JP6347710B2 - Curable composition and optical component - Google Patents

Description

  The present invention relates to a curable composition and an optical component.

  Conventionally, performance such as high refractive index and high heat resistance has been continuously demanded for plastic lenses and the like. As a material such as a plastic lens having a high refractive index and heat resistance, a fluorene compound having at least two carbon-carbon double bonds in one molecule and an organic compound having at least two SiH groups in one molecule Has been introduced (for example, Patent Document 1).

JP 2012-229356 A

  However, even the curable composition described above has insufficient properties in applications such as optical parts that require high refractive index and high heat resistance.

  In view of the above circumstances, an object of the present invention is to provide a curable composition having both a higher refractive index and higher heat resistance than conventional in cured products in order to satisfy high demands in applications such as optical components. To do.

  The present inventors have found that the above problem can be solved by using a novel vinyl group-containing fluorene compound together with a compound having at least two SiH groups in one molecule, and to complete the present invention. It came. Specifically, the present invention provides the following.

（式中、Ｗ^１及びＷ^２は独立に下記式（２）で表される基を示し、環Ｙ^１及び環Ｙ^２は同一の又は異なる芳香族炭化水素環を示し、Ｒは単結合；置換基を有してもよいメチレン基；置換基を有してもよく、２個の炭素原子間にヘテロ原子を含んでもよいエチレン基；−Ｏ−で示される基；−ＮＨ−で示される基；又は−Ｓ−で示される基；を示し、Ｒ^１ａ及びＲ^１ｂは独立にシアノ基、ハロゲン原子、又は１価炭化水素基を示し、ｎ１及びｎ２は独立に０〜４の整数を示す。）

（式中、環Ｚは芳香族炭化水素環を示し、Ｘは単結合又は−Ｓ−で示される基を示し、Ｒ^２は１価炭化水素基；水酸基；−ＯＲ^３ａで示される基；−ＳＲ^３ｂで示される基；アシル基；アルコキシカルボニル基；ハロゲン原子；ニトロ基；シアノ基；メルカプト基；カルボキシ基；アミノ基；カルバモイル基；−ＮＨＲ^３ｃで示される基；−Ｎ（Ｒ^３ｄ）_２で示される基；（メタ）アクリロイルオキシ基；スルホ基；又は１価炭化水素基、−ＯＲ^３ａで示される基、−ＳＲ^３ｂで示される基、アシル基、アルコキシカルボニル基、−ＮＨＲ^３ｃで示される基、若しくは−Ｎ（Ｒ^３ｄ）_２で示される基に含まれる炭素原子に結合した水素原子の少なくとも一部が１価炭化水素基、水酸基、−ＯＲ^３ａで示される基、−ＳＲ^３ｂで示される基、アシル基、アルコキシカルボニル基、ハロゲン原子、ニトロ基、シアノ基、メルカプト基、カルボキシ基、アミノ基、カルバモイル基、−ＮＨＲ^３ｃで示される基、−Ｎ（Ｒ^３ｄ）_２で示される基、（メタ）アクリロイルオキシ基、メシルオキシ基、若しくはスルホ基で置換された基；を示し、Ｒ^３ａ〜Ｒ^３ｄは独立に１価炭化水素基を示し、ｍは０以上の整数を示す。）
［２］本発明の第二の態様は、上記［１］記載の硬化性組成物を硬化してなる光学部品である。 [1] A first aspect of the present invention is as follows: (A) a vinyl group-containing compound represented by the following formula (1); (B) a compound having at least two SiH groups in one molecule; And a hydrosilylation catalyst.

(Wherein W ¹ and W ² independently represent a group represented by the following formula (2), ring Y ¹ and ring Y ² represent the same or different aromatic hydrocarbon rings, and R represents a single bond; An 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— R ^1a and R ^1b independently represent a cyano group, a halogen atom, or a monovalent hydrocarbon group, and n1 and n2 independently represent an integer of 0 to 4. .)

(In the formula, ring Z represents an aromatic hydrocarbon ring, X represents a single bond or a group represented by —S—, R ² represents a monovalent hydrocarbon group; a hydroxyl group; a group represented by —OR ^3a ; groups represented by SR ^3b; 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 3c; -N (R 3d)}} 2 A (meth) acryloyloxy group; a sulfo group; or a monovalent hydrocarbon group, a group represented by —OR ^3a , a group represented by —SR ^3b , an acyl group, an alkoxycarbonyl group, or —NHR ^3c Or at least part of the hydrogen atoms bonded to the carbon atom contained in the group represented by —N (R ^3d ) ₂ are a monovalent hydrocarbon group, a hydroxyl group, a group represented by —OR ^3a , and —SR ^3b Shown That group, 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 ^3c, a group represented by ^{-N (R} _{3d) 2} And a group substituted with a (meth) acryloyloxy group, a mesyloxy group, or a sulfo group; R ^{3a to} R ^3d independently represent a monovalent hydrocarbon group, and m represents an integer of 0 or more.)
[2] A second aspect of the present invention is an optical component obtained by curing the curable composition according to the above [1].

  ADVANTAGE OF THE INVENTION According to this invention, the curable composition which gives the hardened | cured material which has a high refractive index and high heat resistance, and the optical component formed by hardening | curing the said curable composition can be provided.

[Curable composition]
The curable composition of the present invention comprises (A) a vinyl group-containing compound represented by the above formula (1), (B) a compound having at least two SiH groups in one molecule, and (C) a hydrosilylation catalyst. And containing. Hereinafter, each component contained in the curable composition of the present invention will be described in detail.

[(A) Vinyl group-containing compound represented by formula (1)]
The vinyl group-containing compound contained in the curable composition of the present invention is represented by the following formula (1). In the present specification, the “vinyl group-containing compound represented by the formula (1)” may be referred to as “vinyl group-containing compound (A)” or “(A) component”. The said vinyl group containing compound (A) can be used individually or in combination of 2 or more types.

In the above formula (1), W ¹ and W ² independently represent a group represented by the following formula (2).

In the above formula (2), examples of the ring Z include a benzene ring, a condensed polycyclic aromatic hydrocarbon ring [for example, a condensed bicyclic hydrocarbon ring (for example, a C _8-20 condensed bicyclic ring such as a naphthalene ring). Condensed hydrocarbon rings, preferably C _10-16 condensed bicyclic hydrocarbon rings), condensed tricyclic aromatic hydrocarbon rings (eg, anthracene ring, phenanthrene ring, etc.), etc. Hydrogen ring] and the like. Ring Z is preferably a benzene ring or a naphthalene ring, and more preferably a naphthalene ring. Ring Z contained in W ¹ and ring Z contained in W ² may be the same or different. For example, one ring may be a benzene ring, the other ring may be a naphthalene ring, etc. It is particularly preferable that the ring is a naphthalene ring. The substitution position of the ring Z which both W ¹ and W ² are bonded via X to the carbon atoms directly connected is not particularly limited. For example, when the ring Z is a naphthalene ring, the group corresponding to the ring Z bonded to the carbon atom may be a 1-naphthyl group, a 2-naphthyl group, or the like.

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

In the above formula (2), R ² is, 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, a butyl group, preferably a C _1-8 alkyl group). More preferably a C _1-6 alkyl group, etc.), a cycloalkyl group (C _5-10 cycloalkyl group such as a cyclohexyl group, preferably a C _5-8 cycloalkyl group, more preferably a C _5-6 cycloalkyl group). Group), aryl group (for example, C _6-14 aryl group such as phenyl group, tolyl group, xylyl group, naphthyl group, preferably C _6-10 aryl group, more preferably C _6-8 aryl group), hydroxyl; alkoxy group (methoxy group, an aralkyl group monovalent hydrocarbon group, (benzyl, _{C 6-10} aryl _{-C 1-4} alkyl group such as a phenethyl group) Butoxy group, a propoxy group, _{C 1-12} alkoxy group or a butoxy group, preferably a _{C 1-8} alkoxy group, more preferably a _{C 1-6} alkoxy group, etc.), _{C 5,} such as a cycloalkoxy group (hexyloxy group cycloheteroalkyl _-10 cycloalkoxy groups, etc.), aryloxy groups (C _6-10 aryloxy groups such as phenoxy groups), aralkyloxy groups (for example, C _6-10 aryl-C _1-4 alkyloxy groups such as benzyloxy groups) A group represented by —OR ^3a such as R ^3a represents a monovalent hydrocarbon group (such as the monovalent hydrocarbon group exemplified above). An alkylthio group (a C _1-12 alkylthio group such as a methylthio group, an ethylthio group, a propylthio group or a butylthio group, preferably a C _1-8 alkylthio group, more preferably a C _1-6 alkylthio group), a cycloalkylthio group ( C _5-10 cycloalkylthio group such as cyclohexylthio group), arylthio group (C _6-10 arylthio group such as phenylthio group), aralkylthio group (for example, C _6-10 aryl-C ₁₋ such as benzylthio group) _A group represented by —SR ^3b such as ( ₄ alkylthio group) [wherein R ^3b represents a monovalent hydrocarbon group (such as the monovalent hydrocarbon group exemplified above)]. An acyl group (a C _1-6 acyl group such as an acetyl group); an alkoxycarbonyl group (a C _1-4 alkoxy-carbonyl group such as a methoxycarbonyl group); a halogen atom (a fluorine atom, a chlorine atom, a bromine atom, Nitro group; cyano group; mercapto group; carboxy group; amino group; carbamoyl group; alkylamino group (C _1-12 alkylamino such as methylamino group, ethylamino group, propylamino group, butylamino group) Group, preferably C _1-8 alkylamino group, more preferably C _1-6 alkylamino group, etc.), cycloalkylamino group (C _5-10 cycloalkylamino group such as cyclohexylamino group), arylamino group (C _6-10 arylamino group such as phenylamino group), aralkylamino group (for example, benzylamino group) A group represented by —NHR ^3c such as a C _6-10 aryl-C _1-4 alkylamino group such as a non-group [wherein R ^3c is a monovalent hydrocarbon group (such as the monovalent hydrocarbon group exemplified above)] Indicates. Dialkylamino group (di (C _1-12 alkyl) amino group such as dimethylamino group, diethylamino group, dipropylamino group, dibutylamino group, preferably di (C _1-8 alkyl) amino group, more preferably Di (C _1-6 alkyl) amino group etc.), dicycloalkylamino group (di (C _5-10 cycloalkyl) amino group such as dicyclohexylamino group), diarylamino group (diphenylamino group etc. C _6-10 aryl) amino group), diaralkylamino group (for example, di (C _6-10 aryl-C _1-4 alkyl) amino group such as dibenzylamino group) and the like —N (R ^3d ) ₂ [In the formula, R ^3d independently represents a monovalent hydrocarbon group (such as the monovalent hydrocarbon group exemplified above)]. A (meth) acryloyloxy group; a sulfo group; a monovalent hydrocarbon group, a group represented by —OR ^3a , a group represented by —SR ^3b , an acyl group, an alkoxycarbonyl group, a group represented by —NHR ^3c Or at least a part of the hydrogen atoms bonded to the carbon atom contained in the group represented by -N (R ^3d ) ₂ is the above monovalent hydrocarbon group, hydroxyl group, group represented by -OR ^3a , or -SR ^3b A group represented by the following formula: an acyl group, an alkoxycarbonyl group, a halogen atom, a nitro group, a cyano group, a mercapto group, a carboxy group, an amino group, a carbamoyl group, a group represented by -NHR ^3c , represented by -N (R ^3d ) ₂ A group substituted with a group, a (meth) acryloyloxy group, a mesyloxy group, or a sulfo group [for example, an alkoxyaryl group (for example, a methoxyphenyl group, etc. _1-4 alkoxy _{C 6-10} aryl group), an alkoxycarbonyl aryl group (e.g., methoxycarbonyl phenyl group, _{C 1-4} alkoxy such as ethoxy carbonyl phenyl - carbonyl _{C 6-10} aryl group)], and the like .

Among these, R ² is typically a monovalent hydrocarbon group, a group represented by —OR ^3a , a group represented by —SR ^3b , an acyl group, an alkoxycarbonyl group, a halogen atom, a nitro group, or a cyano group. , A group represented by -NHR ^3c , a group represented by -N (R ^3d ) ₂ , or the like.

Preferable R ² is a monovalent hydrocarbon group [eg, alkyl group (eg, C _1-6 alkyl group), cycloalkyl group (eg, C _5-8 cycloalkyl group), aryl group (eg, C _{6-6 10} aryl group), aralkyl group (for example, C _6-8 aryl-C _1-2 alkyl group) and the like], alkoxy group (C _1-4 alkoxy group and the like) and the like. In particular, R ² represents a monovalent hydrocarbon group (particularly an alkyl group [C _1-4 alkyl group (particularly methyl group) etc.)] or an aryl group [eg C _6-10 aryl group (particularly phenyl group)]. And an alkyl group).

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

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

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

In the above 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, -O A group represented by-, a group represented by -NH-, or a group represented by -S- is typically represented by a single bond. Here, as the substituent, for example, a cyano group, a halogen atom (fluorine atom, chlorine atom, bromine atom, etc.), a monovalent hydrocarbon group [for example, an alkyl group (methyl group, ethyl group, propyl group, isopropyl group, Butyl group, C _1-6 alkyl group such as t-butyl group), aryl group (C _6-10 aryl group such as phenyl group) and the like], and the hetero atom includes, for example, oxygen atom, nitrogen atom , Sulfur atom, silicon atom and the like.

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

Since the compound represented by the above formula (1) has a vinyloxy group while maintaining excellent optical properties and thermal properties, it has high reactivity. In particular, when ring Y ¹ and ring Y ² are benzene rings and R is a single bond, the compound represented by the above formula (1) has a fluorene skeleton, and further improves optical characteristics and thermal characteristics. Excellent. The compound represented by the above formula (1) can be suitably used as a crosslinking agent because two vinyl groups contained in the form of a vinyloxy group can react with different molecules. The compound represented by the above formula (1) gives a cured product having high hardness and is preferable as a base component in the composition. The compound represented by the above formula (1) can be used for optical members; optical materials such as optical fibers, optical waveguides, prism sheets, holograms, high refractive films, retroreflective films, and the like.

As described above, when ring Y ¹ and ring Y ² are benzene rings and R is a single bond, the compound represented by the general formula (1) has a fluorene skeleton, and has light transmittance and refractive index. It is preferable because it is further excellent in optical characteristics and thermal characteristics. The compound represented by the general formula (1), since the vinyloxy groups are bonded directly in the general formula (2) as W ¹ and W ^2, in particular, optical and thermal properties are markedly improved This is preferable. When X in the general formula (2) is a single bond, optical characteristics such as light transmittance and refractive index tend to be more excellent.

Among the compounds represented by the above formula (1), particularly preferred specific examples include compounds represented by the following formulas.

  The content of the vinyl group-containing compound represented by the above formula (1) is preferably 1 to 95% by mass, and 3 to 80% by mass with respect to the solid content of the curable composition of the present invention. It is more preferable, and it is still more preferable that it is 5-50 mass%. When the content of the vinyl group-containing compound is within the above range, the resulting composition is excellent in curability, and a cured product having a high refractive index and high heat resistance is easily obtained.

[Method for Producing Vinyl Group-Containing Compound (A) Represented by Formula (1)]
The vinyl group-containing compound (A) represented by the above formula (1) can be produced, for example, by the following production methods 1 to 3.

・ Production method 1
The vinyl group-containing compound (A) represented by the above formula (1) is prepared by the following formula (13) in the presence of a transition element compound catalyst and an inorganic base, for example, according to the production method described in JP-A-2008-266169. It can synthesize | combine by making the vinyl ester compound represented by these, and the hydroxyl-containing compound represented by following formula (3) react. 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. Specifically, the vinyl group-containing compound (A) represented by the above formula (1) can be synthesized as in Synthesis Examples 1 and 2 described later.

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

（式中、Ｗ^３及びＷ^４は独立に下記式（４）で表される基を示し、環Ｙ^１、環Ｙ^２、Ｒ、Ｒ^１ａ、Ｒ^１ｂ、ｎ１、及びｎ２は上記のとおりである。）

(Wherein W ³ and W ^{4 each} independently represent a group represented by the following formula (4), and ring Y ¹ , ring Y ² , R, R ^1a , R ^1b , n1 and n2 are as described above. is there.)

（式中、環Ｚ、Ｘ、Ｒ^２、及びｍは上記のとおりである。）

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

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

（式中、環Ｙ^１、環Ｙ^２、環Ｚ、Ｒ、Ｒ^２、Ｒ^１ａ、Ｒ^１ｂ、ｍ、ｎ１、及びｎ２は上記のとおりである。）

(In the formula, ring Y ¹ , ring Y ² , ring Z, R, R ² , R ^1a , R ^1b , m, n1, and n2 are as described above.)

  Examples of the acid catalyst used in the synthesis of the hydroxyl group-containing compound represented by the above formula (3), reaction conditions, and the like are disclosed in, for example, JP-A-2011-201791 and JP-A-2002-255929. What is described that it can be used for the manufacturing method of the described fluorene type compound is mentioned.

・ Production method 2
The vinyl group-containing compound (A) represented by the above formula (1) is, for example, from the hydroxyl group-containing compound represented by the above formula (3) via the leaving group-containing compound represented by the following formula (5). And it can also synthesize | combine with the manufacturing method including obtaining the vinyl group containing compound (A) represented by the said Formula (1).

（式中、Ｗ^５及びＷ^６は独立に下記式（６）で表される基を示し、環Ｙ^１、環Ｙ^２、Ｒ、Ｒ^１ａ、Ｒ^１ｂ、ｎ１、及びｎ２は上記のとおりである。）

(Wherein W ⁵ and W ⁶ independently represent a group represented by the following formula (6), and ring Y ¹ , ring Y ² , R, R ^1a , R ^1b , n1 and n2 are as described above. is there.)

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

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

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

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

・ Production method 3
The vinyl group-containing compound (A) represented by the above formula (1) is, for example, from a hydroxyalkyloxy group-containing compound represented by the following formula (7), which contains a leaving group represented by the above formula (5). It can also synthesize | combine with the manufacturing method including obtaining the vinyl group containing compound (A) represented by the said Formula (1) via a compound.

（式中、Ｗ^７及びＷ^８は独立に下記式（８）で表される基を示し、環Ｙ^１、環Ｙ^２、Ｒ、Ｒ^１ａ、Ｒ^１ｂ、ｎ１、及びｎ２は上記のとおりである。）

(Wherein W ⁷ and W ⁸ independently represent a group represented by the following formula (8), and ring Y ¹ , ring Y ² , R, R ^1a , R ^1b , n1 and n2 are as described above. is there.)

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

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

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

（式中、環Ｚ、Ｒ^２、ｌ及びｍは上記のとおりである。）

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

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

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

[(B) Compound having at least two SiH groups in one molecule]
The curable composition of the present invention contains a compound having at least two SiH groups in one molecule. In the present specification, the “compound having at least two SiH groups in one molecule” may be referred to as “compound (B)” or “component (B)”. By reacting this compound (B) with the vinyl group-containing compound (A) represented by the above formula (1), a cured product having a high refractive index and high heat resistance and excellent optical characteristics is formed. The The said compound (B) can be used individually or in combination of 2 or more types.

The compound (B) having at least two SiH groups in one molecule is not particularly limited, but is preferably an organosiloxane compound having at least two SiH groups in one molecule.
The organosiloxane compound having at least two SiH groups in one molecule is not particularly limited. For example, the main chain in a cyclic compound or a linear or branched chain compound is composed only of a siloxane unit (—Si—O—). It is preferable that it is the comprised organosiloxane (B1).
In the present specification, the “main chain” for the organosiloxane compound means a chain that causes the cyclic compound to be cyclic, and a chain that causes the linear or branched chain compound to be linear or branched, In a compound having both a cyclic part and a chain part, it means a chain composed of a chain that makes the cyclic part cyclic and a chain that makes the chain part chain. In the present specification, the “chain” means a part composed of a bond connecting at least two adjacent atoms and the atom in the compound. For example, in the case of a linear organosiloxane represented by the following formula (21), the “main chain” is —Si—O— (Si—O) _y —Si— (y is as described below. ).

（式中、Ｒ^４は水素原子又は炭素数１〜５０の一価の有機基であり、Ｒ^５は一価の有機基であり、ｘは０〜２の整数を示す。）
上記加水分解縮合物（Ｂ１ａ）は、上述した、主鎖がシロキサン単位（−Ｓｉ−Ｏ−）のみから構成されるオルガノシロキサン（Ｂ１）に属する。 The organosiloxane compound having at least two SiH groups in one molecule is obtained by hydrolytic condensation of one or more organosilanes represented by the following formula (20), and has at least 2 SiH groups in one molecule. A hydrolytic condensate (B1a) having at least one monovalent organic group having 1 to 50 carbon atoms derived from R ⁴ below in one molecule is preferable.

(Wherein R ⁴ is a hydrogen atom or a monovalent organic group having 1 to 50 carbon atoms, R ⁵ is a monovalent organic group, and x represents an integer of 0 to 2)
The hydrolysis-condensation product (B1a) belongs to the organosiloxane (B1) whose main chain is composed of only the siloxane unit (—Si—O—).

Here, examples of the monovalent organic group include an alkyl group, an aryl group, an allyl group, and a glycidyl group, and among them, an alkyl group and an aryl group are preferable.
The monovalent organic group having 1 to 50 carbon atoms as R ⁴ is preferably an alkyl group or aryl group having 1 to 20 carbon atoms.
As carbon number of an alkyl group, 1-5 are preferable, and a methyl group, an ethyl group, a propyl group, a butyl group etc. are mentioned as a specific alkyl group. The alkyl group may be linear or branched, and the hydrogen atom of the alkyl group may be substituted with a fluorine atom. As an aryl group, a C6-C20 thing is preferable, for example, a phenyl group, a naphthyl group, etc. are mentioned.

  Specific examples of the organosilane represented by the above formula (20) include the following compounds.

((20-1) when x = 0)
When x = 0, examples of the organosilane represented by the above formula (20) include tetraalkoxysilanes such as tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, and tetrabutoxysilane.

(20-2) When x = 1
When x = 1, examples of the organosilane represented by the above formula (20) include trialkoxysilanes such as trimethoxysilane, triethoxysilane, and tripropoxysilane; monomethyltrimethoxysilane, monomethyltriethoxysilane, monomethyltrimethyl Monoalkyltrialkoxysilanes such as propoxysilane, monoethyltrimethoxysilane, monoethyltriethoxysilane, monoethyltripropoxysilane, monopropyltrimethoxysilane, monopropyltriethoxysilane; monophenyltrimethoxysilane, monophenyltriethoxy Examples include monophenyltrialkoxysilane such as silane.

((20-3) when x = 2)
When x = 2, examples of the organosilane represented by the above formula (20) include dialkoxysilanes such as dimethoxysilane, diethoxysilane, and dipropoxysilane; monomethyldimethoxysilane, monomethyldiethoxysilane, and monomethyldipropoxysilane Monoalkyldialkoxysilanes such as monoethyldimethoxysilane, monoethyldiethoxysilane, monoethyldipropoxysilane, monopropyldimethoxysilane, monopropyldiethoxysilane, monopropyldipropoxysilane; dimethyldimethoxysilane, dimethyldiethoxysilane , Dimethyldipropoxysilane, diethyldimethoxysilane, diethyldiethoxysilane, diethyldipropoxysilane, dipropyldimethoxysilane, dipropyldiethoxysilane, dip Dialkyl dialkoxy silanes such as pills dipropoxy silane; diphenyldimethoxysilane, such as diphenyl dialkoxysilane such as diphenyl diethoxy silane.

  As said hydrolysis-condensation product (B1a), the 2-1000mer of organosilane represented by the said Formula (20) is preferable, a 2-100mer is more preferable, a 2-10mer is further more preferable, 2 The ˜hexamer is particularly preferred.

As the organosilane represented by the above formula (20), it is preferable to use a mixture of x = 2 compound and x = 3 compound or x = 2 compound, and in particular, dialkyl dialkoxy. Silane and diphenyl dialkoxysilane are more preferably used, and dimethyldimethoxysilane and diphenyldimethoxysilane are more preferably used.
In addition, as the hydrolysis condensate (B1a), a main chain composed of a siloxane bond (Si—O—Si) formed by hydrolysis condensation of the organosilane represented by the above formula (20) is a chain. Either a chain-like organosilane or a cyclic organosilane that is cyclic may be used. The chain organosilane may be either linear or branched, but is preferably a linear organosilane from the viewpoint of compatibility with the vinyl group-containing compound (A).

（式中、Ｒ^６及びＲ^７は、それぞれ同一若しくは異なって、水素原子又は炭素数１〜５０の一価の有機基であり、Ｒ^６及びＲ^７のうち少なくとも２個は水素原子である。ｙは０〜１０００の整数を示す。）
Ｒ^６及びＲ^７としては、特に限定されないが、例えば、上述のＲ^４と同様である。 Of the organosiloxane compounds having at least two SiH groups in one molecule, examples of the linear compounds include linear organosiloxanes represented by the following formula (21).

(In formula, R < ⁶ > and R < ⁷ > are the same or different, respectively, and are a hydrogen atom or a C1-C50 monovalent organic group, and at least 2 is a hydrogen atom among R < ⁶ > and R < ⁷ >. y represents an integer of 0 to 1000.)
The R ⁶ and ^{R 7,} not particularly limited, for example, is the same as ^{R 4} above.

（式中、Ｒ^８は、それぞれ同一若しくは異なって、水素原子又は炭素数１〜６の有機基であり、それぞれのＲ^８のうち少なくとも２個は水素原子である。ｚは２〜１０の整数を示す。）
上記式（２２）におけるＲ^８としては、炭素原子、水素原子及び酸素原子から構成される炭素数１〜６の有機基であることが好ましく、炭素数１〜６の炭化水素基であることがより好ましく、炭素数１〜６のアルキル基であることが更に好ましい。また、ｚは３〜１０の整数であることが好ましい。 Of the organosiloxane compounds having at least two SiH groups in one molecule, examples of the cyclic compound include cyclic organosiloxanes represented by the following formula (22).

(Wherein, R ⁸ are the same or different and each is a hydrogen atom or an organic group having 1 to 6 carbon atoms, .z at least two hydrogen atoms of each of R ⁸ is 2-10 integer Is shown.)
R ⁸ in the above formula (22) is preferably an organic group having 1 to 6 carbon atoms composed of a carbon atom, a hydrogen atom and an oxygen atom, and preferably a hydrocarbon group having 1 to 6 carbon atoms. More preferably, it is a C1-C6 alkyl group. Moreover, it is preferable that z is an integer of 3-10.

  Examples of the cyclic organosiloxane represented by the above formula (22) include 1,3,5-trimethylcyclotrisiloxane, 1,3,5,7-tetramethylcyclotetrasiloxane, 1,3,5,7,9- Pentamethylcyclopentasiloxane is preferred.

The linear organosiloxane represented by the above formula (21) and the cyclic organosiloxane represented by the above formula (22) are obtained by hydrolytic condensation of the organosilane represented by the above formula (20). However, there are some commercially available products.
The hydrolytic condensation reaction of the organosilane represented by the above formula (20) is not particularly limited, but can be performed, for example, by a conventional method, and after the organosilane is introduced into an organic solvent, the organosilane is hydrolyzed. Therefore, it is preferable to add water for reaction in the presence of an acid catalyst or a base catalyst.

  From the viewpoint of availability, the compound (B) having at least two SiH groups in one molecule is a chain and / or cyclic and / or network organosiloxane having at least two SiH groups in one molecule. Is preferred. From the viewpoint of compatibility with the vinyl group-containing compound (A), a cyclic organosiloxane having at least two SiH groups in one molecule or a linear organosiloxane having a molecular weight of 10,000 or less is preferable. From the viewpoint of heat resistance, a cyclic organosiloxane having at least 3 SiH groups in one molecule is preferable.

  As the compound (B) having at least two SiH groups in one molecule, a compound (b1) having at least two carbon-carbon double bonds reactive with the SiH group in one molecule, and an SiH group It is preferable that it is a compound (B2) obtained by a hydrosilylation reaction with an organosiloxane compound (b2) having at least two per molecule and having at least two SiH groups per molecule.

  The compound (b1) having at least two carbon-carbon double bonds having reactivity with SiH groups in one molecule is at least two carbon-carbon double bonds having reactivity with SiH groups in one molecule. Although it will not specifically limit if it is an organic compound which has, For example, what consists of an organic skeleton part and the group which has a carbon-carbon double bond reactive with SiH group covalently bonded to the organic skeleton part is mentioned. It is done. The group having a carbon-carbon double bond reactive with the SiH group may be covalently bonded to any part of the organic skeleton.

（式中、Ｒ^９は水素原子又はメチル基である。）
得られる硬化物の耐熱性の高さの観点から、下記式（２４）で表されるアルケニル基が好ましい。

（式中、Ｒ^１０及びＲ^１１は、同一若しくは異なって、水素原子又はメチル基である。） The carbon-carbon double bond having reactivity with the SiH group in the compound (b1) is not particularly limited as long as it has reactivity with the SiH group. For example, the viewpoint of easy availability of raw materials To an alkenyl group represented by the following formula (23):

(In the formula, R ⁹ is a hydrogen atom or a methyl group.)
From the viewpoint of high heat resistance of the resulting cured product, an alkenyl group represented by the following formula (24) is preferable.

(Wherein R ¹⁰ and R ¹¹ are the same or different and are a hydrogen atom or a methyl group.)

The alkenyl group represented by the above formula (23) is preferably H ₂ C═CH— from the viewpoint of high reactivity.
Examples of the carbon-carbon double bond having reactivity with the SiH group in the compound (b1) include a vinyl group, an allyl group, an acrylic group, a phenoxyethylacryl group, a phenoxyethylvinyl group, a phenoxyethylallyl group, and a phenoxyacrylic group. Group, phenoxyvinyl group and phenoxyallyl group are more preferred.

（式中、Ｒ^１２は、同一又は異なって、エチレン性の不飽和結合を有する基を示す。） The compound (b1) having at least two carbon-carbon double bonds having reactivity with SiH groups in one molecule is at least two carbon-carbon double bonds having reactivity with SiH groups in one molecule. The fluorene compound etc. which have are mentioned, The fluorene compound represented by following formula (25) is preferable.

(In formula, R <^12> is the same or different and shows group which has an ethylenically unsaturated bond.)

  As a carbon-carbon double bond having reactivity with the SiH group, the fluorene compound represented by the above formula (25) has a vinyl group, an allyl group, a phenoxyethylvinyl group, and a phenoxyethylallyl group from the viewpoint of reactivity. , A phenoxyvinyl group and a phenoxyallyl group are preferable.

As the fluorene compound represented by the above formula (25), for example, the vinyl group-containing compound (A) represented by the above formula (1) can be used.
As the fluorene compound represented by the above formula (25), divinyl fluorene, diallyl fluorene, fluorene bisphenoxyethyl acrylate, fluorene bisphenoxyethyl vinyl ether, fluorene bisphenoxyethyl allyl ether, fluorene bis, from the viewpoint of high refractive index. Phenoxy acrylate, fluorene bisphenoxy vinyl, and fluorene bis phenoxy allyl are preferable. From the viewpoint of reactivity, divinyl fluorene, diallyl fluorene, fluorene bisphenoxy ethyl vinyl ether, fluorene bisphenoxy ethyl allyl ether, fluorene bisphenoxy vinyl, fluorene bisphenoxy Allyl is preferred.

  The organosiloxane compound (b2) having at least two SiH groups in one molecule is not particularly limited. For example, the above-described organosiloxane having a main chain composed only of a siloxane unit (-Si-O-) ( B1) and the like, and the organosiloxane (B1) may be either a cyclic organosiloxane or a linear or branched chain organosiloxane, especially from the viewpoint of a high refractive index. Cyclic organosiloxane is preferable, and cyclic organosiloxane represented by the above formula (22) is more preferable.

  Hydrosilylation reaction between a compound (b1) having at least two carbon-carbon double bonds having reactivity with SiH groups and an organosiloxane compound (b2) having at least two SiH groups in one molecule There is no particular limitation. The mixing ratio of the compound (b1) and the organosiloxane compound (b2) is not particularly limited as long as at least two SiH groups remain in one molecule after the hydrosilylation reaction, but the strength of the obtained cured product From the viewpoint of the above, the number of moles (X) of the carbon-carbon double bond having reactivity with the SiH group in the compound (b1) and the number of moles (Y) of the SiH group in the organosiloxane compound (b2) The ratio is preferably Y / X ≧ 2, and more preferably Y / X ≧ 3. The preferable ratio of Y / X can also be applied when the fluorene compound represented by the above formula (25) is used as the compound (b1).

  As the compound (B) having at least two SiH groups in one molecule as described above, a reaction product of bisphenol fluorene allyl ether and 1,3,5,7-tetramethylcyclotetrasiloxane, A reactant of 1,3,5,7-tetramethylcyclotetrasiloxane is preferred.

  The compound (B) having at least two SiH groups in one molecule can be used alone or in combination of two or more. In addition, the compound (B) has the above-described compound (b1) having at least two carbon-carbon double bonds having reactivity with the SiH group, and at least two SiH groups in one molecule. When it is a compound (B2) obtained by hydrosilylation reaction with an organosiloxane compound (b2) and having at least two SiH groups in one molecule, the compound (b1) and / or the organosiloxane compound (b2) ) Can be used alone or in admixture of two or more.

  When the compound (b1) and the organosiloxane compound (b2) are hydrosilylated, an appropriate catalyst may be used. As the catalyst, for example, a hydrosilylation catalyst (C) described later can be used, and the addition amount, cocatalyst, reaction conditions, and the like are described later with the vinyl group-containing compound (A) represented by the formula (1). The hydrosilylation reaction with the compound (B) having at least two SiH groups in one molecule can be set.

However, the temperature of the reaction for hydrosilylating the compound (b1) and the organosiloxane compound (b2) can be variously set, but the lower limit is preferably 30 ° C, more preferably 50 ° C, and the upper limit is preferably 200 ° C. 150 ° C. is more preferable.
If the reaction temperature is not less than the above lower limit, the reaction time for sufficient reaction tends not to be too long, and if it is not more than the above upper limit, it is often industrially advantageous.
The reaction may be carried out at a constant temperature, and the temperature may be changed in multiple steps or continuously as required.

[(C) Hydrosilylation catalyst]
The curable composition of the present invention contains a hydrosilylation catalyst (C).
The hydrosilylation catalyst (C) is not particularly limited as long as it has a catalytic activity for the hydrosilylation reaction. For example, platinum alone; solid platinum supported on a support such as alumina, silica, carbon black; chloroplatinic acid Complexes of chloroplatinic acid with alcohols, aldehydes, ketones, etc .; platinum-olefin complexes (eg, Pt (CH ₂ ═CH ₂ ) ₂ (PPh ₃ ) ₂ , Pt (CH ₂ ═CH ₂ ) ₂ Cl ₂ ); Platinum-vinylsiloxane complexes (eg, Pt (ViMe ₂ SiOSiMe ₂ Vi) _a , Pt [(MeViSiO) ₄ ] _b ); platinum-phosphine complexes (eg, Pt (PPh ₃ ) ₄ , Pt (PBu ₃ ) ₄ ); platinum - phosphite complex _{(e.g., Pt [P (OPh) 3} ] 4, Pt [P (OBu) 3] 4) ( in the formula, Me represents methylcarbamoyl Group, Bu is a butyl group, Vi is a vinyl group, Ph is a phenyl group, and a and b are integers.); Dicarbonyldichloroplatinum; Karlstedt catalyst; Ashby US Pat. No. 3,159,601 And platinum-hydrocarbon composites described in US Pat. No. 3,159,662; platinum alcoholate catalysts described in US Pat. No. 3,220,972 to Lamoreaux. In addition, platinum chloride-olefin complexes described in Modic US Pat. No. 3,516,946 are also useful in the present invention.

The catalyst other than the platinum compound as the hydrosilylation catalyst (C) is not particularly limited. For example, RhCl (PPh) ₃ , RhCl ₃ , RhAl ₂ O ₃ , RuCl ₃ , IrCl ₃ , FeCl ₃ , AlCl ₃ , PdCl ₂ .2H ₂ O, NiCl ₂ , TiCl _{4 and the} like can be mentioned.

As the hydrosilylation catalyst (C), chloroplatinic acid, a platinum-olefin complex, and a platinum-vinylsiloxane complex are preferable from the viewpoint of catalytic activity.
A hydrosilylation catalyst (C) may be used independently and may use 2 or more types together.

The addition amount of the hydrosilylation catalyst (C) is not particularly limited, but it is a compound having at least two SiH groups in one molecule from the viewpoint of sufficient curability and relatively low cost of the curable composition. The lower limit is preferably 10 ^-10 mol, more preferably 10 ^-8 mol, and the upper limit is preferably 10 ^-1 mol, more preferably 10 ^-3 mol, per 1 mol of SiH group (B).
The addition amount of the hydrosilylation catalyst (C) is 0.00001 to 10 parts by mass with respect to 100 parts by mass of [(A) component + (B) component]. (C) If the component is 3 parts by mass or less, and the glass transition temperature of the cured product obtained by curing the curable composition is otherwise the same as the curable composition of the present invention, the heat resistance is low, Moreover, there exists a possibility that the material intensity | strength of hardened | cured material may become low. If the material strength of the cured product is low, cracks are likely to occur.

A cocatalyst can be used in combination with the hydrosilylation catalyst (C). The co-catalyst is not particularly limited, but examples thereof include phosphorus compounds such as triphenylphosphine, 1,2-diester compounds such as dimethyl malate, and acetylene alcohols such as 2-hydroxy-2-methyl-1-butyne. Compounds, sulfur compounds such as simple sulfur, and amine compounds such as triethylamine are exemplified. The addition amount of the co-catalyst is not particularly limited, towards hydrosilylation catalyst 1 mol, preferably 10 ^-2 mol as the lower limit, more preferably 10 ^-1 mol, preferably 10 ² mol upper limit, 10 mole Is more preferable.

The addition amount of the co-catalyst is not particularly limited with respect to the hydrosilylation catalyst (C) 1 mol, preferably 10 ^-5 moles as the lower limit, more preferably 10 ^-3 moles, preferably 10 ² mol upper limit, 10 moles is more preferred.

（式中、Ｒ^１２は、同一又は異なって、エチレン性の不飽和結合を有する基を示し、Ｒ^１３は、−Ｏ−、−ＣＨ_２−、−Ｃ（ＣＨ_３）_２−、−Ｃ（ＣＦ_３）_２−及び−Ｓ（＝Ｏ）_２−から選択される２価の基を示し、ｐ及びｑは、０〜４の整数を示す。） The curable composition of the present invention may further contain at least one of compounds represented by the following formulas (26) to (28).

(In the formula, R ¹² is the same or different and represents a group having an ethylenically unsaturated bond, and R ¹³ represents —O—, —CH ₂ —, —C (CH ₃ ) ₂ —, —C ( A divalent group selected from CF ₃ ) ₂ — and —S (═O) ₂ —, and p and q represent an integer of 0 to 4.)

R ¹² of the compounds represented by the above formulas (26) to (28) is not particularly limited as long as it is a group having a carbon-carbon double bond. For example, a vinyl group, an allyl group, a methallyl group, an acrylic group Group, a methacryl group, etc. are mentioned, and a vinyl group, an allyl group, and a methallyl group are preferable from a reactive viewpoint.

  The molecular weight of the compounds represented by the above formulas (26) to (28) is not particularly limited, but is preferably 50,000 or less from the viewpoint of handleability. In the present specification, the molecular weight indicates a number average molecular weight in terms of polystyrene by GPC.

Although it does not specifically limit as a compound represented by the said Formula (26), For example, it represents to a triallyl isocyanurate, a diallyl monoglycidyl isocyanurate, a tris (2-acryloyloxyethyl) isocyanurate etc. from a heat resistant viewpoint. Isocyanurate derivatives, and the like, which can be represented by the following structural formula, for example.

  As the compound represented by the above formula (26), triallyl isocyanurate and diallyl monoglycidyl isocyanurate are preferable from the viewpoint of availability.

（式中、Ｒ^１３は、上記のとおりである。） Although it does not specifically limit as a compound represented by the said Formula (27), For example, the bisphenol derivative represented by bisphenol F diallyl ether, bisphenol A diallyl ether, bisphenol S diallyl ether, etc. are mentioned from a viewpoint of availability. For example, it can be represented by the following structural formula.

(Wherein R ¹³ is as described above.)

  As the compound represented by the above formula (27), bisphenol A diallyl ether and bisphenol S diallyl ether are preferable from the viewpoint of heat resistance.

  Examples of the compound represented by the formula (28) include divinylbenzenes (having a purity of 50 to 100%, preferably having a purity of 80 to 100%), divinylnaphthalene, and the like from the viewpoint of compatibility. From the viewpoint of refractive index, divinylbenzenes (having a purity of 80 to 100%) and divinylnaphthalene are preferred.

[Other additives]
A silanol condensation catalyst can be used for the purpose of improving the adhesion of the curable composition of the present invention to the substrate. The silanol condensation catalyst that can be used is not particularly limited, but specific examples include tri-2-ethylhexyl borate, normal trioctadecyl borate, trinormal octyl borate, triphenyl borate, trimethylene borate, tris (trimethylsilyl) borate. It is preferable to use trinormal butyl borate, tri-sec-butyl borate, tri-tert-butyl borate, triisopropyl borate, tripropylpropyl borate, triallyl borate, triethyl borate, trimethyl borate, boron methoxyethoxide, etc. it can.

  The curable composition of the present invention can also be improved in workability by adding a solvent to adjust the viscosity. Solvents that can be used are not particularly limited as long as they do not inhibit the hydrosilylation reaction. For example, hydrocarbon solvents such as benzene, toluene, hexane and heptane; tetrahydrofuran, 1,4-dioxane, 1,3-dioxolane, diethyl ether Ether solvents such as acetone, ketone solvents such as methyl ethyl ketone and cyclohexanone; ester solvents such as n-butyl acetate, ethyl cellosolve acetate, diethylene glycol monoethyl ether acetate and propylene glycol monomethyl ether acetate; chloroform, methylene chloride, 1, Examples include halogen solvents such as 2-dichloroethane, and toluene, tetrahydrofuran, 1,3-dioxolane, 1,4-dioxane, and chloroform are preferable. A solvent may be used independently and can also be used as 2 or more types of mixed solvents.

Although the usage-amount of a solvent is not specifically limited, In order to accelerate | stimulate reaction uniformly and, the quantity which can melt | dissolve the vinyl group containing compound (A) represented by Formula (1) completely is preferable. The solvent is preferably 20 parts by weight, more preferably 50 parts by weight, and the upper limit is preferably 500 parts by weight, more preferably 300 parts by weight with respect to 100 parts by weight of the vinyl group-containing compound (A).
The amount of the solvent used is preferably 0.1 parts by weight, more preferably 0.5 parts by weight, and more preferably 1 part by weight with respect to 100 parts by weight of [(A) component + (B) component]. More preferably, as an upper limit, 100 mass parts is preferable, 50 mass parts is more preferable, and 30 mass parts is still more preferable. If the amount of the solvent used is not less than the above lower limit, the effect of lowering the viscosity tends to be obtained, and if it is not more than the above upper limit, problems such as a decrease in heat resistance due to the solvent remaining in the material arise. It tends to be difficult and cost-effective.

  A curing retarder can be used for the purpose of improving the storage stability of the curable composition of the present invention or adjusting the reactivity of the hydrosilylation reaction. Examples of the curing retarder include a compound containing an aliphatic unsaturated bond, an organic phosphorus compound, an organic sulfur compound, a nitrogen-containing compound, a tin compound, and an organic peroxide. These may be used alone or in combination of two or more.

  Examples of the compound containing an aliphatic unsaturated bond include propargyl alcohols, ene-yne compounds, maleate esters and the like. Examples of the organophosphorus compounds include triorganophosphines, diorganophosphines, organophosphones, and triorganophosphites. Examples of the organic sulfur compound include organomercaptans, diorganosulfides, hydrogen sulfide, benzothiazole, thiazole, benzothiazole disulfide and the like. Examples of the nitrogen-containing compound include ammonia, primary alkylamines, arylamines, urea, hydrazine and the like. Examples of tin compounds include stannous halide dihydrate and stannous carboxylate. Examples of the organic peroxide include di-tert-butyl peroxide, dicumyl peroxide, benzoyl peroxide, and tert-butyl perbenzoate.

  Among these curing retarders, from the viewpoint of good retarding activity and good raw material availability, benzothiazole, thiazole, dimethyl malate, 3-hydroxy-3-methyl-1-butyne, 1-ethynyl-1- Cyclohexanol is preferred.

The addition amount of the curing retarder is preferably 10 ⁻¹ mol as the lower limit, more preferably 1 mol, more preferably 10 ³ mol, and 50 mol as the lower limit with respect to 1 mol of the hydrosilylation catalyst (C) used. More preferred.

  Various resins that can be added for the purpose of modifying the properties of the curable composition of the present invention include polycarbonate resin, polyethersulfone resin, polyarylate resin, epoxy resin, cyanate resin, phenol resin, acrylic resin, Examples include, but are not limited to, a polyimide resin, a polyvinyl acetal resin, a urethane resin, and a polyester resin.

  The curable composition of the present invention may be added with an inorganic filler as necessary. Addition of an inorganic filler is effective in increasing the strength of the material and improving flame retardancy. The inorganic filler is preferably in the form of fine particles, and includes ultrafine powder amorphous silica, hydrophobic ultrafine silica and the like.

  Examples of the method for adding the filler include hydrolyzable silane monomers or oligomers such as alkoxysilanes, acyloxysilanes, and halogenated silanes, and metal alkoxides, acyloxides, and halides such as titanium and aluminum. A method of adding an curable composition so as to contain it and reacting in the composition or a partial reaction product of the composition to form an inorganic filler in the composition is also included.

The curable composition obtained in the present invention may have an anti-aging agent added thereto. Examples of the anti-aging agent include citric acid, phosphoric acid, sulfur-based anti-aging agent and the like in addition to the anti-aging agents generally used such as hindered phenol type.
As the hindered phenol-based anti-aging agent, various types such as Irganox 1010 available from Ciba Specialty Chemicals are used.
Sulfur-based antioxidants include mercaptans, mercaptan salts, sulfide carboxylates, sulfides including hindered phenol sulfides, polysulfides, dithiocarboxylates, thioureas, thiophosphates, sulfonium Examples thereof include compounds, thioaldehydes, thioketones, mercaptals, mercaptols, monothioacids, polythioacids, thioamides, and sulfoxides.
Moreover, these anti-aging agents may be used independently and may be used together 2 or more types.

The curable composition of the present invention may be added with a radical inhibitor. Examples of the radical inhibitor include 2,6-di-t-butyl-3-methylphenol (BHT), 2,2′-methylene-bis (4-methyl-6-t-butylphenol), tetrakis (methylene- Phenol radical inhibitors such as 3 (3,5-di-t-butyl-4-hydroxyphenyl) propionate) methane, phenyl-β-naphthylamine, α-naphthylamine, N, N′-secondary butyl-p- Examples include amine radical inhibitors such as phenylenediamine, phenothiazine, N, N′-diphenyl-p-phenylenediamine, and the like.
Moreover, these radical inhibitors may be used alone or in combination of two or more.

The curable composition of the present invention may be added with an ultraviolet absorber. Examples of the ultraviolet absorber include 2 (2′-hydroxy-3 ′, 5′-di-t-butylphenyl) benzotriazole, bis (2,2,6,6-tetramethyl-4-piperidine) sebacate and the like. Can be mentioned.
Moreover, these ultraviolet absorbers may be used independently and may be used together 2 or more types.

  The curable composition of the present invention includes other flame retardants, surfactants, antifoaming agents, emulsifiers, leveling agents, anti-fogging agents, ion trapping agents such as antimony-bismuth, thixotropic agents, tackifiers, Ozone degradation inhibitor, light stabilizer, thickener, plasticizer, antioxidant, heat stabilizer, processing stabilizer, reactive diluent, antistatic agent, radiation blocking agent, nucleating agent, phosphorus peroxide decomposition Agents, lubricants, pigments, metal deactivators, adhesion-imparting agents, physical property modifiers and the like may be added within a range that does not impair the object and effect of the present invention.

[Method for preparing curable composition]
The curable composition of this invention is obtained by mixing said each component.

  Various methods can be used as a catalyst mixing method at the time of the reaction. A mixture of the vinyl group-containing compound (A) represented by the above formula (1) and the hydrosilylation catalyst (C) is used as a SiH group. A method of mixing the compound (B) having at least two in one molecule is preferable. In the method of mixing the hydrosilylation catalyst (C) with the mixture of the vinyl group-containing compound (A) and the compound (B), it may be difficult to control the reaction. Further, in the method of mixing the compound (B) and the hydrosilylation catalyst (C) with the vinyl group-containing compound (A), the compound (B) is mixed in the presence of the hydrosilylation catalyst (C). It may be altered due to its reactivity with moisture.

[Method of curing curable composition]
The method for curing the curable composition of the present invention is not particularly limited, but it can be cured by simply mixing the components, or can be cured by heating. From the viewpoint that a curing reaction is fast and generally a material having high heat resistance is easily obtained, a method of heating and curing is preferred.

The curing temperature can be variously set, but the lower limit is preferably 25 ° C, more preferably 50 ° C, still more preferably 100 ° C, the upper limit is preferably 300 ° C, more preferably 280 ° C, and further preferably 260 ° C. If the curing temperature is not less than the above lower limit, the time for sufficient curing tends not to be too long, and if it is not more than the above upper limit, thermal deterioration of the product tends not to occur.
Curing may be performed at a constant temperature, but the temperature may be changed in multiple steps or continuously as required. Rather than carrying out the reaction at a constant temperature, the reaction is preferably carried out while raising the temperature in a multistage manner or continuously in that a uniform cured product without distortion can be easily obtained.

  The pressure at the time of curing can also be variously set as required, and the reaction can be carried out at normal pressure, high pressure or reduced pressure.

  Various reaction times and pressures during the reaction can be set as required. The reaction time is not particularly limited. From an economic viewpoint, it is preferably within 20 hours, and more preferably within 10 hours. The pressure is also not particularly limited, but atmospheric pressure is preferably −5 MPa, more preferably atmospheric pressure−2 MPa from the viewpoint that a special apparatus is required and the operation becomes complicated.

  After the hydrosilylation reaction, an organic compound (α) containing one carbon-carbon double bond reactive with a solvent and / or an unreacted SiH group in one molecule and at least three SiH in one molecule The polyorganosiloxane (β) having a group can also be removed. By removing these volatile components, the problem of voids and cracks due to the volatilization of the volatile components is less likely to occur during curing. Although it does not specifically limit as a method to remove, For example, the process by activated carbon, an aluminum silicate, a silica gel etc. other than vacuum devolatilization etc. are mentioned. When devolatilizing under reduced pressure, it is preferable to treat at a low temperature. In this case, the upper limit of the temperature is preferably 120 ° C, more preferably 100 ° C. When treated at high temperatures, it tends to be accompanied by alterations such as thickening.

[Characteristics of cured product]
The curable composition of the present invention can be used as an optical component such as a lens, an optical fiber, or an optical waveguide.

Examples and Comparative Examples of the present invention are shown below, but the present invention is not limited to the following.

<Vinyl group-containing compound (A) represented by formula (1) and comparative compound>
As the vinyl group-containing compound represented by the above formula (1), compounds A1 and A2 represented by the following formula were prepared. For comparison, comparative compounds A3 to A5 represented by the following formula were prepared.

化合物Ａ２

比較化合物Ａ３

比較化合物Ａ４

比較化合物Ａ５

Compound A1

Compound A2

Comparative compound A3

Comparative compound A4

Comparative compound A5

  The synthesis methods of Compounds A1 and A2 and Comparative Compound A3 are shown below. The materials used in the synthesis examples are as follows.

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

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

[Hydroxy compounds]
(1) 9,9'-bis (6-hydroxy-2-naphthyl) fluorene (2) 9,9'-bis (4-hydroxyphenyl) fluorene

[Vinyl ester compounds]
(1) Vinyl propionate

[Synthesis Example 1] Synthesis of Compound A1 Into a 1000 ml reaction vessel equipped with a decanter for separating the cooling pipe and the condensate, returning the organic layer to the reaction vessel and discharging the aqueous layer out of the system. -Chlorobis (1,5-cyclooctadiene) diiridium (I) [Ir (cod) Cl] ₂ (839 mg, 1.25 mmol), light ash sodium carbonate (12.7 g, 0.12 mol), 9,9 ' -After charging bis (6-hydroxy-2-naphthyl) fluorene (225 g, 0.5 mol), vinyl propionate (125 g, 1.25 mol), and toluene (300 ml), a stirring blade having a surface area of 10 cm ² was used. The number of revolutions was set to 250 rpm, and the temperature was gradually raised and refluxed while stirring. The reaction was carried out for 5 hours under reflux while removing by-product water with a decanter. When the reaction solution was analyzed by gas chromatography, the conversion of 9,9′-bis (6-hydroxy-2-naphthyl) fluorene was 100%, and 9,9′-bis (6-hydroxy-2-naphthyl). ) Based on fluorene, 9,9′-bis (6-vinyloxy-2-naphthyl) fluorene (Compound 1) was produced in a yield of 81% and bis6-naphtholfluorene monovinyl ether in a yield of 4%.
¹ H-NMR (CDCl ₃ ): 4.47 (dd, 2H, J = 1.5 Hz, 5.0 Hz), 4.81 (dd, 2H, J = 3.5 Hz, 12.0 Hz), 6.71 (Dd, 2H, J = 6.0 Hz), 7.12-7.82 (m, 20H)

[Synthesis Example 2] Synthesis of Compound A2 A 1000-ml reaction vessel equipped with a cooling tube and a decanter for separating the condensate and returning the organic layer to the reaction vessel and discharging the aqueous layer out of the system was added to the di-μ. -Chlorobis (1,5-cyclooctadiene) diiridium (I) [Ir (cod) Cl] ₂ (839 mg, 1.25 mmol), light ash sodium carbonate (12.7 g, 0.12 mol), 9,9 ' -After charging bis (4-hydroxyphenyl) fluorene (186 g, 0.5 mol), vinyl propionate (125 g, 1.25 mol), and toluene (300 ml), the rotational speed was adjusted using a stirring blade with a surface area of 10 cm ^2. The temperature was set to 250 rpm, and the temperature was gradually raised and refluxed while stirring. The reaction was carried out for 5 hours under reflux while removing by-product water with a decanter. When the reaction solution was analyzed by gas chromatography, the conversion of 9,9′-bis (4-hydroxyphenyl) fluorene was 100%. Based on 9,9′-bis (4-hydroxyphenyl) fluorene, 9,9′-bis (4-vinyloxyphenyl) fluorene (Compound 3) was produced in a yield of 72% and bis-4-phenolfluorene monovinyl ether in a yield of 9%.
¹ H-NMR (CDCl ₃ ): 4.47 (dd, 2H), 4.81 (dd, 2H), 6.71 (dd, 2H), 7.12-7.82 (m, 16H)

[Comparative Synthesis Example 1] Synthesis of Comparative Compound A3 A 500 mL flask was charged with 70.1 g of bisphenolfluorene, 60.8 g of potassium carbonate, and 140 g of acetone, heated to 50 ° C. with stirring, and then allyl bromide was added dropwise over 1 hour. did. After dropping, the temperature was raised to 60 ° C. and reacted for 7 hours. After the reaction, 200 g of toluene was added and the residue was filtered. Thereafter, acetone, toluene and allyl bromide were distilled off under reduced pressure, and again dissolved in 200 g of toluene. The solution was washed 3 times with 50 mL of 1N aqueous sodium hydroxide solution, 50 mL of 1N hydrochloric acid and 50 mL of pure water, dehydrated with sodium carbonate, and then toluene was distilled off. The reaction product was recrystallized from hexane to obtain 50 g of a white solid of fluorene bisphenoxy diallyl ether.

化合物Ｂ２

化合物Ｂ３：１，１，３，３−テトラメチルジシロキサン

化合物Ｂ４：１，１，３，３−テトラフェニルジシロキサン

<Compound (B) having at least two SiH groups in one molecule>
As the compound (B), compounds B1 to B4 represented by the following formula were prepared.
Compound B1

Compound B2

Compound B3: 1,1,3,3-tetramethyldisiloxane

Compound B4: 1,1,3,3-tetraphenyldisiloxane

  A synthesis method of compounds B1 and B2 is shown below. The materials used in the synthesis examples are as follows.

[Synthesis Example 3] Synthesis of Compound B1 To a 500 mL flask, 80.0 g of toluene and 130.0 g of 1,3,5,7-tetramethylcyclotetrasiloxane were added and heated so that the internal temperature became 90 ° C. Thereto, a slurry solution of 33.0 g of bisphenol S diallyl ether, 0.65 g of a xylene solution of platinum vinylsiloxane complex (containing 3 wt% as platinum) and 33.0 g of toluene was divided into 5 portions and added at intervals of 30 minutes. Heated to reflux for 2 hours from the final addition. Unreacted 1,3,5,7-tetramethylcyclotetrasiloxane and toluene were distilled off under reduced pressure. According to 1H-NMR, this was obtained by reacting part of the SiH group of 1,3,5,7-tetramethylcyclotetrasiloxane with bisphenol S diallyl ether (compound B1 above), SiH value: 6.8 mmol / g) I found out that

[Synthesis Example 4] Synthesis of Compound B2 To a 200 mL flask, 13.0 g of toluene and 26.0 g of 1,3,5,7-tetramethylcyclotetrasiloxane were added and heated so that the internal temperature became 105 ° C. Thereto, a slurry solution of 8.6 g of bisphenol full orange allyl ether, 0.21 g of a platinum vinylsiloxane complex xylene solution (containing 3 wt% as platinum) and 25.8 g of toluene was divided into 5 portions and added at intervals of 30 minutes. Heated to reflux for 2 hours from the final addition. Unreacted 1,3,5,7-tetramethylcyclotetrasiloxane and toluene were distilled off under reduced pressure. According to 1H-NMR, this was obtained by reacting a part of the SiH group of 1,3,5,7-tetramethylcyclotetrasiloxane with bisphenol fluorenediallyl ether (compound B2 above), SiH value: 7.6 mmol / g )

<Preparation of curable composition and cured product thereof>
[Examples 1 to 8]
The compound A1 or A2 is used as the vinyl group-containing compound (A) represented by the above formula (1), and any one of the compounds B1 to B4 is used as the compound (B) having at least two SiH groups in one molecule. Using a xylene solution of platinum-divinyltetramethyldisiloxane complex (containing 3% by weight of platinum) (C1) as the hydrosilylation catalyst (C), and using 1-ethynyl-1-cyclohexanol as a curing retarder as an additive, Cyclohexanone was used as a solvent and blended at the blending ratio (unit: part by mass) shown in Table 1, followed by stirring and defoaming to prepare a curable composition.
The obtained curable composition was poured into a cell prepared by sandwiching a 1 mm-thick silicone rubber sheet between two glass plates as a spacer, heated from room temperature to 130 ° C. at 6 ° C./min, and 130 ° C. for 40 minutes. And cured at 180 ° C. for 15 minutes to obtain a cured product.

[Comparative Examples 1-6]
Except for using any of the comparative compounds A3 to A5 instead of the vinyl group-containing compound (A), a composition was prepared in the same manner as in the examples with the blending ratio (unit: parts by mass) shown in Table 1. A cured product was obtained.

<Measurement of refractive index>
About the obtained hardened | cured material, the refractive index in wavelength 633nm was measured, and the following references | standards evaluated. The results are shown in Table 1.
A: 1.70 or more, ◯: 1.60 or more and less than 1.70, Δ: 1.50 or more and less than 1.60, ×: less than 1.50

<Measurement of heat resistance>
The obtained cured product is heated from room temperature (about 20 ° C.) at a rate of 10 ° C. per minute and subjected to thermogravimetric analysis in the atmosphere, and the mass is reduced by 5% based on the mass at the start of the analysis. The temperature _{Td 5%} was measured and evaluated according to the following criteria. The results are shown in Table 1.
○: 320 ° C. or higher, Δ: 290 ° C. or higher and lower than 320 ° C., X: lower than 290 ° C.

  As can be seen from Table 1, the curable composition containing Compound A1 or A2 was excellent in refractive index and heat resistance when any of Compounds B1 to B4 was used. In particular, the curable compositions containing Compound A1 and Compound B2 showed a tendency to be excellent in refractive index as compared with other compositions in Examples and Comparative Examples. On the other hand, the composition containing any of the comparative compounds A3 to A5 has a refractive index and a refractive index which is higher than that of the curable composition containing the compound A1 or A2 even when any of the compounds B1 to B4 is used. It was inferior in heat resistance. In particular, the difference in refractive index and heat resistance of the compound A3 was remarkable only in that it had an allyl group, although the compound A3 had a different chemical structure from the compound A2 having a vinyl group.

Claims (3)

(A) Curability containing a vinyl group-containing compound represented by the following formula (1), (B) an organosiloxane compound having at least two SiH groups in one molecule, and (C) a hydrosilylation catalyst. Composition.

(In Formula (1), W ¹ and W ² independently represent a group represented by the following Formula (2), Ring Y ¹ and Ring Y ² represent a benzene ring , R represents a single bond , and R ^1a And R ^1b independently represents a cyano group, a halogen atom, or a monovalent hydrocarbon group, and n1 and n2 independently represent an integer of 0 to 4.)

(In formula (2), ring Z represents a benzene ring or a naphthalene ring , X represents a single bond , R ² represents a monovalent hydrocarbon group; a hydroxyl group; a group represented by —OR ^3a ; and —SR ^3b. An acyl group; an alkoxycarbonyl group; a halogen atom; a nitro group; a cyano group; a mercapto group; a carboxy group; an amino group; a carbamoyl group; a group represented by —NHR ^3c ; a group represented by —N (R ^3d ) ₂ ; (Meth) acryloyloxy group; sulfo group; or monovalent hydrocarbon group, group represented by -OR ^3a , group represented by -SR ^3b , acyl group, alkoxycarbonyl group, group represented by -NHR ^3c , or- N ^(R _3d) at least a portion of the hydrogen atoms bonded to the carbon atoms contained in the group represented by ₂ monovalent hydrocarbon group, a hydroxyl group, a group represented by ^{-OR 3a,} a group represented by ^{-SR 3b} 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 ^3c, a group represented by ^{-N (R} _{3d) 2,} ^(meth A group substituted with an acryloyloxy group, a mesyloxy group, or a sulfo group; R ^{3a to} R ^3d independently represent a monovalent hydrocarbon group, and m represents an integer of 0 or more.) The component (B) is a hydrosilyl of a fluorene compound having at least two carbon-carbon double bonds reactive with SiH groups in one molecule and an organosiloxane compound having at least two SiH groups in one molecule. reaction by obtained, and curable composition of claim 1 comprising a compound having at least two per molecule SiH groups. Claim 1 or 2 cured optical component comprising a curable composition.