beams, and the cation can be a polymerization initiator. The above-mentioned vinyl group-containing compound contained in the curable composition according to the present invention undergoes cationic polymerization. For this reason, by mix|blending the polymerization initiator which generate|occur|produces a cation by irradiation of an active energy ray, hardening reaction based on a polymerization reaction can be made to raise|generate more effectively, and sclerosis|hardenability improves.

As a polymerization initiator, the compound represented, for example by the following general formula (i-1) is mentioned.

Here, in the formula (i-1), R ⁷ and R ⁸ each independently represent a hydrogen atom, a halogen atom, an oxygen atom or a hydrocarbon group which may contain a halogen atom, or an alkoxy group to which a substituent may couple. Further, R ⁹ represents a p-phenylene group in which one or more of the hydrogen atoms may be substituted with a halogen atom or an alkyl group. Moreover, R< ¹⁰ > represents the hydrocarbon group which may contain a hydrogen atom, an oxygen atom, or a halogen atom, the benzoyl group which may have a substituent, and the polyphenyl group which may have a substituent.

In the said general formula (i-1), A ^- represents the counter ion of an onium ion. Specifically, as A ^- , for example, SbF ₆ ^- , PF ₆ ^- , AsF ₆ ^- , BF ₄ ^- , SbCl ₆ ^- , ClO ₄ ^- , CF ₃ SO ₃ ^- , CH ₃ SO ₃ ^- , FSO ₃ ^- , F 2PO ₂ ^- , p _- toluenesulfonate, nonafluorobutanesulfonate, adamantane carboxylate, tetraarylborate, and a fluorinated alkylfluorophosphate anion represented by the following general formula (20);

[(Rf) _b PF _{6 -b} ] ^- (20)

(In the formula (20), Rf represents an alkyl group in which 80% or more of hydrogen atoms are substituted with fluorine atoms. b represents the number and is an integer of 1 to 5. The b pieces of Rf may be the same or different. )

Examples of such polymerization initiators include 4-(2-chloro-4-benzoylphenylthio)phenyldiphenylsulfoniumhexafluoroantimonate, 4-(2-chloro-4-benzoylphenylthio)phenylbis( 4-fluorophenyl) sulfonium hexafluoroantimonate, 4- (2-chloro-4-benzoylphenylthio) phenylbis (4-chlorophenyl) sulfonium hexafluoroantimonate, 4- (2- Chloro-4-benzoylphenylthio)phenylbis(4-methylphenyl)sulfoniumhexafluoroantimonate, 4-(2-chloro-4-benzoylphenylthio)phenylbis(4-(β-hydroxyethoxy) Phenyl) sulfonium hexafluoroantimonate, 4- (2-methyl-4-benzoylphenylthio) phenylbis (4-fluorophenyl) sulfonium hexafluoroantimonate, 4- (3-methyl-4 -benzoylphenylthio)phenylbis(4-fluorophenyl)sulfoniumhexafluoroantimonate, 4-(2-fluoro4-benzoylphenylthio)phenylbis(4-fluorophenyl)sulfoniumhexafluoro Antimonate, 4- (2-methyl-4-benzoylphenylthio) phenylbis (4-fluorophenyl) sulfonium hexafluoroantimonate, 4- (2,3,5,6-tetramethyl-4 -benzoylphenylthio)phenylbis(4-fluorophenyl)sulfonium hexafluoroantimonate, 4-(2,6-dichloro-4-benzoylphenylthio)phenylbis(4-fluorophenyl)sulfoniumhexa Fluoroantimonate, 4-(2,6-dimethyl-4-benzoylphenylthio)phenylbis(4-fluorophenyl)sulfoniumhexafluoroantimonate, 4-(2,3-dimethyl-4- Benzoylphenylthio)phenylbis(4-fluorophenyl)sulfoniumhexafluoroantimonate, 4-(2-methyl-4-benzoylphenylthio)phenylbis(4-chlorophenyl)sulfoniumhexafluoroantimonate Nate, 4-(3-methyl-4-benzoylphenylthio)phenylbis(4-chlorophenyl)sulfoniumhexafluoroantimonate, 4-(2-fluoro4-benzoylphenylthio)phenylbis(4- Chlorophenyl) sulfonium hexafluoroantimonate, 4- (2-methyl-4-benzoylphenylthio) phenylbis (4-chlorophenyl) sulfonium hexafluoroantimonate, 4- (2,3,5 ,6-Tetramethyl-4-benzoylphenylthio)phenylbis(4-chlorophenyl)sulfoniumhexafluoroantimonate, 4-(2,6-dichloro-4-benzoylphenylthio)phenylbis(4-chloro Phenyl) sulfonium hexafluoroantimonate, 4- (2,6-dimethyl-4-benzoylphenyl) Thio) phenylbis (4-chlorophenyl) sulfonium hexafluoroantimonate, 4- (2,3-dimethyl-4-benzoylphenylthio) phenylbis (4-chlorophenyl) sulfonium hexafluoroantimonate , 4- (2-chloro-4-acetylphenylthio) phenyldiphenylsulfonium hexafluoroantimonate, 4- (2-chloro-4- (4-methylbenzoyl) phenylthio) phenyldiphenylsulfonium hexa Fluoroantimonate, 4- (2-chloro-4- (4-fluorobenzoyl) phenylthio) phenyldiphenylsulfonium hexafluoroantimonate, 4- (2-chloro-4- (4-methyl Toxybenzoyl) phenylthio) phenyldiphenylsulfonium hexafluoroantimonate, 4- (2-chloro-4-dodecanoylphenylthio) phenyldiphenylsulfonium hexafluoroantimonate, 4- (2- Chloro-4-acetylphenylthio)phenylbis(4-fluorophenyl)sulfoniumhexafluoroantimonate, 4-(2-chloro-4-(4-methylbenzoyl)phenylthio)phenylbis(4-fluoro Rophenyl) sulfonium hexafluoroantimonate, 4- (2-chloro-4- (4-fluorobenzoyl) phenylthio) phenylbis (4-fluorophenyl) sulfonium hexafluoroantimonate, 4 -(2-chloro-4- (4-methoxybenzoyl) phenylthio) phenylbis (4-fluorophenyl) sulfonium hexafluoroantimonate, 4- (2-chloro-4- dodecanoylphenylthio ) phenylbis (4-fluorophenyl) sulfonium hexafluoroantimonate, 4- (2-chloro-4-acetylphenylthio) phenylbis (4-chlorophenyl) sulfonium hexafluoroantimonate, 4 - (2-chloro-4- (4-methylbenzoyl) phenylthio) phenylbis (4-chlorophenyl) sulfonium hexafluoroantimonate, 4- (2-chloro-4- (4-fluorobenzoyl) Phenylthio) phenylbis (4-chlorophenyl) sulfonium hexafluoroantimonate, 4- (2-chloro-4- (4-methoxybenzoyl) phenylthio) phenylbis (4-chlorophenyl) sulfonium hexa Fluoroantimonate, 4- (2-chloro-4-dodecanoylphenylthio) phenylbis (4-chlorophenyl) sulfonium hexafluoroantimonate, 4- (2-chloro-4-benzoylphenylthio) ) Phenyldiphenylsulfonium hexafluorophosphate, 4-(2-chloro-4-benzoylphenylthio)phenyldiphenylsulfoniumtetrafluoroborate, 4-(2-chloro-4-benzoylphenylthio)phenyldiphenyl Sulfonium perchlorate, 4- (2-chloro-4-benzoylphenylthio) phenyldiphenylsulfonium trifluoro Romethanesulfonate, 4-(2-chloro-4-benzoylphenylthio)phenylbis(4-fluorophenyl)sulfoniumhexafluorophosphate, 4-(2-chloro-4-benzoylphenylthio)phenylbis( 4-fluorophenyl)sulfoniumtetrafluoroborate, 4-(2-chloro-4-benzoylphenylthio)phenylbis(4-fluorophenyl)sulfoniumperchlorate, 4-(2-chloro-4-benzoylphenyl) Thio) phenylbis (4-fluorophenyl) sulfonium trifluoromethanesulfonate, 4- (2-chloro-4-benzoylphenylthio) phenylbis (4-fluorophenyl) sulfonium p-toluenesulfonate; 4- (2-chloro-4-benzoylphenylthio) phenylbis (4-fluorophenyl) sulfonium camphorsulfonate, 4- (2-chloro-4-benzoylphenylthio) phenylbis (4-fluorophenyl) Sulfonium nonafluorobutanesulfonate, 4- (2-chloro-4-benzoylphenylthio) phenylbis (4-chlorophenyl) sulfonium hexafluorophosphate, 4- (2-chloro-4-benzoylphenylthio) Phenylbis (4-chlorophenyl) sulfonium tetrafluoroborate, 4- (2-chloro-4-benzoylphenylthio) phenylbis (4-chlorophenyl) sulfonium perchlorate, 4- (2-chloro-4-benzoyl Phenylthio) phenylbis (4-chlorophenyl) sulfonium trifluoromethanesulfonate, diphenyl [4- (phenylthio) phenyl] sulfonium trifluorotrispentafluoroethyl phosphate, diphenyl [4- (p -terphenylthio)phenyl]sulfonium hexafluoroantimonate, diphenyl [4-(p-terphenylthio)phenyl]sulfonium trifluorotrispentafluoroethyl phosphate, etc. are mentioned. Among these compounds, 4-(2-chloro-4-benzoylphenylthio)phenylbis(4-fluorophenyl)sulfoniumhexafluoroantimonate (made by ADEKA Corporation, Adekaoptomer SP-172), diphenyl [4- (phenylthio) phenyl] sulfonium trifluorotrispentafluoroethyl phosphate (San Apro Co., Ltd., CPI-210S), diphenyl [4- (p-terphenylthio) phenyl] sulfonium hexafluoro Antimonate and diphenyl[4-(p-terphenylthio)phenyl]sulfonium trifluorotrispentafluoroethyl phosphate (manufactured by San Apro Corporation, HS-1PG) are preferable.

Although it does not specifically limit as content of the polymerization initiator in the curable composition which concerns on this invention, 0.1 to 10 weight% is preferable with respect to solid content in a composition, and it is more preferable that it is 0.5 to 5 weight%. When content of a polymerization initiator shall be 0.1 weight% or more with respect to solid content, the hardening time by exposure of the active energy ray of a curable composition can be made suitable. Moreover, when the content shall be 10 weight% or less with respect to solid content, the developability after exposure by an active energy ray can be made favorable.

<crosslinking agent>

The curable composition which concerns on this invention may contain a crosslinking agent further. The crosslinking agent promotes crosslinking of the vinyl group-containing compound represented by the general formula (1) to improve curability. As this crosslinking agent, it can be used individually by 1 type or in combination of 2 or more type. Although it does not specifically limit as a crosslinking agent, The crosslinking agent which has a hydroxyl group, the crosslinking agent which has a carboxyl group, etc. are mentioned.

(crosslinking agent having a hydroxyl group)

For example, the crosslinking agent having a hydroxyl group is not particularly limited as long as it is a compound capable of causing a crosslinking reaction with the vinyl group-containing compound represented by the general formula (1), but it is preferable to contain an organic group having a cyclic structure. .

Specific examples thereof include compounds represented by the following general formula (c-1).

HO-R ¹¹ -OH (c-1)

Here, in the general formula (c-1), R ¹¹ represents an organic group, and examples thereof include a divalent hydrocarbon group, a divalent heterocyclic group, and a group formed by combining them with each other. A divalent hydrocarbon group is preferable. . The divalent hydrocarbon group and the divalent heterocyclic group may have a substituent. Among them, R ¹¹ preferably has a cyclic structure.

Examples of the divalent hydrocarbon group include a divalent aliphatic hydrocarbon group, a divalent alicyclic hydrocarbon group, a divalent aromatic hydrocarbon group, and a group formed by bonding two or more thereof. Examples of the divalent aliphatic hydrocarbon group include a methylene group, an ethylene group, a propylene group, an isopropylene group, a butylene group, an isobutylene group, an s-butylene group, a t-butylene group, a pentylene group, a hexylene group, and a decylene group. , an alkylene group having 1 to 20 carbon atoms, such as a dodecylene group, preferably 1 to 10, more preferably 1 to 3 carbon atoms; an alkenylene group having 2 to 20 carbon atoms, preferably 2 to 10, more preferably 2 to 3 carbon atoms, such as a vinylene group, a propenylene group, and a 1-butenylene group; C2-C20, such as an ethynylene group and a propynylene group, Preferably it is 2-10, More preferably, a 2-3 alkynylene group etc. are mentioned. Moreover, as a bivalent alicyclic hydrocarbon group, C3-C20, such as a cyclopropylene group, a cyclobutylene group, a cyclopentylene group, a cyclohexylene group, a cyclooctylene group, Preferably it is 3-15, More preferably, it is 5 a cycloalkylene group of 8; a cycloalkenylene group having 3 to 20 carbon atoms, preferably 3 to 15 carbon atoms, more preferably 5 to 8 carbon atoms, such as a cyclopentenylene group and a cyclohexylene group; Perhydronaphthylene group, norbornylene group, adamantylene group, tetracyclo [4. 4. 0. 1 ^{2, 5} . 1 ^{7, 10} ] a divalent cross-linked hydrocarbon group having 4 to 20 carbon atoms, preferably 6 to 16 carbon atoms, more preferably 7 to 12 carbon atoms, such as dodecylene group, etc. are mentioned. Moreover, as a divalent aromatic hydrocarbon group, C6-C20, such as a phenylene group, a naphthylene group, and a fluorenylene group, Preferably a 6-13 allylene group is mentioned.

Examples of the group formed by bonding a divalent aliphatic hydrocarbon group and a divalent alicyclic hydrocarbon group include a cycloalkylene-alkylene group such as a cyclopentylenemethylene group, a cyclohexylenemethylene group, and a cyclohexyleneethylene group (for example, , C _3-20 cycloalkylene-C _1-4 alkylene group, etc.) and the like. In addition, as a group formed by bonding a divalent aliphatic hydrocarbon group and a divalent aromatic hydrocarbon group, for example, an allylene-alkylene group (eg, C _{6-20 allylene} -C _1-4 alkylene group, etc.), allylene -alkylene-allylene group (For example, C _{6-20 allylene} -C _1-4 alkylene group-C _6-20 allylene group, etc.) and the like. In addition, as a group formed by bonding two or more divalent aromatic hydrocarbon groups to each other, for example, an allylene-allylene group (eg, C _{6-20 allylene} -C _6-20 allylene group, etc.), allylene -Allylene-allylene group (For example, C _6-10 allylene-C _6-13 allylene-C _6-10 allylene group, etc.) etc. are mentioned.

Among these divalent hydrocarbon groups, those having a cyclic structure are preferable, and C _6-10 allylene-C _6-13 allylene group-C _6-10 allylene group, C _{6-20 allylene} -C _1-4 alkylene group- A C _6-20 allylene group or a divalent cross-linked hydrocarbon group having 7 to 12 carbon atoms is particularly preferable.

The divalent hydrocarbon group includes various substituents, for example, a halogen atom, an iodine group, a hydroxyl group, a substituted oxy group (eg, an alkoxy group, an aryloxy group, an aralkyloxy group, an acyloxy group, etc.), a carboxyl group, a substituted oxycarbonyl group ( alkoxycarbonyl group, aryloxycarbonyl group, aralkyloxycarbonyl group, etc.), a substituted or unsubstituted carbamoyl group, a cyano group, a nitro group, a substituted or unsubstituted amino group, a sulfo group, a heterocyclic group, or the like. The hydroxyl group and the carboxyl group may be protected by a protecting group commonly used in the field of organic synthesis. Moreover, the aromatic or non-aromatic heterocycle may condensate to the ring of a bivalent alicyclic hydrocarbon group and a divalent aromatic hydrocarbon group.

A divalent heterocyclic group is a group formed by removing two hydrogen atoms from a heterocyclic compound. The heterocyclic compound may be an aromatic heterocyclic compound or a non-aromatic heterocyclic compound. As such a heterocyclic compound, for example, a heterocyclic compound containing an oxygen atom as a hetero atom (for example, a 3-membered heterocyclic compound such as oxirane, a 4-membered heterocyclic compound such as oxetane, furan, 5-membered heterocyclic compounds such as tetrahydrofuran, oxazole and γ-butyrolactone, 6-membered heterocyclic compounds such as 4-oxo-4H-pyran, tetrahydropyran and morpholine, benzofuran, and 4-oxo Heterocyclic compound having a condensed ring such as -4H-chromene and chroman, 3-oxatricyclo[4. 3. 1. 1 ^{4, 8} ]undecan-2-one, 3-oxatricyclo[4. 2. 1. 0 ^{4, 8} ] a heterocyclic compound having a cross-exchange such as nonan-2-one), a heterocyclic compound containing a sulfur atom as a hetero atom (eg, thiophene, thiazole, thiadia) 5-membered heterocyclic compounds such as sol, 6-membered heterocyclic compounds such as 4-oxo-4H-thiopyran, heterocyclic compounds having a condensed ring, such as benzothiophene), containing a nitrogen atom as a hetero atom (For example, 5-membered heterocyclic compounds such as pyrrole, pyrrolidine, pyrazole, imidazole, triazole, pyridine, pyridazine, pyrimidine, pyrazine, piperidine, piperazine, etc. 6-membered ring heterocyclic compounds, indole, indoline, quinoline, acridine, naphthylidene, quinazoline, and purine, etc.) In addition to the substituents that the divalent hydrocarbon group may have, the divalent heterocyclic group includes an alkyl group (eg, a C _1-4 alkyl group such as a methyl group and an ethyl group), a cycloalkyl group, an aryl group (eg, a phenyl group, You may have a substituent, such as a C _6-10 aryl group, such as a naphthyl group).

As a specific example of the crosslinking agent which has the above hydroxyl groups, the compound represented by a following formula is mentioned, for example. In addition, other 2,6-naphthalenediol, 2,7-naphthalenediol, spiro[9Hfluorene-9,9'-[9H]-xanthene]-3',6'-diol, spiro[9Hfluorene -9,9'-[9H]-xanthene]-2',7'-diol, spiro[9Hfluorene-9,9'-[9H]carbazine]-3',6'-diol, spiro[ 9H fluorene-9,13'-[13H]-6-oxapentacene]-2',10'-diol, spiro[9H-fluorene 9,13'-[13H]-6-oxapentacene]- 3',9'-diol, 1,3,6,8,10,10-hexamethylspiro[dihydro-9,9'-fluorene]-2,7-diol, 1,3,6,8- Tetrabromo-10,10-dimethylspiro[dihydro-9,9'-fluorene]-2,7-diol, 1,3,6,8-tetramethylspiro[dihydro-9,9'-flu orene] -2,7-diol; and the like.

(crosslinking agent having a carboxyl group)

The crosslinking agent having a carboxyl group is not particularly limited as long as it is a compound capable of causing a crosslinking reaction with the vinyl group-containing compound represented by the general formula (1), but it is preferable to contain an organic group having a cyclic structure.

Specifically, for example, the compound represented by the said General formula (c-2) is mentioned.

HO-CO-R ¹⁴ -CO-OH (c-2)

Here, in the general formula (c-2), R ¹⁴ represents an organic group, for example, a divalent hydrocarbon group, a divalent heterocyclic group, and a group formed by combining them with each other, preferably a divalent hydrocarbon group . The divalent hydrocarbon group and the divalent heterocyclic group may have a substituent. Among these, it is preferable that R ¹⁴ has a cyclic structure. Examples of these organic groups are the same as those described for the compound of the general formula (c-1).

As a specific example of the crosslinking agent which has the above carboxyl groups, the compound represented, for example by a following formula is mentioned.

Although it does not specifically limit as content of the crosslinking agent in the curable composition which concerns on this invention, 1-50 weight part is preferable with respect to 100 weight part of vinyl group containing compounds represented by the said General formula (1), It is more that 5-40 weight part desirable. When content of a crosslinking agent shall be 1 weight part or more with respect to solid content, it becomes possible to fully exhibit the accelerating effect of a crosslinking formation reaction. Moreover, when the content shall be 50 weight part or less with respect to solid content, crosslinking reaction can be accelerated|stimulated further and sclerosis|hardenability can further be improved.

<Organic solvent>

The curable composition according to the present invention may further contain an organic solvent. Examples of the organic solvent include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol-n-propyl ether, ethylene glycol mono-n-butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, Diethylene glycol mono-n-propyl ether, diethylene glycol mono-n-butyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono- n-propyl ether, propylene glycol mono-n-butyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol mono-n-propyl ether, dipropylene glycol mono-n-butyl ether, tripropylene (poly)alkylene glycol monoalkyl ethers such as glycol monomethyl ether and tripropylene glycol monoethyl ether; (poly)alkylenes such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, and propylene glycol monoethyl ether acetate glycol monoalkyl ether acetates; other ethers such as diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, and tetrahydrofuran; Ketones, such as methyl ethyl ketone, cyclohexanone, 2-heptanone, and 3-heptanone; lactic acid alkyl esters such as methyl 2-hydroxypropionate and ethyl 2-hydroxypropionate; 2-hydroxy-2-methyl ethyl propionate, 3-methoxy methyl propionate, 3-methoxy ethyl propionate, 3-ethoxy methyl propionate, 3-ethoxy ethyl propionate, ethoxy ethyl acetate, ethyl hydroxyacetate, 2 -Hydroxy-3-methylbutanoate, 3-methyl-3-methoxybutyl acetate, 3-methyl-3-methoxybutylpropionate, ethyl acetate, n-propyl acetate, isopropyl acetate, n-acetic acid Butyl, isobutyl acetate, n-pentyl formate, isopentyl acetate, n-butyl propionate, ethyl butyrate, n-propyl butyrate, isopropyl butyrate, n-butyl butyrate, methyl pyruvate, ethyl pyruvate, n-propyl pyruvate, acetoacetic acid other esters such as methyl, ethyl acetoacetate, and ethyl 2-oxobutanoate; aromatic hydrocarbons such as toluene and xylene; Amides, such as N-methylpyrrolidone, N,N- dimethylformamide, and N,N- dimethylacetoamide, etc. are mentioned. Organic solvents can be used individually or in combination of 2 or more types.

It is preferable that it is the quantity used as 1 to 50 weight% of solid content concentration of the curable composition which concerns on this invention, and, as for content of the organic solvent, it is more preferable that it is the quantity used as 5 to 30 weight%.

<Other ingredients>

The curable composition concerning this invention may contain other components, for example, surfactant, a coloring agent, a dispersing agent, a sensitizer, other various additives, etc. as needed.

≪2. Preparation of curable composition≫

The curable composition concerning this invention can be prepared by mixing each component mentioned above with a stirrer. In addition, you may filter using a membrane filter etc. so that the prepared curable composition may become uniform.

≪3. Cured product≫

By hardening the curable composition which concerns on this invention, hardened|cured material can be obtained. The curable composition according to the present invention can be cured, for example, by heating. Although heating conditions are not specifically limited, As a heating temperature, it can be set as about 200-250 degreeC, for example, As a heating time, it can be set as about 2-120 minutes, for example.

Moreover, when the curable composition which concerns on this invention contains the polymerization initiator mentioned above, it can harden|cure also by irradiation of actinic light or a radiation. Examples of the actinic light or radiation used for exposure include ultraviolet rays, electron beams, and laser beams radiated from a low pressure mercury lamp, a high pressure mercury lamp, a metal halide lamp, a g-ray stepper, an i-ray stepper, and the like. Although the exposure amount changes with the light source to be used, the film thickness of a coating film, etc., it is preferable to set it as 1-1000 mJ/cm< ² >, and it is more preferable to set it as 10-500 mJ/cm< ² >.

≪4. Cured film, insulating film, color filter, display device, optical member, etc.≫

The cured film which consists of the hardened|cured material can be formed using the curable composition which concerns on this invention. Moreover, an insulating film and a color filter can also be formed other than a cured film. For example, a cured film can be obtained with the manufacturing method including the process of apply|coating a curable composition on a board|substrate to form a coating film, and the process of hardening this coating film.

More specifically, as a manufacturing method of a cured film, first, a coating film is formed on a board|substrate by an appropriate application|coating method. For example, a coating film can be formed by coating the composition on a substrate and drying it using a contact transfer type coating device such as a roll coater, reverse coater, or bar coater, or a non-contact type coating device such as a spinner (rotary coating device) or a curtain flow coater. there is. It does not specifically limit as a drying method, For example, (1) On a hotplate, for example, 80-120 degreeC, Preferably, the method of prebaking at the temperature of 90-100 degreeC for 60 to 120 second, (2) ) for several hours to several days at room temperature, (3) a method of removing the solvent by leaving it for several tens of minutes to several hours in a warm air heater or infrared heater.

Although it does not specifically limit as thickness of a coating film, It is preferable that it is typically 2-100 micrometers, and it is more preferable that it is 3-50 micrometers. In addition, the thickness of a coating film can be suitably controlled by adjusting the solid content concentration and viscosity of a coating method or a curable composition.

It does not specifically limit as a board|substrate, A conventionally well-known thing can be used. For example, a glass substrate, a board|substrate made from transparent conductive materials, such as ITO, the resin board|substrate containing resin, such as polyethylene terephthalate (PET), etc. are mentioned.

Then, a cured film is obtained by hardening the coating film formed on the board|substrate. The coating film can be cured in the same way as curing the curable composition.

As a curable composition, when the thing which does not contain a coloring agent is used, for example, a transparent cured film and an insulating film can be obtained. Such a cured film or an insulating film is used as a planarization film, such as a liquid crystal display display and organic electroluminescent display, or as an interlayer insulating film and a carbon hard mask, for example.

In addition, when what contains a photosensitive component is used as a curable composition, what was patterned may be sufficient as the cured film and insulating film mentioned above. A patterned cured film or insulating film can be obtained by irradiating and developing an actinic ray or radiation in a predetermined pattern shape with respect to a coating film so that it may mention later. The patterned cured film is used as a spacer or partition, such as a liquid crystal display display and an organic electroluminescent display, for example.

As a pattern formation method, a coating film is formed using the curable composition containing a photosensitive component, and it develops by irradiating actinic light or radiation in a predetermined pattern shape with respect to this coating film. More specifically, first, a coating film is formed in the same manner as described above. Next, the coating film is exposed by irradiating actinic light or radiation in a predetermined pattern shape. An actinic light or a radiation may be irradiated through a negative mask, and may be irradiated directly. The type, exposure amount, etc. of actinic light or radiation are as described above. Then, the coating film after exposure is patterned into a desired shape by developing with a developing solution. It does not specifically limit as a developing method, For example, an immersion method, a spray method, etc. can be used. Examples of the developer include organic substances such as monoethanolamine, diethanolamine, and triethanolamine, and aqueous solutions of sodium hydroxide, potassium hydroxide, sodium carbonate, ammonia, and quaternary ammonium salt. And about the pattern after image development, it is preferable to post-baking on temperature conditions of about 200-250 degreeC.

Moreover, by forming a coating film using the curable composition containing a coloring agent and a photosensitive component, irradiating actinic light or radiation in a predetermined pattern shape with respect to this coating film and developing, for example, the pixel or black of the color filter of a liquid crystal display display. It is also possible to form a matrix.

Such a cured film, an insulating film, and a color filter can be used for a display apparatus. That is, the display device includes the cured film, the insulating film, and/or the color filter described above. Moreover, as a display apparatus, a liquid crystal display display, an organic electroluminescent display, etc. are mentioned.

Further, by molding and curing the curable composition according to the present invention, optical members such as lenses (eg, microlenses), optical fibers, optical waveguides, prism sheets, and holograms can be obtained.

[ Example ]

Hereinafter, although an Example is shown and this invention is demonstrated more concretely, this invention is not limited to the following Example.

≪Material≫

Materials used in Examples and Comparative Examples are as follows.

<Vinyl group-containing compound (compound represented by general formula (1) and comparative compound)>

As a compound represented by the said General formula (1), the compound 1 which is a vinyl ether compound represented by a following formula was prepared. Moreover, Comparative Compounds 1 to 3 which are vinyl ether compounds represented by the following formulas were prepared for comparison.

The synthesis method of the said compound 1 is shown below (Synthesis Example 1). In addition, the materials used in Synthesis Example 1 are as follows.

・Inorganic base

(1) Gyeonghoe (輕灰) Sodium Carbonate

Particle diameter distribution: 250 µm or more; 3% by weight

150 μm or more and less than 250 μm; 15% by weight

75 μm or more and less than 150 μm; 50% by weight

less than 75 μm; 32% by weight

In addition, the above particle diameter distribution was divided using a sieve of 60 mesh (250 μm), 100 mesh (150 μm), and 200 mesh (75 μm), and the weight of each component above and below the sieve finally obtained It calculated by measuring.

・Transition element compound catalyst

(1) di-μ-chlorobis (1,5-cyclooctadiene) 2 iridium (I): [Ir (cod) Cl] ₂

・Hydroxy compound

(1) 9,9'-bis(6-hydroxy-2-naphthyl)fluorene

・Vinyl ester compound

(1) Vinyl propionate

(Synthesis Example 1) Synthesis of compound 1

Di-μ-chlorobis(1,5-cyclooctadiene) 2 iridium (I) [ Ir(cod)Cl] ₂ (839mg, 1.25mmol), hard lime sodium carbonate (12.7g, 0.12mol), 9,9'-bis(6-hydroxy-2-naphthyl)fluorene (225g, 0.5mol), After adding vinyl propionate (125 g, 1.25 mol) and toluene (300 mL), the rotation speed was set to 250 rpm using a stirring blade having a surface area of 10 cm ² , and the temperature was gradually increased while stirring to reflux. Under reflux, it was made to react for 5 hours, removing by-product water with a decanter. As a result of analyzing the reaction solution by gas chromatography, the conversion rate of 9,9'-bis(6-hydroxy-2-naphthyl)fluorene was 100%, and 9,9'-bis(6-hydroxy- Based on 2-naphthyl)fluorene, 9,9'-bis(6-vinyloxy-2-naphthyl)fluorene (Compound 1) was 81%, and bis6-naphtholfluorene monovinyl ether was 4 % yield.

¹ H-NMR (CDCl ₃ ): 4.47 (dd, 2H, J=1.5 Hz, 5.0 Hz), 4.81 (dd, 2H, J=3.5 Hz, 12.0 Hz), 6.71 (dd, 2H, J=6.0 Hz) , 7.12-7.82 (m, 20H)

<Electron pair donor compound>

As the electron pair donating compound, the following electron pair donating compound 1, electron pair donating compound 2, and electron pair donating compound 3 were used.

<Polymerization Initiator>

The following polymerization initiator 1 was used as a polymerization initiator.

<crosslinking agent>

As the crosslinking agent, the following crosslinking agent 1 or crosslinking agent 2 was used.

«Preparation of curable composition»

[Example 1]

5 parts by weight of the vinyl group-containing compound represented by the above compound 1, 0.5 parts by weight of the electron pair donating compound 1, and 0.5 parts by weight of the polymerization initiator 1 are mixed, and dissolved in 58 parts by weight of propylene glycol monomethyl ether acetate A solution was obtained. Thereafter, the obtained solution was filtered using a polyethylene filter having a pore size of 0.10 µm and a polyethylene filter having a pore size of 0.05 µm to prepare a curable composition.

[Example 2]

In Example 2, a solution comprising a curable composition was prepared in the same manner as in Example 1 except that the electron pair donating compound 2 was mixed in an amount of 0.5 parts by weight as the electron pair donating compound.

[Example 3]

In Example 3, a solution comprising a curable composition was prepared in the same manner as in Example 1, except that no polymerization initiator was contained and the crosslinking agent 1 having a hydroxyl group was mixed in an amount of 2 parts by weight.

[Example 4]

In Example 4, a solution comprising a curable composition was prepared in the same manner as in Example 1 except that the electron pair donating compound 1 was mixed in an amount of 0.3 parts by weight.

[Example 5]

In Example 5, a solution comprising a curable composition was prepared in the same manner as in Example 1 except that the electron pair donating compound 1 was mixed in an amount of 1 part by weight.

[Example 6]

In Example 6, 5 parts by weight of the vinyl group-containing compound represented by the above compound 1, 5 parts by weight of the crosslinking agent 2, 0.5 parts by weight of the polymerization initiator 1, and 94.5 parts by weight of the electron pair donating compound 3 were mixed. Thereafter, the obtained solution was filtered using a polyethylene filter having a pore size of 0.10 µm and a polyethylene filter having a pore size of 0.05 µm to prepare a curable composition.

[Comparative Example 1]

In Comparative Example 1, a solution comprising a curable composition was prepared in the same manner as in Example 1 except that the electron pair donating compound was not contained.

[Comparative Example 2]

In Comparative Example 2, a solution comprising a curable composition was prepared in the same manner as in Example 1 except that the electron pair donating compound and the polymerization initiator were not contained.

[Comparative Example 3]

In Comparative Example 3, a solution comprising a curable composition was prepared in the same manner as in Example 1, except that the crosslinking agent 1 having a hydroxyl group was mixed in an amount of 2 parts by weight without containing the electron pair donating compound and the polymerization initiator.

[Comparative Example 4]

In Comparative Example 4, a solution comprising a curable composition was prepared in the same manner as in Example 1 except that Comparative Compound 1 was mixed in an amount of 5 parts by weight as a vinyl group-containing compound.

[Comparative Example 5]

In Comparative Example 5, in the same manner as in Example 1, except that Comparative Compound 1 was mixed in an amount of 5 parts by weight as a vinyl group-containing compound, and electron pair donating compound 2 was mixed in an amount of 0.5 parts by weight as an electron pair donating compound. Thus, a solution comprising a curable composition was prepared.

[Comparative Example 6]

In Comparative Example 6, a solution comprising a curable composition was prepared in the same manner as in Example 1, except that Comparative Compound 2 was mixed in an amount of 5 parts by weight as a vinyl group-containing compound.

[Comparative Example 7]

In Comparative Example 7, in the same manner as in Example 1, except that the comparative compound 2 was mixed in an amount of 5 parts by weight as a vinyl group-containing compound, and the electron pair donating compound 2 was mixed in an amount of 0.5 parts by weight as an electron pair donating compound. Thus, a solution comprising a curable composition was prepared.

[Comparative Example 8]

In Comparative Example 8, a solution comprising a curable composition was prepared in the same manner as in Example 1, except that Comparative Compound 3 was mixed in an amount of 5 parts by weight as a vinyl group-containing compound.

[Comparative Example 9]

In Comparative Example 9, in the same manner as in Example 1, except that the comparative compound 3 was mixed in an amount of 5 parts by weight as the vinyl group-containing compound, and the electron pair donating compound 2 was mixed in an amount of 0.5 parts by weight as the electron pair donating compound. Thus, a solution comprising a curable composition was prepared.

≪Evaluation≫

(Evaluation of heat resistance)

A solution comprising the curable composition prepared in each of the Examples and Comparative Examples described above was applied to a glass substrate using a spin coater, and heated with a hot plate under conditions of 100° C. for 2 minutes to obtain a cured product. UV irradiation (exposure dose 200 mJ/cm ² ) is applied to the obtained cured product, and then a cured film (film thickness: 1.0 μm) is formed by further performing a baking treatment at 230° C. for 20 minutes on a hot plate. did.

In order to evaluate the heat resistance of the formed cured film, the cured film was heated up at room temperature (about 20 degreeC) at the ratio of 10 degreeC in 1 minute, and thermogravimetric analysis (TGDTA) was performed in air|atmosphere. Based on the weight at the start of the analysis, the temperature at which the weight decreases by 5% (the temperature at which the weight decreases by 5%) T _d5% was measured. Specific heat resistance evaluation was evaluated by classifying as follows. Table 1 below shows the results of this heat resistance evaluation together with the compositions of each Example and Comparative Example.

『◎』: 5% weight loss temperature (T _d5% ) is 430℃ or higher

『△』: 5% weight loss temperature (T _d5% ) is 400℃ or more and less than 430℃

『×』: 5% weight loss temperature (T _d5% ) is less than 400℃

(Evaluation of solvent resistance)

In addition, a cured film (film thickness: 1.0 µm) was formed under the same conditions as when formed in the above-described heat resistance evaluation, and the formed cured film was placed in an N-methylpyrrolidone (NMP) solution at room temperature for 10 minutes. The solvent resistance of a cured film was also evaluated by making it immerse over and measuring the change of the film thickness at that time. Specific solvent resistance evaluation was classified and evaluated as follows. The results of this solvent resistance evaluation are also shown in Table 1 below.

『◎』: change in film thickness less than 3%

『Δ』: change in film thickness of 3% or more and less than 10%

『×』: change in film thickness by 10% or more

As shown in Table 1, in curable compositions (Examples 1 to 6) containing Compound 1 and containing an electron pair donating compound, cured products obtained by curing the same were excellent in heat resistance and solvent resistance. In contrast, a curable composition containing compound 1 but not containing an electron pair donating compound (Comparative Examples 1 to 3), and a curable composition containing the vinyl group-containing compound of Comparative Compounds 1 to 3 (Comparative Examples 4 to 9) In this case, the cured product obtained by curing it was inferior in both heat resistance and solvent resistance.

Claims (6)

A vinyl group-containing compound represented by the following general formula (1), and an electron pair donating compound,
The said electron pair donating compound is a nitrogen-containing compound represented by the following general formula (p-1), a nitrogen-containing compound represented by the following general formula (p-2), a nitrogen-containing compound represented by the following general formula (p-3), a chain alkyl The curable composition which is at least 1 sort(s) selected from the group which consists of an ester compound, a cyclic alkylester compound, a β-ketoester compound, and a β-diketone compound.

(Wherein, W ¹ and W ² independently represent a group represented by the following general formula (2), a hydroxyl group, or a (meth)acryloyloxy group, provided that W ¹ and W ² are not simultaneously a hydroxyl group, and the ring Y ¹ and ring Y ² represents the same or different aromatic hydrocarbon ring, R represents a single bond, a methylene group which may have a substituent, an ethylene group which may have a substituent and may contain a hetero atom between two carbon atoms, -O represents a group represented by -, 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 are independently 0 to Represents an integer of 4.)

(Wherein, ring Z represents an aromatic hydrocarbon ring, X represents a single bond or a group represented by -S-, R ¹ represents a single bond, R ² represents a monovalent hydrocarbon group, a hydroxyl group, or 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, a group represented by -NHR ^4c , a group represented by -N(R ^4d ) ₂ A group, a (meth)acryloyloxy group, a sulfo group or a monovalent hydrocarbon group, a group represented by -OR ^4a , a group represented by -SR ^4b , an acyl group, an alkoxycarbonyl group, a group represented by -NHR ^4c , or -N(R ^4d ) at least a part of hydrogen atoms bonded to carbon atoms contained in the group represented by ₂ is 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, a group represented by -NHR ^4c , a group represented by -N(R ^4d ) ₂ , a (meth)acryloyloxy group, a mesyloxy group, or a sulfo group represents a group, R ^4a to R ^4d independently represent a monovalent hydrocarbon group, and m represents an integer of 0 or more.)

(wherein, R ^p1 represents an optionally substituted C1-C5 alkylene group, R ^p2 represents a C1-C3 alkyl group, j represents an integer of 1 to 5, and k represents 0-4 represents an integer, provided that j+k is an integer of 1 to 5, and when j is an integer of 2 or more, R ^p1 may be the same or different, and when k is 2 or more, R ^p2 may be the same or different, and R ^p2 At least two of them may combine with each other to form a ring.)

(Wherein, R ^p3 and R ^p4 represent an alkyl group, and R ^p5 represents any group selected from the group consisting of a hydrogen atom, an organic group, an amino group, a hydroxy group, a sulfanyl group and a sulfo group.)
R ^p6 -NH-C(O)-V ¹ -R ^p7 -V ² ‥ ‥ ‥ ‥ (p-3)
(Wherein, R ^p6 is an alkyl group which may have a substituent, V ¹ is -NH-, -O- or -S-, R ^p7 is a single bond or an alkylene group, and V ² is an alkyl group which may have a substituent or a monocyclic ring. It is a nitrogen-containing heteroaryl group which may be continuous or polycyclic, the ring bonded to -V ¹ -R ^p7 - in V ² is a nitrogen-containing 6-membered aromatic ring, and -V ¹ -R ^p7 - is carbon in the nitrogen-containing 6-membered aromatic ring. bonds with atoms.) The method according to claim 1,
The curable composition wherein the ring Z is a benzene ring or a naphthalene ring. The method according to claim 1,
A curable composition further comprising a polymerization initiator. The method according to claim 1,
A curable composition further comprising a crosslinking agent having a hydroxyl group and/or a carboxyl group. The cured film which consists of hardened|cured material of the curable composition of any one of Claims 1-4. delete