JP6555485B2 - Polymerizable resin composition containing reactive silicone compound - Google Patents

Description

  The present invention relates to a polymerizable resin composition containing a reactive silicone compound, and in particular, a cured product having excellent optical properties (high refractive index, low Abbe number) and high heat resistance (heat yellowing resistance, crack resistance). It is related with polymerizable composition which can form.

  Plastic lenses are used for mobile phone cameras, digital cameras, vehicle-mounted cameras, and the like, and are required to have excellent optical characteristics according to the purpose of the device. Moreover, high durability, for example, heat resistance, weather resistance, and the like, and high productivity that can be molded with a high yield are required in accordance with the usage mode.

  In recent years, for the purpose of reducing the mounting cost, a method of mounting camera modules in a batch by solder reflow has been proposed, and the plastic lens material used therefor can withstand a high temperature thermal history (eg, 260 ° C.) in the solder reflow process. Things are sought. However, conventional plastic lenses have low heat resistance, and it has been difficult to satisfactorily adapt to the reflow process.

  In particular, a plurality of lenses are used in a high-resolution camera module, and an optical material having a high refractive index and a low Abbe number is required as one wavelength correction lens. However, as shown in Patent Document 1, most of the conventional materials proposed with features of a high refractive index and a low Abbe number are those having a temperature of 200 ° C. or less even when the heat resistance is improved.

  Further, in the production of resin lenses, in order to improve yield and production efficiency, there is a shift from injection molding of thermoplastic resin to pressing molding using a liquid curable resin at room temperature. In particular, in press molding, it is possible to spread a large number of lenses in a wafer shape and take a large number of them, which is very useful. Casting lens molding, which is one of the methods, can be said to be a method that can maximize the advantages of pressing molding such as low cost and high production efficiency because lens molding is performed using only a curable resin without using expensive optical glass. In addition, a lens molded using only a curable resin without using the glass support is called a monolithic lens, and has recently been attracting attention because the lens can be thinned.

JP 09-31136 A

However, although the above-described monolithic lens used as a lens for a high-resolution camera module has a thickness of about 800 μm, a conventionally known lens material as shown in Patent Document 1 has a temperature of 200 ° C. or higher. It has not yet been possible to guarantee the heat resistance to withstand, and there is a risk that cracks may occur due to a high-temperature heat history (for example, 260 ° C.) in the solder reflow process.
In this way, optical characteristics (high refractive index, low Abbe number) that can be used as monolithic lenses, especially lenses for high-resolution camera modules, and heat resistance (heat yellowing resistance, crack resistance) suitable for mounting processes such as solder reflow No curable resin material satisfying (1) has yet been developed.

  The present invention has been made in view of such circumstances, and the cured product maintains a high refractive index and a low Abbe number, and further suppresses discoloration (thermal yellowing) and cracks caused by high-temperature thermal history. It is an object of the present invention to provide a polymerizable composition suitable for making a molded product.

  As a result of intensive studies to solve the above-mentioned problems, the present inventors have found that reactive silicone compounds obtained by polycondensation such as diaryl silicic acid compounds and alkoxy silicon compounds, and specific fluorene structures, bisphenol structures, etc. By forming a composition containing a (meth) acrylate compound and a specific polymer having a phenylethylene, naphthylethylene, or biphenylethylene structure as a unit structure, the cured product (optical lens) has a high refractive index and a low refractive index. The inventors have found that the Abbe number can be maintained and that thermal yellowing and cracks caused by high-temperature heat history can be effectively suppressed, and the present invention has been completed.

（式中、Ａｒ¹及びＡｒ²はそれぞれ独立して、炭素原子数１乃至６のアルキル基で置換されていてもよいフェニル基、炭素原子数１乃至６のアルキル基で置換されていてもよいナフチル基、又は炭素原子数１乃至６のアルキル基で置換されていてもよいビフェニル基を表す。）

（式中、Ａｒ³は重合性二重結合を有する基を少なくとも１つ有するフェニル基、重合性二重結合を有する基を少なくとも１つ有するナフチル基、又は重合性二重結合を有する基を少なくとも１つ有するビフェニル基を表し、Ｒ¹はメチル基又はエチル基を表し、Ｒ²はメチル基、エチル基又はビニルフェニル基を表し、ａは２又は３を表す。）
第２観点として、前記（ｃ）ポリマーが、少なくとも式［３］で表されるモノマー単位を有するポリマーである、第１観点に記載の重合性組成物に関する。

（式中、Ａｒ⁴は炭素原子数１乃至６のアルキル基で置換されていてもよいフェニル基、炭素原子数１乃至６のアルキル基で置換されていてもよいナフチル基、又は炭素原子数１乃至６のアルキル基で置換されていてもよいビフェニル基を表し、Ｒ³は水素原子又はメチル基を表す。）
第３観点として、前記（ｃ）ポリマーが、さらに式［４］で表されるモノマー単位を有するポリマーである、第２観点に記載の重合性組成物に関する。

（式中、Ｒ⁴は水素原子又はメチル基を表し、Ｒ⁵は炭素原子数１乃至１２のアルキル基を表す。）
第４観点として、前記（ｃ）ポリマーがポリ（スチレン−ｃｏ−（メタ）アクリル酸メチル）である、第３観点に記載の重合性組成物に関する。
第５観点として、前記（ｂ）（メタ）アクリレート化合物が、式［５］で表されるフルオレン化合物Ｄ、及び式［６］で表されるビスフェノール化合物Ｅからなる群から選ばれる少なくとも一種である、第１観点乃至第４観点のうち何れか一つに記載の重合性組成物に関する。

（式中、Ｒ⁶及びＲ⁷はそれぞれ独立して、水素原子又はメチル基を表し、Ｌ¹及びＬ²はそれぞれ独立して、置換基を有していてもよいフェニレン基、又は置換基を有していてもよいナフタレンジイル基を表し、Ｌ³及びＬ⁴はそれぞれ独立して、炭素原子数１乃至６のアルキレン基を表し、ｍ及びｎはｍ＋ｎが０乃至４０となる０又は正の整数を表す。）

（式中、Ｒ⁸及びＲ⁹はそれぞれ独立して、水素原子又はメチル基を表し、Ｒ¹⁰及びＲ¹¹はそれぞれ独立して、水素原子、メチル基又はトリフルオロメチル基を表し、Ｌ⁵及びＬ⁶はそれぞれ独立して、炭素原子数１乃至６のアルキレン基を表し、ｐ及びｑはｐ＋ｑが０乃至４０となる０又は正の整数を表す。）
第６観点として、前記（ｂ）（メタ）アクリレート化合物として、前記フルオレン化合物Ｄ及び前記ビスフェノール化合物Ｅの二種を少なくとも含む、第５観点に記載の重合性組成物に関する。
第７観点として、さらに（ｄ）式［７］で表される基を有する化合物である光安定剤Ｆ、及び式［８］で表される基を有する化合物である酸化防止剤Ｇからなる群から選ばれる少なくとも一種の安定化剤０．０１〜５質量部を含む、第１観点乃至第６観点のうち何れか一つに記載の重合性組成物に関する。

（式中、Ｒ¹²は水素原子、炭素原子数１乃至１０のアルキル基、又は炭素原子数１乃至１２のアルコキシ基を表し、黒点は結合手を表す。）

（式中、Ｒ¹³は炭素原子数１乃至１０のアルキル基を表し、Ｒ¹⁴乃至Ｒ¹⁶はそれぞれ独立して、水素原子、又は炭素原子数１乃至１０のアルキル基を表し、黒点は結合手を表す。）
第８観点として、さらに（ｅ）チオール化合物Ｈ及びジスルフィド化合物Ｉからなる群から選ばれる少なくとも一種の硫黄化合物０．０１〜５質量部を含む、第１観点乃至第７観点のうち何れか一つに記載の重合性組成物に関する。
第９観点として、前記（ａ）反応性シリコーン化合物が、式［１］で表されるジアリールケイ酸化合物Ａと、式［２］で表されるアルコキシケイ素化合物Ｂと、さらに式［９］で表されるアルコキシケイ素化合物Ｃとを少なくとも含む重縮合性化合物を、酸又は塩基の存在下重縮合して得られる反応性シリコーン化合物である、第１観点乃至第８観点のうち何れか一つに記載の重合性組成物に関する。

（式中、Ｒｆは炭素原子数１乃至１２のフルオロアルキル基、又はフルオロフェニル基を表し、Ｒ¹⁷はメチル基又はエチル基を表し、Ｒ¹⁸はメチル基、エチル基又はビニルフェニル基を表し、ｂは２又は３を表す。）
第１０観点として、第１観点乃至第９観点のうち何れか一つに記載の重合性組成物を重合して得られる、硬化物に関する。
第１１観点として、第１観点乃至第９観点のうち何れか一つに記載の重合性組成物を重合して得られる、光学レンズに関する。
第１２観点として、第１観点乃至第９観点のうち何れか一つに記載の重合性組成物からなる高屈折率樹脂レンズ用材料に関する。That is, as a first aspect, the present invention provides (a) a polycondensable compound containing at least a diaryl silicate compound A represented by the formula [1] and an alkoxysilicon compound B represented by the formula [2]. 100 parts by mass of a reactive silicone compound obtained by polycondensation in the presence of an acid or a base,
The present invention relates to a polymerizable composition comprising (b) 1 to 200 parts by mass of a (meth) acrylate compound and (c) 0.1 to 50 parts by mass of a polymer having a weight average molecular weight of 5,000 to 100,000.

(In the formula, Ar ¹ and Ar ² are each independently a phenyl group which may be substituted with an alkyl group having 1 to 6 carbon atoms, or an alkyl group having 1 to 6 carbon atoms. It represents a naphthyl group or a biphenyl group optionally substituted with an alkyl group having 1 to 6 carbon atoms.)

(In the formula, Ar ³ represents at least a phenyl group having at least one group having a polymerizable double bond, a naphthyl group having at least one group having a polymerizable double bond, or a group having a polymerizable double bond. 1 represents a biphenyl group, R ¹ represents a methyl group or an ethyl group, R ² represents a methyl group, an ethyl group, or a vinylphenyl group, and a represents 2 or 3.)
As a second aspect, the present invention relates to the polymerizable composition according to the first aspect, in which the polymer (c) is a polymer having at least a monomer unit represented by the formula [3].

(In the formula, Ar ⁴ is a phenyl group which may be substituted with an alkyl group having 1 to 6 carbon atoms, a naphthyl group which may be substituted with an alkyl group having 1 to 6 carbon atoms, or 1 carbon atom. Represents a biphenyl group which may be substituted with 1 to 6 alkyl groups, and R ³ represents a hydrogen atom or a methyl group.)
As a third aspect, the present invention relates to the polymerizable composition according to the second aspect, in which the polymer (c) is a polymer further having a monomer unit represented by the formula [4].

(In the formula, R ⁴ represents a hydrogen atom or a methyl group, and R ⁵ represents an alkyl group having 1 to 12 carbon atoms.)
As a fourth aspect, the present invention relates to the polymerizable composition according to the third aspect, in which the polymer (c) is poly (styrene-co- (methyl) acrylate).
As a fifth aspect, the (b) (meth) acrylate compound is at least one selected from the group consisting of a fluorene compound D represented by the formula [5] and a bisphenol compound E represented by the formula [6]. Further, the present invention relates to the polymerizable composition according to any one of the first aspect to the fourth aspect.

(In the formula, R ⁶ and R ⁷ each independently represent a hydrogen atom or a methyl group, and L ¹ and L ² each independently represent a phenylene group which may have a substituent, or a substituent. An optionally substituted naphthalenediyl group, L ³ and L ⁴ each independently represents an alkylene group having 1 to 6 carbon atoms, and m and n are 0 or positive in which m + n is 0 to 40 Represents an integer.)

(Wherein R ⁸ and R ⁹ each independently represent a hydrogen atom or a methyl group, R ¹⁰ and R ¹¹ each independently represent a hydrogen atom, a methyl group or a trifluoromethyl group, L ⁵ and L ⁶ independently represents an alkylene group having 1 to 6 carbon atoms, and p and q represent 0 or a positive integer in which p + q is 0 to 40.)
As a sixth aspect, the present invention relates to the polymerizable composition according to the fifth aspect, which includes at least two of the fluorene compound D and the bisphenol compound E as the (b) (meth) acrylate compound.
As a seventh aspect, the group consisting of (d) a light stabilizer F that is a compound having a group represented by formula [7] and an antioxidant G that is a compound having a group represented by formula [8]. The polymerizable composition according to any one of the first to sixth aspects, comprising 0.01 to 5 parts by mass of at least one stabilizer selected from:

(Wherein R ¹² represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or an alkoxy group having 1 to 12 carbon atoms, and a black dot represents a bond.)

(Wherein R ¹³ represents an alkyl group having 1 to 10 carbon atoms, R ^{14 to} R ¹⁶ each independently represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and a black dot represents a bond. Represents.)
As an eighth aspect, any one of the first aspect to the seventh aspect further includes 0.01 to 5 parts by mass of at least one sulfur compound selected from the group consisting of (e) a thiol compound H and a disulfide compound I. The polymerizable composition as described in 1. above.
As a ninth aspect, the (a) reactive silicone compound includes a diaryl silicic acid compound A represented by the formula [1], an alkoxysilicon compound B represented by the formula [2], and a formula [9]. Any one of the first to eighth aspects, which is a reactive silicone compound obtained by polycondensation of a polycondensable compound containing at least an alkoxysilicon compound C represented in the presence of an acid or a base. It relates to the polymerizable composition described.

Wherein Rf represents a fluoroalkyl group having 1 to 12 carbon atoms or a fluorophenyl group, R ¹⁷ represents a methyl group or an ethyl group, R ¹⁸ represents a methyl group, an ethyl group or a vinylphenyl group; b represents 2 or 3.)
As a tenth aspect, the present invention relates to a cured product obtained by polymerizing the polymerizable composition according to any one of the first to ninth aspects.
As an 11th viewpoint, it is related with the optical lens obtained by superposing | polymerizing the polymeric composition as described in any one among a 1st viewpoint thru | or a 9th viewpoint.
As a 12th viewpoint, it is related with the material for high refractive index resin lenses which consists of a polymeric composition as described in any one among a 1st viewpoint thru | or a 9th viewpoint.

The polymerizable composition of the present invention has not only the cured product having desirable optical characteristics (high refractive index, low Abbe number) as an optical device, for example, a lens for a high-resolution camera module, but also a high-resolution camera module. It also has heat resistance (yellowing resistance, crack resistance) that can be suitable for the process. In particular, even a monolithic lens having a film thickness obtained by a casting lens molding process has optical characteristics and heat resistance suitable for a mounting process of a high-resolution camera module.
Therefore, the high refractive index resin lens material of the present invention comprising the polymerizable composition can be suitably used as a lens for a high resolution module.

1 is a diagram showing a ¹ H NMR spectrum of the reactive fluorine-containing silicone compound obtained in Production Example 1. FIG. FIG. 2 is a diagram showing a ¹ H NMR spectrum of the reactive silicone compound obtained in Production Example 2.

<< Polymerizable composition >>
The present invention provides (a) a polycondensable compound containing at least a diaryl silicic acid compound A represented by the above formula [1] and an alkoxysilicon compound B represented by the above formula [2]. 100 parts by weight of a reactive silicone compound obtained by polycondensation in the presence, 1 to 200 parts by weight of (b) (meth) acrylate compound, and (c) a polymer having a weight average molecular weight of 5,000 to 100,000. The present invention relates to a polymerizable composition containing 1 to 50 parts by mass.

<(A) Reactive silicone compound>
The reactive silicone compound (a) used in the present invention is obtained by polycondensing a polycondensable compound containing at least a diaryl silicate compound A having a specific structure and an alkoxysilicon compound B having a specific structure in the presence of an acid or a base. It is a compound obtained.
Hereinafter, details of each component will be described.

上記式［１］中、Ａｒ¹及びＡｒ²はそれぞれ独立して、炭素原子数１乃至６のアルキル基で置換されていてもよいフェニル基、炭素原子数１乃至６のアルキル基で置換されていてもよいナフチル基、又は炭素原子数１乃至６のアルキル基で置換されていてもよいビフェニル基を表す。[Polycondensable compound]
[Diaryl Silicic Acid Compound A]
The diaryl silicate compound A is a compound represented by the following formula [1].

In the above formula [1], Ar ¹ and Ar ² are each independently substituted with a phenyl group which may be substituted with an alkyl group having 1 to 6 carbon atoms, or an alkyl group with 1 to 6 carbon atoms. A naphthyl group which may be substituted, or a biphenyl group which may be substituted with an alkyl group having 1 to 6 carbon atoms.

Examples of the phenyl group which may be substituted with an alkyl group having 1 to 6 carbon atoms represented by Ar ¹ and Ar ² include a phenyl group, an o-tolyl group, an m-tolyl group, a p-tolyl group, 4- Ethylphenyl group, 4-isopropylphenyl group, 4-tert-butylphenyl group, 3,5-dimethylphenyl group, 3,5-diethylphenyl group, 3,5-diisopropylphenyl group, 2,4,6-trimethylphenyl Groups and the like.
Examples of the naphthyl group optionally substituted with an alkyl group having 1 to 6 carbon atoms represented by Ar ¹ and Ar ² include a 1-naphthyl group, a 2-naphthyl group, a 4-methylnaphthalen-1-yl group, Examples include 6-methylnaphthalen-2-yl group.
Examples of the biphenyl group optionally substituted by an alkyl group having 1 to 6 carbon atoms represented by Ar ¹ and Ar ² include [1,1′-biphenyl] -2-yl group, [1,1′- Biphenyl] -3-yl group and [1,1′-biphenyl] -4-yl group.

  Specific examples of the compound represented by the above formula [1] include diphenylsilanediol, di-p-tolylsilanediol, bis (4-ethylphenyl) silanediol, bis (4-isopropylphenyl) silanediol, dinaphthyl. Silane diol, bis ([1,1′-biphenyl] -4-yl) silane diol, and the like are exemplified, but the silane diol is not limited thereto.

上記式［２］中、Ａｒ³は重合性二重結合を有する基を少なくとも１つ有するフェニル基、重合性二重結合を有する基を少なくとも１つ有するナフチル基、又は重合性二重結合を有する基を少なくとも１つ有するビフェニル基を表し、Ｒ¹はメチル基又はエチル基を表し、Ｒ²はメチル基、エチル基又はビニルフェニル基を表し、ａは２又は３を表す。[Alkoxysilicon compound B]
The alkoxysilicon compound B is a compound represented by the following formula [2].

In the above formula [2], Ar ³ has a phenyl group having at least one group having a polymerizable double bond, a naphthyl group having at least one group having a polymerizable double bond, or a polymerizable double bond. A biphenyl group having at least one group is represented, R ¹ represents a methyl group or an ethyl group, R ² represents a methyl group, an ethyl group or a vinylphenyl group, and a represents 2 or 3.

Examples of the phenyl group having at least one group having a polymerizable double bond represented by Ar ³ include 2-vinylphenyl group, 3-vinylphenyl group, 4-vinylphenyl group, 4-vinyloxyphenyl group, 4 -An allylphenyl group, 4-allyloxyphenyl group, 4-isopropenylphenyl group, etc. are mentioned.
Examples of the naphthyl group having at least one group having a polymerizable double bond represented by Ar ³ include 4-vinylnaphthalen-1-yl group, 5-vinylnaphthalen-1-yl group, and 6-vinylnaphthalene-2. -Yl group, 4-allylnaphthalen-1-yl group, 4-allyloxynaphthalen-1-yl group, 5-allyloxynaphthalen-1-yl group, 8-allyloxynaphthalen-1-yl group, 5-vinyl Oxynaphthalen-1-yl group, 5-allylnaphthalen-1-yl group, 5-isopropenylnaphthalen-1-yl group, 6-vinylnaphthalen-2-yl group, 6-allylnaphthalen-2-yl group, etc. Can be mentioned.
As a biphenyl group having at least one group having a polymerizable double bond represented by Ar ³ , for example, a 4′-vinyl- [1,1′-biphenyl] -2-yl group, 4′-vinyl- [1 , 1′-biphenyl] -3-yl group, 4′-vinyl- [1,1′-biphenyl] -4-yl group, 4′-vinyloxy- [1,1′-biphenyl] -4-yl group, 4'-allyl- [1,1'-biphenyl] -4-yl group, 4'-allyloxy- [1,1'-biphenyl] -4-yl group, 4'-isopropenyl- [1,1'- And biphenyl] -4-yl group.

  Specific examples of the compound represented by the formula [2] include, for example, trimethoxy (4-vinylphenyl) silane, triethoxy (4-vinylphenyl) silane, (4-isopropenylphenyl) trimethoxysilane, and dimethoxy (methyl). ) (4-vinylphenyl) silane, dimethoxybis (4-vinylphenyl) silane, trimethoxy (4-vinyl-1-naphthyl) silane, trimethoxy (5-vinyl-1-naphthyl) silane, trimethoxy (6-vinyl-2) -Naphtyl) silane, trimethoxy (4'-vinyl- [1,1'-biphenyl] -4-yl) silane, and the like, but are not limited thereto.

[Alkoxysilicon compound C]
The polycondensable compound used in the reactive silicone compound (a) used in the present invention may contain an alkoxysilicon compound C having a specific structure in addition to the aforementioned diaryl silicate compound A and alkoxysilicon compound B. .

上記式［９］中、Ｒｆは炭素原子数１乃至１２のフルオロアルキル基、又はフルオロフェニル基を表し、Ｒ¹⁷はメチル基又はエチル基を表し、Ｒ¹⁸はメチル基、エチル基又はビニルフェニル基を表し、ｂは２又は３を表す。
中でも、Ｒｆが式［１０］で表される基であることが好ましい。

上記式［１０］中、Ｘは水素原子又はフッ素原子を表し、ｒは０乃至２の整数を表し、ｓは１乃至６の整数を表し、黒点はケイ素原子への結合手を表す。The alkoxysilicon compound C is a compound represented by the following formula [9].

In the above formula [9], Rf represents a fluoroalkyl group having 1 to 12 carbon atoms or a fluorophenyl group, R ¹⁷ represents a methyl group or an ethyl group, and R ¹⁸ represents a methyl group, an ethyl group or a vinylphenyl group. And b represents 2 or 3.
Especially, it is preferable that Rf is group represented by Formula [10].

In the above formula [10], X represents a hydrogen atom or a fluorine atom, r represents an integer of 0 to 2, s represents an integer of 1 to 6, and a black dot represents a bond to a silicon atom.

  Examples of the fluoroalkyl group having 1 to 12 carbon atoms represented by Rf include a trifluoromethyl group, a pentafluoroethyl group, a heptafluoropropyl group, a perfluorobutyl group, a perfluoropentyl group, a perfluorohexyl group, 2, 2, 2-trifluoroethyl group, 2,2,3,3,3-pentafluoropropyl group, 3,3,3-trifluoropropyl group, 2- (perfluorobutyl) ethyl group, 2- (perfluorohexyl) Ethyl group, 2- (perfluorooctyl) ethyl group, 2- (perfluorodecyl) ethyl group, 2- (perfluoro-3-methylbutyl) ethyl group, 2- (perfluoro-5-methylhexyl) ethyl group, 2- (perfluoro-7-methyloctyl) ethyl group, 1H, 1H, 3H-tetrafluoropropyl group, 1H, 1 , 4H-hexafluorobutyl group, 1H, 1H, 5H-octafluoropentyl group, 1H, 1H, 7H-dodecafluoroheptyl group, 1H, 1H, 9H-hexadecafluorononyl group, 1H-1- (trifluoromethyl ) Trifluoroethyl group and the like.

  Examples of the fluorophenyl group represented by Rf include 2-fluorophenyl group, 3-fluorophenyl group, 4-fluorophenyl group, 2,4,6-trifluorophenyl group, perfluorophenyl group and the like.

  Specific examples of the compound represented by the above formula [9] include, for example, trimethoxy (trifluoromethyl) silane, trimethoxy (3,3,3-trifluoropropyl) silane, triethoxy (3,3,3-trifluoro). Propyl) silane, dimethoxy (methyl) (3,3,3-trifluoropropyl) silane, dimethoxy (3,3,3-trifluoropropyl) (4-vinylphenyl) silane, and the like. It is not something.

[Other polycondensable compounds]
The polycondensable compound used in the reactive silicone compound (a) used in the present invention includes other polycondensable compounds other than the aforementioned diaryl silicic acid compound A, alkoxysilicon compound B and alkoxysilicon compound C. May be.
Other polycondensable compounds are not particularly limited as long as they are compounds capable of polycondensation with these compounds, such as hydrolyzable silane compounds other than the above-mentioned compounds A to C.
Other polycondensable compounds include, for example, tetramethoxysilane, tetraethoxysilane, trimethoxy (methyl) silane, trimethoxy (vinyl) silane, 3- (meth) acryloyloxypropyl (trimethoxy) silane, trimethoxy (phenyl) silane, Trimethoxy (1-naphthyl) silane, dimethoxy (dimethyl) silane, dimethoxy (diphenyl) silane, dimethoxy (methyl) (vinyl) silane, 3- (meth) acryloyloxypropyl (dimethoxy) (methyl) silane, dimethoxy (methyl) ( Phenyl) silane and the like.

上記式［２ａ］中、Ｒ¹は前記と同じ意味を表す。

上記式［９ａ］中、Ｒｆ及びＲ¹⁷は前記と同じ意味を表す。[Preferred examples of reactive silicone compound]
As the reactive silicone compound (a), diphenylsilane diol as diaryl silicic acid compound A and a compound represented by the following formula [2a] as alkoxy silicon compound B are polycondensed in the presence of an acid or a base. The resulting reactive silicone compound is preferred. In addition, diphenylsilanediol as the diaryl silicate compound A, a compound represented by the following formula [2a] as the alkoxysilicon compound B, and a compound represented by the following formula [9a] as the alkoxysilicon compound C A reactive silicone compound obtained by polycondensation in the presence of a base is preferred.

In the above formula [2a], R ¹ represents the same meaning as described above.

In the above formula [9a], Rf and R ¹⁷ have the same meaning as described above.

[Blending ratio of diaryl silicate compound A and alkoxy silicon compound B]
Although the compounding molar ratio concerning the polycondensation reaction of the diaryl silicic acid compound A represented by the formula [1] and the alkoxysilicon compound B represented by the formula [2] used for the reactive silicone compound is not particularly limited, In order to prevent block copolymerization, the range of diaryl silicic acid compound A: alkoxy silicon compound B = 2: 1 to 1: 2 is usually preferable. More preferably, it is the range mix | blended between 1.1: 0.9-0.9: 1.1.
When the polycondensable compound includes the alkoxysilicon compound C represented by the formula [9] in addition to the compound A and the compound B, the molar ratio of the compound is not particularly limited. The range of silicic acid compound A: alkoxysilicon compound B and C = 2: 1 to 1: 2 is preferred. More preferably, it is the range mix | blended between 1.1: 0.9-0.9: 1.1. Usually, the range of alkoxysilicon compound B: alkoxysilicon compound C = 99.9: 0.1 to 90:10 is preferred.
Further, when the polycondensable compound includes other polycondensable compounds other than the above compounds A to C, the blending ratio is not particularly limited, but is usually preferably 50 mol% or less with respect to the alkoxysilicon compound B. .

  The above-mentioned diaryl silicic acid compound A, alkoxy silicon compound B and alkoxy silicon compound C can be used by appropriately selecting compounds as necessary, and a plurality of types can be used in combination. In this case, the molar ratio of the diaryl silicate compound A, the alkoxy silicon compound B, and the alkoxy silicon compound C is in the above range.

[Acid or basic catalyst]
The diaryl silicate compound A represented by the formula [1] and the alkoxysilicon compound B represented by the formula [2] (and optionally the alkoxysilicon compound C represented by the formula [9] and / or other heavy compounds. The polycondensation reaction with the condensable compound) is preferably carried out in the presence of an acid or basic catalyst.
The type of the catalyst used for the polycondensation reaction is not particularly limited as long as it is dissolved or uniformly dispersed in the solvent described later, and can be appropriately selected and used as necessary.
Examples of the catalyst that can be used include B (OR) ₃ , Al (OR) ₃ , Ti (OR) ₄ , Zr (OR) _4, etc. as acidic compounds; alkali metal hydroxides as basic compounds, Alkaline earth metal hydroxides, ammonium salts, amines, etc .; Examples of fluoride salts include NH ₄ F, NR ₄ F, and the like. Here, R represents a hydrogen atom, a linear alkyl group having 1 to 12 carbon atoms, a branched alkyl group having 3 to 12 carbon atoms, or a cyclic alkyl group having 3 to 12 carbon atoms. One or more selected groups.

  Examples of the acidic compound include boric acid, trimethoxyboron, triethoxyboron, tri-n-propoxyboron, triisopropoxyboron, tri-n-butoxyboron, triisobutoxyboron, tri-sec-butoxyboron, Tri-tert-butoxyboron, trimethoxyaluminum, triethoxyaluminum, tri-n-propoxyaluminum, triisopropoxyaluminum, tri-n-butoxyaluminum, triisobutoxyaluminum, tri-sec-butoxyaluminum, tri-tert- Butoxyaluminum, tetramethoxytitanium, tetraethoxytitanium, tetra-n-propoxytitanium, tetraisopropoxytitanium (titanium tetraisopropoxide), tetra-n-butoxytitanium, tet Isobutoxy titanium, tetra-sec-butoxy titanium, tetra-tert-butoxy titanium, tetramethoxy zirconium, tetraethoxy zirconium, tetra-n-propoxy zirconium, tetraisopropoxy zirconium, tetra-n-butoxy zirconium, tetraisobutoxy zirconium, Tetra-sec-butoxyzirconium, tetra-tert-butoxyzirconium and the like can be mentioned.

  Examples of the basic compound include sodium hydroxide, potassium hydroxide, magnesium hydroxide, calcium hydroxide, strontium hydroxide, barium hydroxide, ammonium hydroxide, tetramethylammonium hydroxide, tetrabutylammonium hydroxide, triethylamine. Etc.

  Examples of the fluoride salt include ammonium fluoride, tetramethylammonium fluoride, and tetrabutylammonium fluoride.

Among these catalysts, one or more selected from the group consisting of tetraisopropoxy titanium (titanium tetraisopropoxide), magnesium hydroxide, calcium hydroxide, strontium hydroxide, and barium hydroxide is preferably used.
The usage-amount of a catalyst is 0.01-10 mass% with respect to the total mass of the said diaryl silicate compound and an alkoxy silicon compound, Preferably it is 0.1-5 mass%. The reaction proceeds more favorably when the amount of the catalyst used is 0.01% by mass or more. In consideration of economy, the use of 10% by mass or less is sufficient.

[Polycondensation reaction]
The reactive silicone compound according to the present invention is characterized by the structure of the alkoxysilicon compound. The reactive group (polymerizable double bond) contained in the alkoxysilicon compound used in the present invention is easily polymerized radically or ionically (anion, cation), and has high heat resistance after polymerization (after curing). Show.
When such an alkoxysilicon compound and a diarylsilicate compound are polycondensed to obtain a silicone compound having high heat resistance, it is necessary to stop the reaction at an appropriate degree of polymerization so that the product maintains a liquid state. Since the alkoxysilicon compound used in the present invention does not actively hydrolyze, the polycondensation reaction with the diaryl silicate compound is gentle, and the degree of polymerization is easily controlled.
The polycondensation reaction of the alkoxy silicon compound and the diaryl silicate compound by dealcoholization can be performed in the absence of a solvent, but it is also possible to use a solvent inert to the alkoxy silicon compound such as toluene described later as the reaction solvent. It is. When there is no solvent, there is an advantage that the alcohol as a reaction by-product can be easily distilled off. On the other hand, when a reaction solvent is used, there are advantages that the reaction system can be easily made uniform and a more stable polycondensation reaction can be performed.

The reactive reaction of the reactive silicone compound may be performed without a solvent as described above, but there is no problem even if a solvent is used in order to make it more uniform. The solvent is not particularly limited as long as it does not react with the diaryl silicate compound and the alkoxysilicon compound and dissolves the condensate thereof.
Examples of such a reaction solvent include ketones such as acetone and methyl ethyl ketone (MEK); aromatic hydrocarbons such as benzene, toluene and xylene; glycols such as ethylene glycol, propylene glycol and hexylene glycol; ethyl cellosolve , Glycol ethers such as butyl cellosolve, ethyl carbitol, butyl carbitol, diethyl cellosolve, diethyl carbitol; amides such as N-methyl-2-pyrrolidone (NMP) and N, N-dimethylformamide (DMF) It is done. These solvents may be used alone or in combination of two or more. Among these, toluene is preferable.

The reactive silicone compound used in the present invention is represented by the diaryl silicate compound A represented by the formula [1] and the alkoxysilicon compound B represented by the formula [2] (and optionally represented by the formula [9]. It is obtained by subjecting the alkoxysilicon compound C and / or other polycondensable compound) to dealcoholization condensation in the presence of an acid or a basic catalyst. The polycondensation reaction is preferably carried out without positively adding water, and is preferably carried out in an inert gas atmosphere such as nitrogen gas for the purpose of preventing water contamination. The reaction temperature is 20 to 150 ° C, more preferably 30 to 120 ° C.
The reaction time is not particularly limited as long as it is longer than the time necessary for the molecular weight distribution of the polycondensate to increase and to stabilize the molecular weight distribution, and more specifically, several hours to several days.

  After completion of the polycondensation reaction, the obtained reactive silicone compound is preferably collected by any method such as filtration and solvent distillation, and appropriately subjected to purification treatment as necessary.

  The polycondensate obtained by such a reaction has a weight average molecular weight Mw measured in terms of polystyrene by gel permeation chromatography (GPC) of 500 to 10,000, and a dispersity Mw (weight average molecular weight) / Mn. (Number average molecular weight) is 1.0-10.

<(B) (Meth) acrylate compound>
The (b) (meth) acrylate compound contained in the polymerizable composition of the present invention preferably comprises a fluorene compound D represented by the following formula [5] and a bisphenol compound E represented by the following formula [6]. It is at least one selected from the group. In this specification, (meth) acrylate refers to both acrylate and methacrylate.

上記式［５］中、Ｒ⁶及びＲ⁷はそれぞれ独立して、水素原子又はメチル基を表し、Ｌ¹及びＬ²はそれぞれ独立して、置換基を有していてもよいフェニレン基、又は置換基を有していてもよいナフタレンジイル基を表し、Ｌ³及びＬ⁴はそれぞれ独立して、炭素原子数１乃至６のアルキレン基を表し、ｍ及びｎはｍ＋ｎが０乃至４０となる０又は正の整数を表す。[Fluorene compound D]
The fluorene compound D is a compound represented by the following formula [5].

In the above formula [5], R ⁶ and R ⁷ each independently represent a hydrogen atom or a methyl group, and L ¹ and L ² each independently represent a phenylene group which may have a substituent, or Represents an optionally substituted naphthalenediyl group, L ³ and L ⁴ each independently represent an alkylene group having 1 to 6 carbon atoms, and m and n are 0 in which m + n is 0 to 40 Or it represents a positive integer.

Examples of the phenylene group optionally having a substituent represented by L ¹ and L ² include an o-phenylene group, an m-phenylene group, a p-phenylene group, a 2-methylbenzene-1,4-diyl group, 2-chlorobenzene-1,4-diyl group, 2-bromobenzene-1,4-diyl group, 2-aminobenzene-1,4-diyl group, 2-methylbenzene-1,5-diyl group, 2-chlorobenzene -1,5-diyl group, 2-bromobenzene-1,5-diyl group, 2-aminobenzene-1,5-diyl group and the like. Of these, a p-phenylene group is preferable.
Examples of the naphthalenediyl group optionally having a substituent represented by L ¹ and L ² include a naphthalene-1,4-diyl group, a naphthalene-1,5-diyl group, and a naphthalene-2,6-diyl group. Etc.

Examples of the alkylene group having 1 to 6 carbon atoms represented by L ³ and L ⁴ include a methylene group, an ethylene group, a trimethylene group, a methylethylene group, a tetramethylene group, a 1-methyltrimethylene group, and a 2-methyltrimethylene group. Group, 1,1-dimethylethylene group, pentamethylene group, 1-methyltetramethylene group, 2-methyltetramethylene group, 1,1-dimethyltrimethylene group, 1,2-dimethyltrimethylene group, 2,2- Dimethyltrimethylene group, 1-ethyltrimethylene group, hexamethylene group, 1-methylpentamethylene group, 2-methylpentamethylene group, 3-methylpentamethylene group, 1,1-dimethyltetramethylene group, 1,2- Dimethyltetramethylene group, 2,2-dimethyltetramethylene group, 1-ethyltetramethylene group, 1,1,2-trimethyl Examples thereof include a methyltrimethylene group, 1,2,2-trimethyltrimethylene group, 1-ethyl-1-methyltrimethylene group, 1-ethyl-2-methyltrimethylene group and the like. Of these, an ethylene group and a methylethylene group are preferable.

  In the compound represented by the formula [5], m and n are preferably such that m + n is 0 to 30, and more preferably m + n is 2 to 20.

  Specific examples of such fluorene compound D include, for example, 9,9-bis (4- (2- (meth) acryloyloxy) phenyl) -9H-fluorene, 9,9-bis (4- (2- ( (Meth) acryloyloxyethoxy) phenyl) -9H-fluorene, ethoxylated (ethylene oxide modified) (9H-fluorene-9,9-diyl) bis (4,1-phenylene) di (meth) acrylate, propoxylated (propylene oxide modified) ) (9H-fluorene-9,9-diyl) bis (4,1-phenylene) di (meth) acrylate, 9,9-bis (6- (2- (meth) acryloyloxy) naphthalen-2-yl)- 9H-fluorene, 9,9-bis (6- (2- (meth) acryloyloxyethoxy) naphthalen-2-yl) -9H-fluorene, Gusol (registered trademark) EA-0200, EA-0300, EA-F5003, EA-F5503, EA-F5510, EA-F5710, GA-5000 [above, manufactured by Osaka Gas Chemical Co., Ltd.] NK ester A-BPEF [manufactured by Shin-Nakamura Chemical Co., Ltd.] and the like are exemplified, but not limited thereto.

上記式［６］中、Ｒ⁸及びＲ⁹はそれぞれ独立して、水素原子又はメチル基を表し、Ｒ¹⁰及びＲ¹¹はそれぞれ独立して、水素原子、メチル基又はトリフルオロメチル基を表し、Ｌ⁵及びＬ⁶はそれぞれ独立して、炭素原子数１乃至６のアルキレン基を表し、ｐ及びｑはｐ＋ｑが０乃至４０となる０又は正の整数を表す。[Bisphenol compound E]
The bisphenol compound E is a compound represented by the following formula [6].

In the above formula [6], R ⁸ and R ⁹ each independently represent a hydrogen atom or a methyl group, R ¹⁰ and R ¹¹ each independently represent a hydrogen atom, a methyl group or a trifluoromethyl group, L ⁵ and L ⁶ each independently represent an alkylene group having 1 to 6 carbon atoms, and p and q each represents 0 or a positive integer in which p + q is 0 to 40.

Examples of the alkylene group having 1 to 6 carbon atoms represented by L ⁵ and L ⁶ include the same groups as those exemplified as L ³ and L ⁴ in the above formula [5]. Of these, an ethylene group and a methylethylene group are preferable.

  In the compound represented by the formula [6], p and q are preferably such that p + q is 0 to 30, and more preferably p + q is 2 to 20.

  Specific examples of such bisphenol compound E include, for example, bisphenol A di (meth) acrylate, ethoxylated (ethylene oxide modified) bisphenol A di (meth) acrylate (2.3 mol addition of ethoxy groups, 2.6 mol addition, 3 mol addition) 4 mol addition, 6 mol addition, 10 mol addition, 17 mol addition, 30 mol addition, etc.), propoxylation (propylene oxide modification) bisphenol A di (meth) acrylate (propoxy group 3 mol addition, etc.), ethoxy / propoxylation (ethylene oxide / propylene oxide modification) ) Bisphenol A di (meth) acrylate (6 mol of ethoxy group / 12 mol of propoxy group added, etc.), ethoxylated (ethylene oxide modified) bisphenol F di (meth) acrylate (ethoxy) 4 mol addition, etc.), ethoxylated (ethylene oxide modified) bisphenol AF di (meth) acrylate, NK ester A-B1206PE, ABE-300, A-BPE-10, A-BPE-20, A-BPE-30 A-BPE-4, A-BPP-3, BPE-80N, BPE-100, BPE-200, BPE-500, BPE-900, BPE-1300N [above, Shin-Nakamura Chemical Industrial Co., Ltd.], Blemmer (registered trademark) PDBE-200, PDBE-250, PDBE-450, PDBE-1300 [above, manufactured by NOF Corporation], KAYARAD (registered trademark) R-712 [ Nippon Kayaku Co., Ltd.]. Among them, ethoxylated (ethylene oxide modified) bisphenol A di (meth) acrylate and propoxylated (propylene oxide modified) bisphenol A di (meth) acrylate are preferable.

In the polymerizable composition of the present invention, the blending amount of the (b) (meth) acrylate compound is preferably 1 to 200 parts by weight and more preferably 25 to 150 parts by weight with respect to 100 parts by weight of the (a) reactive silicone compound. Preferably, 50-100 mass parts is especially preferable.
The (b) (meth) acrylate compound contained in the polymerizable composition of the present invention is a mixture of at least one selected from the group consisting of the fluorene compound D and the bisphenol compound E, and a mixture of two or more. It may be used.
(B) When two or more of the above-mentioned compounds D and E are used as a (meth) acrylate compound, it is preferable that the above-mentioned fluorene compound D is contained as an essential compound, and the fluorene compound D and the bisphenol compound E It is preferable to use at least the species.
When two or more kinds are mixed and used, for example, when fluorene compound D and bisphenol compound E are mixed and used, these should be fluorene compound D: bisphenol compound E = 20: 1 to 1: 1. Is preferable, and 10: 1 to 2: 1 is more preferable.

<(C) Polymer>
The polymer (c) contained in the polymerizable composition of the present invention has a weight average molecular weight Mw measured in terms of polystyrene by gel permeation chromatography (GPC) of 5,000 to 100,000, preferably 10,000 to 80. 20,000, more preferably 20,000-60,000 polymers.
In addition, a polymer having at least a monomer unit represented by the formula [3] or a monomer unit represented by the formula [4] is preferable, and is represented by at least the monomer unit represented by the formula [3] and the formula [4]. A polymer having monomer units is more preferred.

上記式［３］中、Ａｒ⁴は炭素原子数１乃至６のアルキル基で置換されていてもよいフェニル基、炭素原子数１乃至６のアルキル基で置換されていてもよいナフチル基、又は炭素原子数１乃至６のアルキル基で置換されていてもよいビフェニル基を表し、Ｒ³は水素原子又はメチル基を表す。

In the above formula [3], Ar ⁴ is a phenyl group which may be substituted with an alkyl group having 1 to 6 carbon atoms, a naphthyl group which may be substituted with an alkyl group having 1 to 6 carbon atoms, or carbon. It represents a biphenyl group which may be substituted with an alkyl group having 1 to 6 atoms, and R ³ represents a hydrogen atom or a methyl group.

Ar ⁴ represents a phenyl group which may be substituted with an alkyl group having 1 to 6 carbon atoms, a naphthyl group which may be substituted with an alkyl group having 1 to 6 carbon atoms, and an alkyl group having 1 to 6 carbon atoms. Examples of the biphenyl group optionally substituted with an alkyl group include the same groups as those exemplified as Ar ¹ and Ar ² in the above formula [1].

  Specific examples of the monomer unit represented by the formula [3] include, for example, 1-phenylethylene group, 1-methyl-1-phenylethylene group, 1- (naphthalen-1-yl) ethylene group, 1- ( [1,1′-biphenyl] -2-yl) ethylene group, 1-([1,1′-biphenyl] -3-yl) ethylene group, 1-([1,1′-biphenyl] -4-yl ) Ethylene group and the like. Of these, a 1-phenylethylene group is preferable.

上記式［４］中、Ｒ⁴は水素原子又はメチル基を表し、Ｒ⁵は炭素原子数１乃至１２のアルキル基を表す。

In the above formula [4], R ⁴ represents a hydrogen atom or a methyl group, and R ⁵ represents an alkyl group having 1 to 12 carbon atoms.

Examples of the alkyl group having 1 to 12 carbon atoms represented by R ⁵ include, for example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, isoamyl group, neopentyl group, tert-amyl group, sec-isoamyl group, cyclopentyl group, n-hexyl group, cyclohexyl group, n-heptyl group, n-octyl group, 2-ethylhexyl group, n-nonyl Group, n-decyl group, n-dodecyl group, benzyl group, phenethyl group and the like.

  Specific examples of the monomer unit represented by the above formula [4] include 1-methoxycarbonylethylene group, 1-methoxycarbonyl-1-methylethylene group and the like.

Specific examples of such a polymer include, for example, polystyrene, acrylonitrile-chlorinated polyethylene-styrene copolymer (ACS), acrylonitrile-butadiene-styrene copolymer (ABS), acrylonitrile-EPDM (ethylene-propylene-dienter). Polymer) -styrene copolymer (AES), acrylonitrile-styrene copolymer (AS), acrylonitrile-styrene-acrylate copolymer (ASA), methyl methacrylate-butadiene-styrene copolymer (MBS), methyl methacrylate -Styrene polymers such as styrene copolymer (MS), silicone-acrylonitrile-styrene copolymer (SAS), styrene-butadiene copolymer (SBC), styrene-maleic anhydride copolymer (SMA); poly ( Acry (Meth acid), (meth) acrylic polymers such as poly (methyl methacrylate) (PMMA); polyolefins such as polyethylene (PE) and polypropylene (PP); polyamide (PA); polycarbonate (PC); polyethylene terephthalate (PET), Polybutylene terephthalate (PBT) and other polyesters; cyclic polyolefin (COP); polyaryl ethers; polyether ether ketone (PEEK); polyether sulfone (PES); polyurethane (PU); fluorene polyester resin (for example, Osaka Gas Chemical) (Okp4 manufactured by Co., Ltd.).
Of these, styrene polymers are preferable, and polystyrene and methyl methacrylate-styrene copolymers are more preferable.

  (C) When using a copolymer as a polymer, the molar ratio of each monomer unit constituting the copolymer is not particularly limited. For example, in the case of a copolymer having a monomer unit represented by the above formula [3] and a monomer unit represented by the formula [4], these are molar ratios of the monomer unit represented by the formula [3]: formula The monomer unit represented by [4] is preferably 99: 1 to 10:90.

  In the polymerizable composition of the present invention, the polymer (c) may be used alone or in combination of two or more. Moreover, 0.1-50 mass parts is preferable with respect to 100 mass parts of (a) reactive silicone compound, its 0.5-30 mass parts is more preferable, and its 1-20 mass parts is especially preferable.

<(D) Stabilizer>
In addition to the above-mentioned (a) reactive silicone compound, (b) (meth) acrylate compound and (c) polymer, the polymerizable composition of the present invention includes a light stabilizer F and an antioxidant as a component (d). At least one stabilizer selected from the group consisting of the agent G may be included.

上記式［７］中、Ｒ¹²は水素原子、炭素原子数１乃至１０のアルキル基、又は炭素原子数１乃至１２のアルコキシ基を表し、黒点は結合手を表す。[Light stabilizer F]
Among the components (d) used in the present invention, the light stabilizer F is a compound having a group represented by the following formula [7].

In the above formula [7], R ¹² represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or an alkoxy group having 1 to 12 carbon atoms, and a black dot represents a bond.

Examples of the alkyl group having 1 to 10 carbon atoms represented by R ¹² include, for example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, isoamyl group, neopentyl group, tert-amyl group, sec-isoamyl group, cyclopentyl group, n-hexyl group, cyclohexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl Groups and the like.

Examples of the alkoxy group having 1 to 12 carbon atoms represented by R ¹² include a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, an isobutoxy group, a sec-butoxy group, and a tert-butoxy group. , N-pentyloxy group, isoamyloxy group, neopentyloxy group, tert-amyloxy group, sec-isoamyloxy group, cyclopentyloxy group, n-hexyloxy group, cyclohexyloxy group, n-heptyloxy group, n-octyl And group oxy, n-nonyloxy, n-decyloxy, n-undecyloxy and the like.

Among these, R ¹² is preferably a hydrogen atom, a methyl group, a cyclohexyloxy group, or an n-octyloxy group.

  As such a light stabilizer F, for example, TINUVIN (registered trademark) 123, 144, 152, 292, 770 [above, manufactured by BASF Japan Ltd.], ADK STAB (registered trademark) LA-52, LA-57, LA-63P, LA-68, LA-72, LA-77Y, LA-77G, LA-81, LA-82, LA-87 [above, Co., Ltd.] ADEKA] and the like.

上記式［８］中、Ｒ¹³は炭素原子数１乃至１０のアルキル基を表し、Ｒ¹⁴乃至Ｒ¹⁶はそれぞれ独立して、水素原子、又は炭素原子数１乃至１０のアルキル基を表し、黒点は結合手を表す。[Antioxidant G]
Among the components (d) used in the present invention, the antioxidant G is a compound having a group represented by the following formula [8].

In the above formula [8], R ¹³ represents an alkyl group having 1 to 10 carbon atoms, R ^{14 to} R ¹⁶ each independently represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and a black spot Represents a bond.

Examples of the alkyl group having 1 to 10 carbon atoms represented by R ¹³ and R ^{14 to} R ¹⁶ include the same groups as those exemplified as R ¹² in the above formula [7]. Among them, R ¹³ is preferably a tert-butyl group.
Examples of such a group represented by the formula [8] include 3-tert-butyl-4-hydroxy-5-methylphenyl group, 3-tert-butyl-4-hydroxy-6-methylphenyl group, 3 , 5-di-tert-butyl-4-hydroxyphenyl group and the like.

  Examples of such an antioxidant G include IRGANOX (registered trademark) 245, 1010, 1035, 1076, 1135 [above, manufactured by BASF Japan Ltd.], Sumilizer (registered trademark) GA-80, GP, MDP-S, BBM-S, WX-R [above, manufactured by Sumitomo Chemical Co., Ltd.], ADK STAB (registered trademark) AO-20, AO-30, AO-40, AO- 50, the same AO-60, the same AO-80, the same AO-330 [above, manufactured by ADEKA Corporation] and the like.

When (d) component is mix | blended in the polymeric composition of this invention, it is preferable to contain (d) component in 0.01-5 mass parts with respect to 100 mass parts of said (a) component, More preferably, it is 0.05-1 mass part.
In the present invention, as the component (d), the light stabilizer F may be used alone or in combination of two or more, or the antioxidant G may be used alone or in combination of two or more. Alternatively, one or more light stabilizers F and one or more antioxidants G may be mixed and used. When a plurality of types of compounds are used as the component (d), the total amount of the plurality of types of compounds used is within the above range.

<(E) Sulfur compound>
In addition to the above-mentioned (a) reactive silicone compound, (b) (meth) acrylate compound and (c) polymer, or the above-mentioned components (a) to (d), the polymerizable composition of the present invention comprises: e) The component may contain at least one sulfur compound selected from the group consisting of the thiol compound H and the disulfide compound I.

[Thiol Compound H]
Among the components (e) used in the present invention, examples of the thiol compound H include, for example, methyl mercaptoacetate, methyl 3-mercaptopropionate, 3-mercaptopropionic acid = 4-methoxybutyl, 3-mercaptopropionic acid = 2− Ethylhexyl, n-octyl 3-mercaptopropionate, stearyl 3-mercaptopropionate, 1,4-bis (3-mercaptopropionyloxy) butane, 1,4-bis (3-mercaptobutyryloxy) butane, trimethylolethane Tris (3-mercaptopropionate), trimethylolethane tris (3-mercaptobutyrate), trimethylolpropane tris (3-mercaptopropionate), trimethylolpropane tris (3-mercaptobutyrate), pentaerythritol te Lakis (3-mercaptopropionate), pentaerythritol tetrakis (3-mercaptobutyrate), dipentaerythritol hexakis (3-mercaptopropionate), dipentaerythritol hexakis (3-mercaptobutyrate), tris [ Mercaptocarboxylic acid esters such as 2- (3-mercaptopropionyloxy) ethyl] isocyanurate and tris [2- (3-mercaptobutyryloxy) ethyl] isocyanurate; ethyl mercaptan, 1,2-dimercaptoethane, 1 Mercaptoalkanes such as 1,3-dimercaptopropane, tert-butyl mercaptan, n-dodecanethiol, tert-dodecanethiol; mercaptoalcos such as 2-mercaptoethanol and 4-mercapto-1-butanol Aromatic ring mercaptans such as thiophenol, benzylthiol, m-toluenethiol, p-toluenethiol, 2-naphthalenethiol, 2-pyridylthiol, 2-mercaptobenzimidazole, 2-mercaptobenzothiazole; Silane-containing thiols such as (mercaptopropyl) trimethoxysilane and (γ-mercaptopropyl) triethoxysilane. Among these, mercaptoalkanes are preferable, and n-dodecanethiol is more preferable.

[Disulfide Compound I]
Among the components (e) used in the present invention, the disulfide compound I includes, for example, diethyl disulfide, dipropyl disulfide, diisopropyl disulfide, dibutyl disulfide, di-tert-butyl disulfide, dipentyl disulfide, diisopentyl disulfide, dihexyl disulfide , Dicyclohexyl disulfide, didecyl disulfide, di-tert-dodecyl disulfide, bis (2-hydroxyethyl) disulfide, bis (2,2-diethoxyethyl) disulfide, and other alkyl disulfides; diphenyl disulfide, ditolyl disulfide, dibenzyl Disulfide, 2,2'-dipyridyl disulfide, 2,2'-dibenzimidazolyl disulfide, 2,2'-dibenzothiazolyl disulfide含芳 incense ring disulfides of; tetramethyl thiuram disulfide, tetraethyl thiuram disulfide, tetrabutyl thiuram disulfide, thiuram disulfides such as di-pentamethylene thiuram disulfide and the like. Of these, alkyl disulfides are preferable, and didecyl disulfide is more preferable.

When (e) component is mix | blended in the polymeric composition of this invention, it is preferable to contain (e) component in 0.01-5 mass parts with respect to 100 mass parts of said (a) component, More preferably, it is 0.1-1 mass part.
In the present invention, as the component (e), the thiol compound H may be used alone or in combination of two or more, or the disulfide compound I may be used alone or in combination of two or more, or A mixture of one or more thiol compounds H and one or more disulfide compounds I may be used. When a plurality of types of compounds are used as the component (e), the total amount of the plurality of types of compounds used is within the above range.

<(F) Polymerization initiator>
The polymerizable composition of the present invention may contain (f) a polymerization initiator in addition to the components (a) to (c) or the components (a) to (e). As the polymerization initiator, either a thermal polymerization initiator or a photopolymerization initiator can be used.

Examples of the thermal polymerization initiator include azos and organic peroxides.
Examples of commercially available azo-based thermal polymerization initiators include V-30, V-40, V-59, V-60, V-65, and V-70 [above, manufactured by Wako Pure Chemical Industries, Ltd.] Etc.
Examples of commercially available organic peroxide thermal polymerization initiators include Parkadox (registered trademark) CH, BC-FF, 14, 16 and Trigonox (registered trademark) 22, 23, 121. , Kayaester (registered trademark) P, O, Kayabutyl (registered trademark) B [above, manufactured by Kayaku Akzo Co., Ltd.], Perhexa (registered trademark) HC, Parkmill (registered trademark) H, Perocta (registered trademark) O Perhexyl (registered trademark) O, Z, perbutyl (registered trademark) O, Z [above, manufactured by NOF Corporation] and the like, but is not limited thereto.

Examples of the photopolymerization initiator include alkylphenones, benzophenones, acylphosphine oxides, Michler's benzoylbenzoates, oxime esters, tetramethylthiuram monosulfides, and thioxanthones.
In particular, photocleavable photoradical polymerization initiators are preferred. Examples of the photocleavable photoradical polymerization initiator include those described in the latest UV curing technology (p. 159, publisher: Kazuhiro Takahisa, publisher: Technical Information Association, published in 1991). .
Examples of commercially available radical photopolymerization initiators include IRGACURE (registered trademark) 184, 369, 651, 500, 819, 907, 784, 2959, CGI 1700, CGI 1750, CGI1850, CG24-61, TPO, Darocur (registered trademark) 1116, 1173 [above, manufactured by BASF Japan Ltd.], ESACURE KIP150, KIP65LT, KIP100F, KT37, KT55, KTO46, KIP75 [Above, manufactured by Lamberti Co., Ltd.].

  When adding a polymerization initiator, you may use a polymerization initiator individually by 1 type or in mixture of 2 or more types. Moreover, as the addition amount, it is 0.1-20 mass parts with respect to 100 mass parts of (a) reactive silicone compound, More preferably, it is 0.3-10 mass parts.

<(G) Diluent>
In the polymerizable composition of the present invention, the aforementioned (a) reactive silicone compound, (b) (meth) acrylate compound and (c) polymer, or the above (a), for the purpose of improving the handling of the polymerizable composition. In addition to the components) to (f), a diluent may be included as the component (g). As the diluent, it is preferable to use a compound having at least one group having a polymerizable double bond and having a viscosity at 25 ° C. of 500 mPa · s or less, more preferably 100 mPa · s or less.

Examples of such a diluent include vinyl compounds such as styrene and divinylbenzene; methyl (meth) acrylate, ethyl (meth) acrylate, 2,2,2-trifluoroethyl (meth) acrylate, n-propyl (meth) ) Acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, sec-butyl (meth) acrylate, isobutyl (meth) acrylate, tert-butyl (meth) acrylate, n-hexyl (meth) acrylate, n-octyl (Meth) acrylate, isobornyl (meth) acrylate, adamantyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, 2- (dicyclopentanyloxy) ethyl (meth) acrylate 2- (dicyclopentenyloxy) ethyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, benzyl (meth) acrylate, phenoxyethyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, ethoxylation Monofunctional (meth) acrylates such as phenyl (meth) acrylate and ethoxylated o-phenylphenol (meth) acrylate; ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, propylene Glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate Relate, 1,3-butanediol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, propoxylated neopentyl glycol di (meth) acrylate, neopentyl glycol mono (Hydroxypivalic acid) ester di (meth) acrylate, 3-methyl-1,5-pentanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 2- (3-hydroxy-2-methylpropyl) -2-yl) -5-ethyl-5-hydroxymethyl-1,3-dioxane di (meth) acrylate (also referred to as dioxane glycol di (meth) acrylate), tricyclo [5.2.1.0 ^2,6 ] Bifunctional such as decanedimethanol di (meth) acrylate (Meth) acrylates; trimethylolethane tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, ethoxylated trimethylolpropane tri (meth) acrylate, propoxylated trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) ) Acrylate, ethoxylated pentaerythritol tetra (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate and other trifunctional or higher (meth) acrylates.

  Among these, monofunctional (meth) acrylates, bifunctional (meth) acrylates, trifunctional or higher (meth) acrylate (meth) acrylate compounds are preferable, and neopentyl glycol di (meth) acrylate is more preferable.

  When adding a diluent, you may use a diluent individually by 1 type or in mixture of 2 or more types. Moreover, as the addition amount, it is 10-300 mass parts with respect to 100 mass parts of (c) polymers, More preferably, it is 50-200 mass parts.

<Other additives>
Furthermore, in the polymerizable composition of the present invention, a reactive diluent, a chain transfer agent, an antioxidant, an ultraviolet absorber, a surfactant, and a leveling agent are added as necessary as long as the effects of the present invention are not impaired. Other components such as an antifoaming agent and an adhesion improver may be added as appropriate.

<Method for Preparing Polymerizable Composition>
The method for preparing the polymerizable composition of the present embodiment is not particularly limited. As a preparation method, for example, the components (a) to (c) and, if necessary, the components (d) to (g) are mixed at a predetermined ratio, and other additives are further added as desired. , A method of forming a uniform solution, or a method of using a conventional solvent in addition to these components.

  When using a solvent, the ratio of the solid content in the polymerizable composition is not particularly limited as long as each component is uniformly dissolved in the solvent, but is, for example, 1 to 50% by mass, or 1 to 30. % By mass or 1 to 25% by mass. Here, the solid content is obtained by removing the solvent component from all components of the polymerizable composition.

  In addition, the solution of the polymerizable composition is preferably used after being filtered using a filter having a pore size of 0.05 to 5 μm.

<< cured product >>
The present invention also relates to a cured product obtained by heat or photopolymerization of the polymerizable composition.
Although it does not specifically limit as heating conditions in thermal polymerization, Usually, it selects suitably from the range of 50-300 degreeC and 1-120 minutes. Moreover, it does not specifically limit as a heating means, For example, a hotplate, oven, etc. are mentioned.
Examples of actinic rays used for photopolymerization include ultraviolet rays, electron beams, and X-rays. As a light source used for ultraviolet irradiation, sunlight, a chemical lamp, a low-pressure mercury lamp, a high-pressure mercury lamp, a metal halide lamp, a xenon lamp, a UV-LED, or the like can be used. In addition, after the photopolymerization, post-bake is performed as necessary. Specifically, the polymerization is usually completed by heating at 50 to 300 ° C. for 1 to 120 minutes using a hot plate, an oven or the like. Can do.

  The cured product of the present invention has a refractive index as high as 1.55 or more at a wavelength of 589 nm, and also has a dimensional stability by suppressing yellowing and cracking due to heating. It is useful as a material for a high refractive index resin lens such as an optical lens.

<< Molded Article >>
The polymerizable composition of the present invention can be formed into various molded products in parallel with the formation of a cured product by using a conventional molding method such as compression molding (imprinting, etc.), casting, injection molding, blow molding and the like. Can be easily manufactured. A molded body (for example, an optical lens) thus obtained is also an object of the present invention.
As a method for producing a molded body, for example, a step of filling the above-described polymerizable composition of the present invention between a lower surface mold or a support and an upper surface mold, and heating the filled composition for thermal polymerization. The manufacturing method including the step of performing and the step of releasing the thermal polymer from the mold is preferable.
The heating and thermal polymerization step can be performed by applying the conditions shown in the above << cured product >>.
The molded body produced by such a method can be suitably used as a camera module lens.

EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated more concretely, this invention is not limited to the following Example.
In the examples, the apparatus and conditions used for sample preparation and physical property analysis are as follows.

(1) ¹ H NMR spectrum apparatus: JNM-ECX300 manufactured by JEOL Ltd.
Measuring solvent: CDCl ₃
Reference substance: Tetramethylsilane (0.00ppm)
(2) Gel permeation chromatography (GPC)
Apparatus: GPC system manufactured by Shimadzu Corporation Column: Shodex (registered trademark) GPC KF-804L, GPC KF-803L manufactured by Showa Denko K.K.
Column temperature: 40 ° C
Solvent: Tetrahydrofuran Detector: UV (254 nm)
Calibration curve: Standard polystyrene (3) Mix rotor Device: MRC-5 manufactured by AS ONE
(4) Agitating and defoaming machine: Rotating / revolving mixer manufactured by Shinky Co., Ltd. Nertaro Awatori (registered trademark) ARE-310
(5) Refractive index n _D , Abbe number ν _D
Apparatus: Multi-wavelength Abbe refractometer DR-M4 manufactured by Atago Co., Ltd.
Measurement temperature: 20 ° C
Intermediate liquid: Monobromonaphthalene (6) Haze Equipment: (Existing) Tokyo Denshoku spectrophotometric colorimetric haze meter TC-1800H
Reference: Air (7) Reflow Oven Device: Desktop Reflow Oven STR-3100, manufactured by Thin Apex Co., Ltd.
(8) Light transmittance device: UV-visible spectrophotometer UV-3100 manufactured by Shimadzu Corporation

Abbreviations represent the following meanings.
BnA: benzyl acrylate [Osaka Organic Chemical Co., Ltd. Viscoat # 160]
BPEA: Ethoxylated bisphenol A diacrylate (addition of 4 mol of ethoxy group) [NK Nakano Chemical Co., Ltd. NK ester A-BPE-4]
FDA: Bisaryl full orange acrylate [Ogsol (registered trademark) EA-F5503 manufactured by Osaka Gas Chemical Co., Ltd.]
HDDA: 1,6-hexanediol diacrylate [Biscoat # 230, manufactured by Osaka Organic Chemical Industry Co., Ltd.]
NPGDA: Neopentylglycol diacrylate [Kyarad (registered trademark) NPGDA manufactured by Nippon Kayaku Co., Ltd.]
TMP3A: Trimethylolpropane triacrylate [Shin Nakamura Chemical Co., Ltd. NK Ester A-TMPT]
MS37: methyl methacrylate-styrene copolymer [manufactured by Negami Kogyo Co., Ltd. MS3703, copolymerization molar ratio: methyl methacrylate / styrene = 30/70, Mw: 36,000]
MS55: Methyl methacrylate-styrene copolymer [manufactured by Negami Kogyo Co., Ltd. MS5503, copolymerization molar ratio: methyl methacrylate / styrene = 50/50, Mw: 40,000]
MS82: Methyl methacrylate-styrene copolymer [manufactured by Negami Kogyo Co., Ltd. MS8203, copolymerization molar ratio: methyl methacrylate / styrene = 80/20, Mw: 40,000]
PS: Polystyrene [manufactured by Negami Kogyo Co., Ltd. MS0103, Mw: 32,000]

[Production Example 1] Production of reactive fluorine-containing silicone compound (F-SC) In a 200 mL eggplant type flask equipped with a condenser, 43.3 g (0.200 mol) of diphenylsilanediol [manufactured by Tokyo Chemical Industry Co., Ltd.] , Trimethoxy (4-vinylphenyl) silane [Shin-Etsu Chemical Co., Ltd.] 44.0 g (0.196 mol), trimethoxy (3,3,3-trifluoropropyl) silane [Shin-Etsu Chemical Co., Ltd.] 0 .873 g (0.004 mol) and 35 g of toluene were charged, and the air in the flask was replaced with nitrogen using a nitrogen balloon. The reaction mixture was heated to 50 ° C., and 38 mg (0.2 mmol) of barium hydroxide monohydrate [manufactured by Aldrich] was added. The mixture was stirred at 50 ° C. for 1 hour as it was, and then further stirred at 85 ° C. for 5 hours to carry out dealcoholization condensation. The reaction mixture was cooled to room temperature (approximately 25 ° C.), and insoluble matters were removed using a membrane filter having a pore size of 0.2 μm. Using a rotary evaporator, toluene and by-product methanol were distilled off from the reaction mixture under reduced pressure at 50 ° C., thereby obtaining 74.9 g of a colorless, transparent oily reactive fluorine-containing silicone compound.
The ¹ H NMR spectrum of the obtained reactive fluorine-containing silicone compound is shown in FIG. Moreover, the weight average molecular weight Mw measured by polystyrene conversion by GPC was 1,400, and dispersion degree Mw (weight average molecular weight) / Mn (number average molecular weight) was 1.3.

[Production Example 2] Production of Reactive Silicone Compound (SC) Into a 1 L eggplant-shaped flask equipped with a condenser, 177 g (0.80 mol) of diphenylsilanediol [manufactured by Tokyo Chemical Industry Co., Ltd.], trimethoxy (4-vinyl) Phenyl) silane [manufactured by Shin-Etsu Chemical Co., Ltd.] 179 g (0.80 mol) and toluene 141 g were charged, and the air in the flask was replaced with nitrogen using a nitrogen balloon. This reaction mixture was heated to 50 ° C., 0.303 g (1.6 mmol) of barium hydroxide monohydrate [manufactured by Aldrich] was added, and the mixture was further stirred at 50 ° C. for 2 days for dealcohol condensation. The reaction mixture was cooled to room temperature (approximately 25 ° C.), and insoluble matters were removed using a membrane filter having a pore size of 0.2 μm. Using a rotary evaporator, toluene and by-product methanol were distilled off from this reaction mixture under reduced pressure at 50 ° C. to obtain 305 g of a colorless transparent oily reactive silicone compound.
The ¹ H NMR spectrum of the obtained reactive silicone compound is shown in FIG. Moreover, the weight average molecular weight Mw measured by polystyrene conversion by GPC was 1,500, and dispersion degree Mw / Mn was 1.3.

[Example 1] Preparation of polymerizable composition FDA 32.5 parts by mass as a (meth) acrylate compound and BPEA 10 parts by mass, MS82 3 parts by mass as a polymer, 3,9-bis (2- (2- ( 3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy) -1,1-dimethylethyl) -2,4,8,10-tetraoxospiro [5.5] undecane [Sumitomo Chemical Co., Ltd.] Co., Ltd. SUMILIZER (registered trademark) GA-80] 0.5 parts by mass, and 4.5 parts by mass of NPGDA as a diluent were mixed using a mixed rotor until uniform at 50 ° C. (approximately 24 hours ). To this mixture, 50 parts by mass of F-SC produced in Example 1 as a reactive silicone compound, 0.5 parts by mass of didecyl disulfide [manufactured by Tokyo Chemical Industry Co., Ltd.] as a sulfur compound, and 2, as a polymerization initiator Add 3 parts by mass of 4,4-trimethylpentan-2-yl peroxy-2-ethylhexanoate [Nippon Yushi Co., Ltd. Perocta (registered trademark) O] and stir and remove at 2000 rpm for about 30 minutes until uniform. Polymerizable composition 1 was prepared by foaming.

[Examples 2 to 8, Comparative Example 1]
Polymerizable compositions 2 to 9 were prepared in the same manner as in Example 1 except that each composition was changed as shown in Table 1.

[Examples 9 to 16, Comparative Example 2] Production and evaluation of cured product [Production of cured product]
The polymerizable composition shown in Table 2 was sandwiched between two glass substrates subjected to release treatment together with a spacer made of silicone rubber having a thickness of 800 μm. The sandwiched polymerizable composition is heated in an oven at 130 ° C. for 15 minutes, cooled to room temperature (approximately 25 ° C.), and then the cured product is peeled off from the glass substrate, whereby a cured product having a diameter of 30 mm and a thickness of 800 μm is obtained. Produced.
[Optical characteristics evaluation]
The obtained cured product was measured for refractive index n _D , Abbe number ν _D and haze (HAZE) at D line (wavelength 589 nm). Moreover, about the obtained hardened | cured material, the light transmittance of wavelength 400nm before and behind the heating test using a reflow furnace was measured, respectively, and the fall of the transmittance | permeability by heating was evaluated. In the heating test, three steps of 1) heating up to 260 ° C. in 3 minutes, 2) holding at 260 ° C. for 20 seconds, and 3) cooling to 50 ° C. were repeated three times. The results are also shown in Table 2.
[Crack resistance evaluation]
A cured product having a diameter of 5 mm and a thickness of 800 μm was produced in accordance with the method described in [Production of Cured Product]. Five of these cured products were heated in a reflow furnace, and the crack resistance was evaluated by the number of cured products having cracks after heating. The heating was performed in three steps: 1) heating up to 260 ° C. over 3 minutes, 2) holding at 260 ° C. for 20 seconds, and 3) cooling to 50 ° C. The results are also shown in Table 2.

As shown in Table 2, all of the cured products (Examples 9 to 16) obtained from the polymerizable composition of the present invention had a low HAZE value of less than 1, a high light transmittance, and heating. It was confirmed that the film had very advantageous heat-resistant yellowing in which the light transmittance hardly changed (no yellowing) before and after (a solder reflow process at 260 ° C.). Furthermore, the cured products obtained from the polymerizable composition of the present invention are all monolithic lens sizes having a diameter of 5 mm and a thickness of 800 μm after heating (such as a solder reflow process at 260 ° C.). It was confirmed that no cracks were generated and the crack resistance was excellent.
On the other hand, it was confirmed that the cured product to which no specific polymer was added (Comparative Example 2) had low crack resistance and could not withstand the solder reflow process.

The polymerizable composition of the present invention has a high refractive index and a low Abbe number that are required for the cured product of the lens for a high resolution camera module. Moreover, the hardened | cured material obtained from the polymeric composition of this invention has heat resistance which does not produce yellowing and a crack also in the high temperature heat history in a solder reflow process, such as 260 degreeC, for example.
As described above, the polymerizable composition of the present invention can obtain a cured product having both excellent optical activity and heat resistance, and thus can be used particularly suitably as a material for a thick camera module lens by, for example, casting molding. .

Claims (11)

(A) Polycondensation of a mixture of a polycondensable compound containing at least the diaryl silicate compound A represented by the formula [1] and the alkoxysilicon compound B represented by the formula [2] in the presence of an acid or a base 100 parts by mass of a reactive silicone compound obtained by
Table with (b) (meth) acrylate compound 1-200 parts by weight, and (c) have a weight average molecular weight of 5,000 to 100,000 monomer units of formula represented by the formula [3] [4] A polymerizable composition containing 0.1 to 50 parts by mass of a polymer containing the monomer unit in a molar ratio of 100: 0 to 20:80 .

(In the formula, Ar ¹ and Ar ² are each independently a phenyl group which may be substituted with an alkyl group having 1 to 6 carbon atoms, or an alkyl group having 1 to 6 carbon atoms. It represents a naphthyl group or a biphenyl group optionally substituted with an alkyl group having 1 to 6 carbon atoms.)

(In the formula, Ar ³ represents at least a phenyl group having at least one group having a polymerizable double bond, a naphthyl group having at least one group having a polymerizable double bond, or a group having a polymerizable double bond). 1 represents a biphenyl group, R ¹ represents a methyl group or an ethyl group, R ² represents a methyl group, an ethyl group, or a vinylphenyl group, and a represents 2 or 3.)

(In the formula, Ar ⁴ is a phenyl group which may be substituted with an alkyl group having 1 to 6 carbon atoms, a naphthyl group which may be substituted with an alkyl group having 1 to 6 carbon atoms, or 1 carbon atom) Represents a biphenyl group which may be substituted with thru 6 alkyl groups, and R ³ represents a hydrogen atom or a methyl group.)

(In the formula, R ⁴ represents a hydrogen atom or a methyl group, and R ⁵ represents an alkyl group having 1 to 12 carbon atoms.) The polymerizable composition according to claim 1, wherein Ar ⁴ in the formula [3] is a phenyl group . The polymerizable composition according to claim 2 , wherein the polymer (c) is poly (styrene-co-methyl (meth) acrylate). The (b) (meth) acrylate compound is at least one selected from the group consisting of a fluorene compound D represented by the formula [5] and a bisphenol compound E represented by the formula [6]. The polymerizable composition according to claim 3 .

(In the formula, R ⁶ and R ⁷ each independently represent a hydrogen atom or a methyl group, and L ¹ and L ² each independently represent a phenylene group which may have a substituent, or a substituent. An optionally substituted naphthalenediyl group, L ³ and L ⁴ each independently represents an alkylene group having 1 to 6 carbon atoms, and m and n are 0 or positive in which m + n is 0 to 40 Represents an integer.)

(Wherein R ⁸ and R ⁹ each independently represent a hydrogen atom or a methyl group, R ¹⁰ and R ¹¹ each independently represent a hydrogen atom, a methyl group or a trifluoromethyl group, L ⁵ and L ⁶ independently represents an alkylene group having 1 to 6 carbon atoms, and p and q represent 0 or a positive integer in which p + q is 0 to 40.) The polymerizable composition according to claim 4 , comprising at least two of the fluorene compound D and the bisphenol compound E as the (b) (meth) acrylate compound. Further, (d) at least one selected from the group consisting of a light stabilizer F, which is a compound having a group represented by formula [7], and an antioxidant G, which is a compound having a group represented by formula [8]. The polymerizable composition according to any one of claims 1 to 5 , comprising 0.01 to 5 parts by mass of a stabilizer.

(Wherein R ¹² represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or an alkoxy group having 1 to 12 carbon atoms, and a black dot represents a bond)

(Wherein R ¹³ represents an alkyl group having 1 to 10 carbon atoms, R ^{14 to} R ¹⁶ each independently represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and a black dot represents a bond. Represents.) Furthermore, (e) Polymerizability as described in any one of Claims 1 thru | or 6 containing 0.01-5 mass parts of at least 1 sort (s) of sulfur compounds chosen from the group which consists of the thiol compound H and the disulfide compound I. Composition. The reactive silicone compound (a) is a diaryl silicate compound A represented by the formula [1], an alkoxy silicon compound B represented by the formula [2], and an alkoxy silicon represented by the formula [9]. The polymerization according to any one of claims 1 to 7 , which is a reactive silicone compound obtained by polycondensation of a mixture of polycondensable compounds containing at least compound C in the presence of an acid or a base. Sex composition.

(Wherein Rf represents a fluoroalkyl group having 1 to 12 carbon atoms or a fluorophenyl group, R ¹⁷ represents a methyl group or an ethyl group, R ¹⁸ represents a methyl group, an ethyl group or a vinylphenyl group; b represents 2 or 3.) Hardened | cured material obtained by superposing | polymerizing the polymeric composition as described in any one of Claims 1 thru | or 8 . An optical lens obtained by polymerizing the polymerizable composition according to any one of claims 1 to 8 . A material for a high refractive index resin lens comprising the polymerizable composition according to any one of claims 1 to 8 .

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