JPWO2017209004A1 - Low viscosity agent for high refractive index polymerizable compound and polymerizable composition containing the same - Google Patents

Abstract

Disclosed is a high-refractive index low-viscosity agent that overcomes the trade-off between low Abbe and low-viscosity and has a low refractive index loss when blended, and a polymerizable composition containing the same.
A compound having a solid state at 23 ° C. under 1013.25 hPa and having a melting point of less than 100 ° C., having a viscosity at 100 ° C. of 10 mPa · s or less, and a D line of the cured product A compound having an Abbe number of 23 or less at (589.3 nm) having at least one polymerizable double bond and a refractive index of the cured product at the D-line (589.3 nm) of 1.60 or higher A method of using as a viscosity reducing agent for a refractive index polymerizable compound.
[Selection figure] None

Description

  The present invention relates to a viscosity reducing agent, and in particular, to a viscosity reducing agent useful as a high refractive index diluent capable of reducing the viscosity of a polymerizable optical material having a high refractive index.

Resin lenses are used in electronic devices such as mobile phones, digital cameras, and in-vehicle cameras, and are required to have excellent optical characteristics according to the purpose of the electronic device. Moreover, high durability, for example, heat resistance and weather resistance, and high productivity that can be molded with a high yield are required in accordance with the usage mode. As a resin lens material that satisfies such requirements, for example, thermoplastic transparent resins such as polycarbonate resin, cycloolefin polymer, and methacrylic resin have been used.
In recent years, in the production of resin lenses, in order to improve yield and production efficiency, and to suppress optical axis misalignment during lens lamination, from injection molding of thermoplastic resin to pressing molding using liquid curable resin at room temperature. The transition to wafer level molding by means of is being actively studied.

A plurality of lenses are used in the high-resolution camera module, and an optical material having high wavelength dispersion, that is, a low Abbe number is required as one of the wavelength correction lenses.
A material characterized by a low Abbe number will require high transparency in addition to a high refractive index, but improving these optical properties will increase the viscosity of the material and significantly degrade handling. There are many. This is because, in general, components that contribute to a high refractive index have a high electron density and are therefore easily increased in viscosity, and deterioration in handling properties can be said to be an essential issue in the development of low Abbe materials.

  In response to such a problem, for example, there is a proposal for a curable composition for a lens material that employs a liquid (meth) acrylate having a relatively high refractive index as a diluent to reduce viscosity and improve handling properties ( Patent Document 1). In addition, there is a proposal of a curable composition that achieves a low viscosity without using a diluent by introducing an oxyalkylene group into a component that contributes to a high refractive index (Patent Document 2).

JP 2012-255914 A Japanese Patent Laying-Open No. 2015-199952

However, the curable composition (Patent Document 1) using the aforementioned diluent has an Abbe number ν _D of 25 or more, for example, 23 or less, although the refractive index n _{D at} 589 nm after photocuring is around 1.61. The low Abbe number requirement is not satisfied. Further, in the curable composition not using a diluent (Patent Document 2), the refractive index n _D after photocuring: 1.60 or more is not realized, and this sufficiently satisfies the optical characteristics. It is not.
As described above, lower Abbe and lower viscosity are in a trade-off relationship, for example, a low viscosity of 10,000 mPa · s or less is achieved, and a high refractive index of 1.60 or more in a cured product is 23 or less. No optical material has yet achieved excellent optical properties such as a low Abbe number.
Conventional diluents for achieving low viscosity generally have a low refractive index. On the other hand, optical properties (high refractive index and low Abbe number) required for recent optical materials for lenses for high-resolution camera modules, etc. Since (high transparency) is further enhanced, the addition of a conventional diluent (low viscosity agent) can lead to a high Abbe of the optical material.
The present invention has been made in view of such circumstances, and has overcome the trade-off between low Abbe and low viscosity, and has low refractive index loss when blended, with high refractive index and low viscosity. It is an object of the present invention to provide an agent and a polymerizable composition containing the agent.

  As a result of intensive studies to solve the above-mentioned problems, the inventors have found that a low Abbe compound that is solid at normal temperature and normal pressure and has a viscosity at 100 ° C. of 10 mPa · s or less has a high refractive index. When used as a viscosity reducing agent for a polymerizable compound, surprisingly, the viscosity of the system is reduced to 10,000 mPa · s or less, or maintained at 10,000 mPa · s or less, and in the cured product of the system The inventors have found that excellent optical characteristics (low Abbe number, high refractive index) can be realized, and completed the present invention.

（式中、Ｘは重合性二重結合を有する置換基を少なくとも１つ有するフェニル基、重合性二重結合を有する置換基を少なくとも１つ有するナフチル基、重合性二重結合を有する置換基を少なくとも１つ有するビフェニル基、又は重合性二重結合を有する置換基を少なくとも１つ有するフェナントリル基を表し、Ａｒ^１は複数のベンゼン環構造を有する縮合環炭化水素基（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）、又は複数の芳香環が単結合で直接結合している炭化水素環集合基（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）を表し、Ｒ^１はメチル基、エチル基、又はイソプロピル基を表す。）
第４観点として、前記低粘度化剤が、下記式［２］で表される化合物である、第２観点に記載の方法に関する。

（式中、Ａｒ^２はｑ価の芳香族炭化水素残基を表し、ｑは１又は２を表し、
Ｙは単結合、−Ｏ−Ｃ（＝Ｏ）−基、又は−Ｏ−基を表し、Ｒ^２は水素原子又はメチル基を表す。）
第５観点として、前記低粘度化剤が、下記式［３−１］又は式［３−２］で表される化合物である、第２観点に記載の方法に関する。

（式中、Ｒ^１はメチル基、エチル基、又はイソプロピル基を表す。）
第６観点として、重合性二重結合を少なくとも１つ有し、その硬化物のＤ線（５８９．３ｎｍ）における屈折率が１．６０以上である高屈折率重合性化合物の低粘度化剤であって、
１０１３．２５ｈＰａ下、２３℃における物質の状態が固体であり、１００℃未満の融点を有する化合物であって、１００℃における粘度が１０ｍＰａ・ｓ以下であり、その硬化物のＤ線（５８９．３ｎｍ）におけるアッベ数が２３以下である化合物からなる、低粘度化剤に関する。
第７観点として、（ａ）重合性二重結合を少なくとも１つ有し、その硬化物のＤ線（５８９．３ｎｍ）における屈折率が１．６０以上である高屈折率重合性化合物 １００質量部、及び
（ｂ）１０１３．２５ｈＰａ下、２３℃における物質の状態が固体であり、１００℃未満の融点を有する化合物であって、１００℃における粘度が１０ｍＰａ・ｓ以下であり、その硬化物のＤ線（５８９．３ｎｍ）におけるアッベ数が２３以下である化合物からなる、低粘度化剤 １０〜５００質量部
を含む、重合性組成物に関する。
第８観点として、前記（ａ）高屈折率重合性化合物が、式［４］で表されるアルコキシケイ素化合物Ａの重縮合物、及び式［４］で表されるアルコキシケイ素化合物Ａと式［５］で表されるアルコキシケイ素化合物Ｂとの重縮合物の少なくとも一方を含む、反応性ポリシロキサンを含む、第７観点に記載の重合性組成物に関する。

（式中、Ｘは重合性二重結合を有する置換基を少なくとも１つ有するフェニル基、重合性二重結合を有する置換基を少なくとも１つ有するナフチル基、重合性二重結合を有する置換基を少なくとも１つ有するビフェニル基、又は重合性二重結合を有する置換基を少なくとも１つ有するフェナントリル基を表し、Ａｒ^３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、複数のベンゼン環構造を有する縮合環炭化水素基（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）、又は複数の芳香環が単結合で直接結合している炭化水素環集合基（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）を表し、Ｒ^３はメチル基、エチル基、又はイソプロピル基を表す。）

（式中、Ａｒ^４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、複数のベンゼン環構造を有する縮合環炭化水素基（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）、又は複数の芳香環が単結合で直接結合している炭化水素環集合基（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）を表し、Ｒ^４はメチル基、エチル基、又はイソプロピル基を表す。）、
第９観点として、前記（ａ）高屈折率重合性化合物が、式［６］で表されるフルオレン化合物を含む、第７観点に記載の重合性組成物に関する。

（式中、Ｒ^５及びＲ^６はそれぞれ独立して、水素原子又はメチル基を表し、Ｌ^１及びＬ^２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、Ｌ^３及びＬ^４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はそれぞれ独立して、０≦ｍ＋ｎ≦４０を満たす０又は正の整数を表す。）
第１０観点として、前記（ａ）高屈折率重合性化合物が、下記式［７−１］で表される化合物、式［７−２］で表される構造単位を有する化合物、並びに式［７−２］で表される構造単位及び式［７−３］で表される構造単位を有する化合物からなる群から選択される、第７観点に記載の重合性組成物に関する。

（式中、２つのＱはそれぞれ同一の基であって、ビニルオキシ基、アリルオキシ基及び（メタ）アクリロイルオキシ基からなる群から選択される基を表し、２つのｐはそれぞれ同一に０乃至３の整数を示す。）

（式中、Ａｒ^５及びＡｒ^６は、それぞれ独立して、フェニル基、ナフチル基、又はフェナントリル基を表す。）
第１１観点として、（ｃ）１０１３．２５ｈＰａ下、２３℃における物質の状態が液体である重合性希釈剤をさらに含む、第７観点乃至第１０観点のうち何れか一に記載の重合性組成物に関する。
第１２観点として、第７観点乃至第１１観点の何れか一に記載の重合性組成物の硬化物に関する。
第１３観点として、第７観点乃至第１１観点の何れか一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。
第１４観点として、第７観点乃至第１１観点の何れか一に記載の重合性組成物から作製された、樹脂レンズに関する。
第１５観点として、第７観点乃至第１１観点の何れか一に記載の重合性組成物を、接し合う支持体と鋳型との間の空間、又は分割可能な鋳型の内部の空間に充填する工程、及び当該充填された組成物を露光して光重合する工程、を含む成形体の製造方法に関する。
第１６観点として、さらに、得られた光重合物を充填された前記空間から取り出して離型する工程、並びに、該光重合物を該離型の前、中途又は後において加熱する工程、を含む第１５観点に記載の製造方法に関する。
第１７観点として、前記成形体がカメラモジュール用レンズである、第１５観点又は第１６観点に記載の製造方法に関する。That is, as a first aspect, the present invention is a compound in which the state of a substance at 23 ° C. is solid at 1013.25 hPa and has a melting point of less than 100 ° C., and the viscosity at 100 ° C. is 10 mPa · s or less, A compound having an Abbe number of 23 or less at the D line (589.3 nm) of the cured product,
The present invention relates to a method for use as a low-viscosity agent for a high refractive index polymerizable compound having at least one polymerizable double bond and having a refractive index at D line (589.3 nm) of the cured product of 1.60 or more.
As a second aspect, the viscosity reducing agent is a phenyl group or phenylene group which may be substituted with an alkyl group having 1 to 6 carbon atoms, monovalent or divalent condensed ring carbonization having a plurality of benzene ring structures. A hydrogen group (which may be substituted with an alkyl group having 1 to 6 carbon atoms), and a monovalent or divalent hydrocarbon ring assembly group in which a plurality of aromatic rings are directly bonded by a single bond (carbon atoms) At least one aromatic group selected from the group consisting of (optionally substituted with an alkyl group of 1 to 6), and
A compound having at least one group having a polymerizable double bond selected from the group consisting of a vinyl group, an allyl group, a (meth) allyloxy group and a (meth) acryloyl group,
The method according to the first aspect.
As a third aspect, the present invention relates to the method according to the second aspect, wherein the viscosity reducing agent is a compound represented by the following formula [1].

(Wherein X represents a phenyl group having at least one substituent having a polymerizable double bond, a naphthyl group having at least one substituent having a polymerizable double bond, and a substituent having a polymerizable double bond. Represents a biphenyl group having at least one or a phenanthryl group having at least one substituent having a polymerizable double bond, and Ar ¹ represents a condensed ring hydrocarbon group having a plurality of benzene ring structures (having 1 to 6 carbon atoms). Or a hydrocarbon ring assembly group (which may be substituted with an alkyl group having 1 to 6 carbon atoms) in which a plurality of aromatic rings are directly bonded with a single bond. R ¹ represents a methyl group, an ethyl group, or an isopropyl group.)
As a fourth aspect, the present invention relates to the method according to the second aspect, wherein the viscosity reducing agent is a compound represented by the following formula [2].

(In the formula, Ar ² represents a q-valent aromatic hydrocarbon residue, q represents 1 or 2,
Y represents a single bond, —O—C (═O) — group, or —O— group, and R ² represents a hydrogen atom or a methyl group. )
As a fifth aspect, the present invention relates to the method according to the second aspect, wherein the viscosity reducing agent is a compound represented by the following formula [3-1] or formula [3-2].

(In the formula, R ¹ represents a methyl group, an ethyl group, or an isopropyl group.)
As a sixth aspect, a low-viscosity agent for a high-refractive index polymerizable compound having at least one polymerizable double bond and having a refractive index of 1.60 or more at the D-line (589.3 nm) of the cured product. There,
A compound having a solid state at 1013.25 hPa at 23 ° C. and having a melting point of less than 100 ° C., having a viscosity at 100 ° C. of 10 mPa · s or less, and a D line (589.3 nm) of the cured product ) In which the Abbe number is 23 or less.
As a seventh aspect, (a) a high refractive index polymerizable compound having at least one polymerizable double bond and having a refractive index at D line (589.3 nm) of the cured product of 1.60 or more 100 parts by mass And (b) a compound having a solid state at 23 ° C. under 1013.25 hPa and having a melting point of less than 100 ° C., the viscosity at 100 ° C. is 10 mPa · s or less, and D of the cured product The present invention relates to a polymerizable composition comprising 10 to 500 parts by mass of a viscosity reducing agent comprising a compound having an Abbe number of 23 or less at a line (589.3 nm).
As an eighth aspect, the high refractive index polymerizable compound (a) is a polycondensate of an alkoxysilicon compound A represented by the formula [4], and an alkoxysilicon compound A represented by the formula [4] and the formula [4]. 5] The polymerizable composition according to the seventh aspect, which contains a reactive polysiloxane containing at least one of the polycondensates with the alkoxysilicon compound B.

(Wherein X represents a phenyl group having at least one substituent having a polymerizable double bond, a naphthyl group having at least one substituent having a polymerizable double bond, and a substituent having a polymerizable double bond. Represents a biphenyl group having at least one, or a phenanthryl group having at least one substituent having a polymerizable double bond, and Ar ³ represents a phenyl group which may be substituted with an alkyl group having 1 to 6 carbon atoms, a plurality of A condensed ring hydrocarbon group having a benzene ring structure (which may be substituted with an alkyl group having 1 to 6 carbon atoms), or a hydrocarbon ring assembly group in which a plurality of aromatic rings are directly bonded by a single bond ( And optionally substituted with an alkyl group having 1 to 6 carbon atoms, and R ³ represents a methyl group, an ethyl group, or an isopropyl group.)

(In the formula, Ar ⁴ is a phenyl group which may be substituted with an alkyl group having 1 to 6 carbon atoms, or a condensed ring hydrocarbon group having a plurality of benzene ring structures (substituted with an alkyl group having 1 to 6 carbon atoms). Or a hydrocarbon ring assembly group in which a plurality of aromatic rings are directly bonded with a single bond (which may be substituted with an alkyl group having 1 to 6 carbon atoms), and R ⁴ is Represents a methyl group, an ethyl group, or an isopropyl group).
As a ninth aspect, the present invention relates to the polymerizable composition according to the seventh aspect, in which the high refractive index polymerizable compound (a) includes a fluorene compound represented by the formula [6].

(In the formula, R ⁵ and R ⁶ 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 represent an alkylene group having 1 to 6 carbon atoms, and m and n each independently represents 0 ≦ m + n ≦ 40. Represents 0 or a positive integer to satisfy.)
As a tenth aspect, the compound (a) having a high refractive index polymerizable compound represented by the following formula [7-1], a compound having a structural unit represented by the formula [7-2], and the formula [7 -2] and the polymerizable composition according to the seventh aspect, selected from the group consisting of compounds having a structural unit represented by the formula [7-3].

(In the formula, two Q's are the same group, and each represents a group selected from the group consisting of a vinyloxy group, an allyloxy group and a (meth) acryloyloxy group, and two p's are each independently 0 to 3) Indicates an integer.)

(In the formula, Ar ⁵ and Ar ⁶ each independently represent a phenyl group, a naphthyl group, or a phenanthryl group.)
As an eleventh aspect, the polymerizable composition according to any one of the seventh aspect to the tenth aspect, further comprising (c) a polymerizable diluent having a liquid state at 23 ° C. under 1013.25 hPa. About.
As a twelfth aspect, the present invention relates to a cured product of the polymerizable composition according to any one of the seventh aspect to the eleventh aspect.
As a thirteenth aspect, the present invention relates to a material for a high refractive index resin lens comprising the polymerizable composition according to any one of the seventh aspect to the eleventh aspect.
As a 14th viewpoint, it is related with the resin lens produced from the polymeric composition as described in any one of a 7th viewpoint thru | or an 11th viewpoint.
As a fifteenth aspect, a step of filling the polymerizable composition according to any one of the seventh aspect to the eleventh aspect into a space between a contacting support and a mold, or a space inside a separable mold. And a step of exposing and photopolymerizing the filled composition, to a method for producing a molded article.
As a sixteenth aspect, the method further includes a step of taking out and releasing the obtained photopolymer from the filled space, and a step of heating the photopolymer before, during or after the release. The manufacturing method according to the fifteenth aspect.
As a seventeenth aspect, the present invention relates to the manufacturing method according to the fifteenth aspect or the sixteenth aspect, in which the molded body is a lens for a camera module.

  The present invention is a compound that has a solid state at 1013.25 hPa at 23 ° C. and a melting point of less than 100 ° C., and has a viscosity at 100 ° C. of 10 mPa · s or less, and the D line of the cured product By using a compound having an Abbe number of 23 or less at (589.3 nm) as a low viscosity agent for a high refractive index polymerizable compound, the viscosity of the system is reduced to 10,000 mPa · s or less, or 10, 000 mPa · s or less, and excellent optical characteristics (low Abbe number, high refractive index) can be realized in the cured product.

In addition, the polymerizable composition of the present invention achieves a low viscosity by blending the viscosity reducing agent, the handling property is improved, and the cured product is an optical device such as a lens for a high resolution camera module. Desirable optical characteristics (low Abbe number, high refractive index) can be achieved.
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 camera module.

Furthermore, since the polymerizable composition of the present invention has a viscosity that can be sufficiently handled in a solvent-free form due to the blending of the viscosity reducing agent, it can be used for pressing a mold such as a mold (imprint technology). ) Can be molded, and it is excellent in releasability from the mold after molding, and a molded product can be suitably produced.
Further, the production method of the present invention can efficiently produce a molded article, particularly a camera module lens, because the polymerizable composition to be used has excellent handling properties.

1 is a diagram showing a ¹ H NMR spectrum of dimethoxy (phenanthren-9-yl) (4-vinylphenyl) silane obtained in Production Example 1. FIG. 2 is a diagram showing a ¹ H NMR spectrum of trimethoxy (9-phenanthryl) silane obtained in Production Example 3. FIG.

The present invention is a compound that has a solid state at 1013.25 hPa at 23 ° C. and a melting point of less than 100 ° C., and has a viscosity at 100 ° C. of 10 mPa · s or less, and the D line of the cured product Abbe number at (589.3 nm), i.e. the compound [nu _D is 23 or less, a method of using a low-viscosity agent described later high refractive index polymerizable compound, and the target is also present invention the viscosity reducing agent To do.
Details of the present invention will be described below.

<< Low viscosity agent >>
As described above, the viscosity reducing agent of the present invention is a solid substance at 23 ° C. under 101.25 hPa (that is, atmospheric pressure), has a melting point of less than 100 ° C., and has a viscosity at 100 ° C. of 10 mPa · s or less. And it will not specifically limit if the Abbe number in D line | wire (589.3 nm) of the hardened | cured material is 23 or less.

Examples of the viscosity reducing agent include compounds having at least one group each having an aromatic group and a polymerizable double bond. Here, the term “polymerizability” refers to the property of causing a polymerization reaction when a part of a molecule undergoes a chemical reaction by an external stimulus such as heat or light and is cleaved or decomposed.
Specific examples of the compound include a phenyl group or a phenylene group which may be substituted with an alkyl group having 1 to 6 carbon atoms, and a monovalent or divalent condensed ring hydrocarbon group having a plurality of benzene ring structures. (Which may be substituted with an alkyl group having 1 to 6 carbon atoms) and a monovalent or divalent hydrocarbon ring assembly group in which a plurality of aromatic rings are directly bonded with a single bond (1 carbon atom Or at least one aromatic group selected from the group consisting of 6 to 6 alkyl groups), and from a vinyl group, an allyl group, a (meth) allyloxy group, and a (meth) acryloyl group. The compound which has at least 1 group which has a polymerizable double bond selected from the group which consists of can be mentioned.

In the aromatic group, the monovalent or divalent condensed ring hydrocarbon group having a plurality of benzene ring structures is derived from, for example, naphthalene, phenanthrene, anthracene, triphenylene, pyrene, chrysene, naphthacene, biphenylene, and fluorene. A monovalent or divalent group is mentioned.
Examples of the monovalent or divalent hydrocarbon ring assembly group in which a plurality of aromatic rings are directly bonded by a single bond include biphenyl, terphenyl, quaterphenyl, binaphthalene, phenylnaphthalene, phenylfluorene, and diphenylfluorene. Examples thereof include a monovalent or divalent group to be derived.
In the phenyl group, phenylene group, monovalent or divalent condensed ring hydrocarbon group and monovalent or divalent hydrocarbon ring assembly group, the alkyl group having 1 to 6 carbon atoms which may be substituted. Are, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, cyclopentyl, n-hexyl, cyclohexyl Groups.
Among these aromatic groups, from the viewpoint of being able to achieve solubility, an effect in maintaining viscosity reduction and low viscosity, and excellent optical properties (high transparency, high refractive index, low Abbe number) in the formulation, Preferred examples include a phenyl group, a naphthyl group, and a phenanthryl group.

上記式［１］中、Ｘ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、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、又は重合性二重結合を有する基を少なくとも１つ有するフェナントリル基を表し、Ａｒ^１は複数のベンゼン環構造を有する縮合環炭化水素基（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）、又は複数の芳香環が単結合で直接結合している炭化水素環集合基（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）を表し、Ｒ^１はメチル基、エチル基、又はイソプロピル基を表す。Specific examples of the compound having at least one each of the specific aromatic group and the group having a polymerizable double bond include a compound represented by the following formula [1].

In the above formula [1], X represents 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, and a group having a polymerizable double bond. Represents a biphenyl group having at least one, or a phenanthryl group having at least one group having a polymerizable double bond, and Ar ¹ represents a condensed ring hydrocarbon group having a plurality of benzene ring structures (an alkyl having 1 to 6 carbon atoms). Or a hydrocarbon ring assembly group in which a plurality of aromatic rings are directly bonded with a single bond (which may be substituted with an alkyl group having 1 to 6 carbon atoms), R ¹ represents a methyl group, an ethyl group, or an isopropyl group.

  Examples of the phenyl group having at least one group having a polymerizable double bond represented by X include, for example, 2-vinylphenyl group, 3-vinylphenyl group, 4-vinylphenyl group, 4-vinyloxyphenyl group, 4- Examples include allylphenyl group, 4-allyloxyphenyl group, and 4-isopropenylphenyl group.

  Examples of the naphthyl group having at least one group having a polymerizable double bond represented by X include 4-vinylnaphthalen-1-yl group, 5-vinylnaphthalen-1-yl group, and 6-vinylnaphthalene-2-yl group. Yl group, 5-vinyloxynaphthalen-1-yl group, 5-allylnaphthalen-1-yl group, 4-allyloxynaphthalen-1-yl group, 5-allyloxynaphthalen-1-yl group, 8-allyloxy Naphthalen-1-yl group and 5-isopropenylnaphthalen-1-yl group can be mentioned.

  Examples of the biphenyl group having at least one group having a polymerizable double bond represented by X include 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'-biphenyl] ] -4-yl group is mentioned.

  Examples of the phenanthryl group having at least one group having a polymerizable double bond represented by X include a 3-vinylphenanthren-9-yl group, a 7-vinylphenanthrene-9-yl group, and a 10-vinylphenanthrene-9-. Yl group, 7-vinylphenanthren-2-yl group, 6-vinylphenanthren-3-yl group, 10-vinylphenanthren-3-yl group, 3-vinyloxyphenanthren-9-yl group, 3-allylphenanthrene-9 -Yl group, 3-allyloxyphenanthren-9-yl group, 3-isopropenylphenanthren-9-yl group.

  X is preferably a phenyl group having at least one group having a polymerizable double bond, and more preferably a vinylphenyl group.

Examples of the condensed ring hydrocarbon group having a plurality of benzene ring structures represented by Ar ¹ include monovalent groups derived from naphthalene, phenanthrene, anthracene, triphenylene, pyrene, chrysene, naphthacene, biphenylene, and fluorene.
Examples of the hydrocarbon ring assembly group in which a plurality of aromatic rings are directly bonded with a single bond include, for example, monovalent derivatives derived from biphenyl, terphenyl, quaterphenyl, binaphthalene, phenylnaphthalene, phenylfluorene, and diphenylfluorene. Groups.
In the condensed ring hydrocarbon group and hydrocarbon ring assembly group, examples of the alkyl group having 1 to 6 carbon atoms that may be substituted include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, n -Butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, cyclopentyl group, n-hexyl group, cyclohexyl group can be mentioned.

Ar ¹ is preferably a condensed ring hydrocarbon group having a plurality of benzene ring structures (which may be substituted with an alkyl group having 1 to 6 carbon atoms), and more preferably a phenanthryl group.

  Specific examples of the compound represented by the formula [1] include, for example, dimethoxy (9-phenanthryl) (4-vinylphenyl) silane, diethoxy (9-phenanthryl) (4-vinylphenyl) silane, diisopropoxy ( 9-phenanthryl) (4-vinylphenyl) silane, dimethoxy (9-phenanthryl) (4-vinylnaphthalen-1-yl) silane, dimethoxy (9-phenanthryl) (4′-vinyl- [1,1′-biphenyl] -4-yl) silane, dimethoxy (9-phenanthryl) (3-vinylphenanthrene-9-yl) silane, dimethoxy (1-naphthyl) (4-vinylphenyl) silane, dimethoxy (2-naphthyl) (4-vinylphenyl) ) Silane, dimethoxy (2-phenanthryl) (4-vinylphenyl) silane, di Toxi (3-phenanthryl) (4-vinylphenyl) silane, dimethoxy (9-phenanthryl) (4-vinylphenyl) silane, [1,1′-biphenyl] -4-yldimethoxy (4-vinylphenyl) silane However, it is not limited to these.

上記式［２］中、Ａｒ^２はｑ価の芳香族炭化水素残基を表し、ｑは１又は２を表し、Ｙは単結合、−Ｏ−Ｃ（＝Ｏ）−基、又は−Ｏ−基を表し、Ｒ^２は水素原子又はメチル基を表す。Moreover, the compound represented by following formula [2] is mentioned as a specific example of the compound which has at least 1 each of the said specific aromatic group and group which has a polymerizable double bond, respectively.

In the above formula [2], Ar ² represents a q-valent aromatic hydrocarbon residue, q represents 1 or 2, Y represents a single bond, —O—C (═O) — group, or —O—. Represents a group, and R ² represents a hydrogen atom or a methyl group.

The q-valent aromatic hydrocarbon residue in Ar ² is benzene, a condensed ring hydrocarbon having a plurality of benzene ring structures, or a hydrocarbon ring assembly in which a plurality of aromatic rings are directly bonded by a single bond. Examples include a group in which q hydrogen atoms are removed, and these may be substituted with an alkyl group having 1 to 6 carbon atoms.
Specifically, a phenyl group or a phenylene group which may be substituted with an alkyl group having 1 to 6 carbon atoms, a monovalent or divalent condensed ring hydrocarbon group having a plurality of benzene ring structures (one carbon atom) Or a monovalent or divalent hydrocarbon ring assembly group in which a plurality of aromatic rings are directly bonded with a single bond (an alkyl group having 1 to 6 carbon atoms). Which may be substituted).

Examples of the phenyl group which may be substituted with an alkyl group having 1 to 6 carbon atoms represented by Ar ² include a phenyl group, an o-tolyl group, an m-tolyl group, a p-tolyl group, 2, 4, 6 -Trimethylphenyl group and 4-tert-butylphenyl group, and examples of the phenylene group optionally substituted with an alkyl group having 1 to 6 carbon atoms include a phenylene group, a 2,4-methylphenylene group, Examples include 2,5-methylphenylene group, 2,4,5-trimethyl-1,3-phenylene group, and 2-tert-butyl-1,4-phenylene group.
Examples of the monovalent or divalent condensed ring hydrocarbon group having a plurality of benzene ring structures represented by Ar ² include monovalent derivatives derived from naphthalene, phenanthrene, anthracene, triphenylene, pyrene, chrysene, naphthacene, biphenylene, and fluorene. Or a bivalent group is mentioned.
Examples of the monovalent or divalent hydrocarbon ring assembly group in which a plurality of aromatic rings are directly bonded by a single bond include biphenyl, terphenyl, quaterphenyl, binaphthalene, phenylnaphthalene, phenylfluorene, and diphenylfluorene. Examples thereof include a monovalent or divalent group to be derived.
In the condensed ring hydrocarbon group and hydrocarbon ring assembly group, examples of the alkyl group having 1 to 6 carbon atoms that may be substituted include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, n -Butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, cyclopentyl group, n-hexyl group, cyclohexyl group can be mentioned.

  Specific examples of the compound represented by the formula [2] include, for example, 1-vinylnaphthalene, 2-vinylnaphthalene, 2-isopropenylnaphthalene, 2,7-bis (4-vinylphenyl) naphthalene, naphthalene-1. -Ilmethyl (meth) acrylate and naphthalen-2-ylmethyl (meth) acrylate are mentioned.

上記式中、Ｒ^１はメチル基、エチル基、又はイソプロピル基を表す。Examples of the viscosity reducing agent according to the present invention include compounds represented by the following formulas [3-1] to [3-4], among which the formulas [3-1] and [3-2] The compound represented by the formula [3-1] is preferable from the viewpoint of realizing the effect of reducing and maintaining the viscosity and achieving excellent optical characteristics (low Abbe number).

In the above formula, R ¹ represents a methyl group, an ethyl group, or an isopropyl group.

A commercially available compound can be suitably used for the viscosity reducing agent according to the present invention.
In addition, for example, an ester compound containing a (meth) acryloyl group such as a compound represented by the formula [3-4] can be produced by a conventional method, and an alcohol and a (meth) acrylic acid halide are present in triethylamine or pyridine. It can manufacture by making it esterify under.

The compounds represented by the above formulas [3-1] and [3-3] (compounds represented by the above formula [1]) can be produced by a conventional method, for example, alkoxysilane compounds and Grignards. The conventional Grignard reaction to obtain an organoalkoxysilane compound by reacting with a reagent, or the conventional coupling reaction to obtain an organoalkoxysilane compound by reacting an alkoxyhydrosilane compound and an aryl halide using a transition metal catalyst. Can be manufactured.
Specifically, a Grignard reagent having Ar ¹ group: Ar ¹ -Mg-Hal is reacted with a trialkoxysilane compound having an aromatic ring group having a polymerizable double bond: X-Si (OR ¹ ) _3. Or a Grignard reagent having an aromatic ring group having a polymerizable double bond: X-Mg-Hal and a trialkoxysilane compound having Ar ¹ group: Ar ¹ -Si (OR ¹ ) ₃ are reacted, A polymerizable silane compound represented by the formula [1] can be obtained (the above Ar ¹ , X, and R ¹ have the same meaning as the formula [1], and Hal represents a halogen atom).
The Grignard reagent is obtained by reacting aryl halide: Ar ¹ -Hal or X-Hal with magnesium.

The production of the Grignard reagent and the reaction between the Grignard reagent and the alkoxysilane compound can be carried out in an organic solvent. Examples of the organic solvent used here include ether solvents such as diethyl ether, tetrahydrofuran, and tert-butyl methyl ether; and inert organic solvents such as hydrocarbon solvents such as hexane, toluene, and xylene. . You may use these organic solvents individually by 1 type or in mixture of 2 or more types.
The above production temperature and reaction temperature are preferably in the range of 0 to 200 ° C, particularly 20 to 150 ° C.
In addition, when oxygen is present in the Grignard reagent or in the reaction system between the Grignard reagent and the alkoxysilane compound, the Grignard reagent reacts with oxygen during the production / reaction stage, and the yield of the target polymerizable silane compound decreases. Therefore, these are preferably performed in an inert atmosphere such as nitrogen or argon.

  The said viscosity reducing agent can be used individually by 1 type or in combination of 2 or more types.

<< High refractive index polymerizable compound >>
The viscosity reducing agent according to the present invention has at least one polymerizable double bond, and has a refractive index at the D-line (589.3 nm) of the cured product, that is, a high refractive index in which n _D is 1.60 or more. Used for polymerizable compounds.
The high refractive index polymerizable compound is not particularly limited as long as it is a compound having a polymerizable group as described above and having a high refractive index of 1.60 or higher in the cured product. And reactive polysiloxanes and specific fluorene compounds.

<Reactive polysiloxane>
The reactive polysiloxane includes a polycondensate of an alkoxysilicon compound A represented by the formula [4], an alkoxysilicon compound A represented by the formula [4], and an alkoxysilicon compound B represented by the formula [5]. And at least one of polycondensates.

上記式［４］中、Ｘは重合性二重結合を有する置換基を少なくとも１つ有するフェニル基、重合性二重結合を有する置換基を少なくとも１つ有するナフチル基、重合性二重結合を有する置換基を少なくとも１つ有するビフェニル基、又は重合性二重結合を有する置換基を少なくとも１つ有するフェナントリル基を表し、Ａｒ^３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、複数のベンゼン環構造を有する縮合環炭化水素基（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）、又は複数の芳香環が単結合で直接結合している炭化水素環集合基（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）を表し、Ｒ^３はメチル基、エチル基、又はイソプロピル基を表す。[Alkoxysilicon compound A]

In the above formula [4], X has a phenyl group having at least one substituent having a polymerizable double bond, a naphthyl group having at least one substituent having a polymerizable double bond, and a polymerizable double bond. Represents a biphenyl group having at least one substituent or a phenanthryl group having at least one substituent having a polymerizable double bond, and Ar ³ is phenyl optionally substituted by an alkyl group having 1 to 6 carbon atoms Group, a condensed ring hydrocarbon group having a plurality of benzene ring structures (which may be substituted with an alkyl group having 1 to 6 carbon atoms), or a hydrocarbon ring in which a plurality of aromatic rings are directly bonded by a single bond It represents an assembly group (which may be substituted with an alkyl group having 1 to 6 carbon atoms), and R ³ represents a methyl group, an ethyl group, or an isopropyl group.

Specific examples of X in the formula [4] include the groups exemplified as the group X in the formula [1] in the compound represented by the formula [1]. The group mentioned as a preferable group in group X can be mentioned.
Further, specific examples of Ar ^{4 in} the above formula [4] include groups exemplified as the group Ar ¹ in the above formula [1], and particularly exemplified as preferred groups in the group Ar ¹ in the formula [4]. The group can be mentioned.
And as a specific example of the compound represented by the said Formula [4], the compound quoted as a specific example of the compound represented by the said Formula [1] is mentioned.

式［５］中、Ａｒ^４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、複数のベンゼン環構造を有する縮合環炭化水素基（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）、又は複数の芳香環が単結合で直接結合している炭化水素環集合基（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）を表し、Ｒ^４はメチル基、エチル基、又はイソプロピル基を表す。）[Alkoxysilicon compound B]

In the formula [5], Ar ⁴ is a phenyl group which may be substituted with an alkyl group having 1 to 6 carbon atoms, a condensed ring hydrocarbon group having a plurality of benzene ring structures (an alkyl group having 1 to 6 carbon atoms) Or a hydrocarbon ring assembly group in which a plurality of aromatic rings are directly bonded with a single bond (which may be substituted with an alkyl group having 1 to 6 carbon atoms), and R ⁴ represents a methyl group, an ethyl group, or an isopropyl group. )

Examples of the phenyl group which may be substituted with an alkyl group having 1 to 6 carbon atoms represented by Ar ⁴ include a phenyl group, an o-tolyl group, an m-tolyl group, a p-tolyl group, 2, 4, 6 -A trimethylphenyl group and 4-tert- butylphenyl group are mentioned.
Examples of the condensed ring hydrocarbon group having a plurality of benzene ring structures represented by Ar ⁴ include monovalent groups derived from naphthalene, phenanthrene, anthracene, triphenylene, pyrene, chrysene, naphthacene, biphenylene, and fluorene.
Examples of the hydrocarbon ring assembly group in which a plurality of aromatic rings are directly bonded with a single bond include, for example, monovalent derivatives derived from biphenyl, terphenyl, quaterphenyl, binaphthalene, phenylnaphthalene, phenylfluorene, and diphenylfluorene. Groups.
In the condensed ring hydrocarbon group and hydrocarbon ring assembly group, examples of the alkyl group having 1 to 6 carbon atoms that may be substituted include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, n -Butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, cyclopentyl group, n-hexyl group, cyclohexyl group can be mentioned.

Ar ⁴ is preferably a condensed ring hydrocarbon group having a plurality of benzene ring structures (which may be substituted with an alkyl group having 1 to 6 carbon atoms), and more preferably a phenanthryl group.

  Specific examples of the compound represented by the above formula [5] include, for example, trimethoxy (phenyl) silane, triethoxy (phenyl) silane, trimethoxy (p-tolyl) silane, trimethoxy (1-naphthyl) silane, triethoxy (1- Naphthyl) silane, triisopropoxy (1-naphthyl) silane, trimethoxy (2-naphthyl) silane, triethoxy (2-naphthyl) silane, triisopropoxy (2-naphthyl) silane, trimethoxy (2-phenanthryl) silane, trimethoxy ( 3-phenanthryl) silane, trimethoxy (9-phenanthryl) silane, triethoxy (9-phenanthryl) silane, triisopropoxy (9-phenanthryl) silane, [1,1′-biphenyl] -4-yltrimethoxysilane, [1 , 1'-Biff Sulfonyl] -4-yl triethoxysilane, [1,1'-biphenyl] -4-yl but triisopropoxysilane include, without being limited thereto.

When the alkoxysilicon compound constituting the reactive polysiloxane includes the alkoxysilicon compound B represented by the formula [5] in addition to the alkoxysilicon compound A represented by the formula [4], Although the compounding molar ratio concerning a condensation reaction is not specifically limited, Usually, the range of 9 mol or less of alkoxy silicon compounds B is preferable with respect to 1 mol of alkoxy silicon compounds A from the objective of stabilizing the physical property of hardened | cured material. More preferably, it is the range mix | blended by 1.5 mol or less. By setting the blending molar ratio of the alkoxysilicon compound B to the blending mole number of the alkoxysilicon compound A to 9 or less, a sufficient crosslinking density is obtained, the dimensional stability against heat is further improved, and a higher refractive index, A cured product having a low Abbe number can be obtained.
As the above-mentioned alkoxysilicon compound A and alkoxysilicon compound B, compounds can be appropriately selected and used as necessary, and plural kinds of compounds can be used in combination. In this case, the molar ratio of the total amount of the alkoxysilicon compound A and the total molar amount of the alkoxysilicon compound B also falls within the above range.

[Acid or basic catalyst]
The polycondensation reaction of the alkoxysilicon compound A represented by the above formula [4], or the alkoxy containing the alkoxysilicon compound A represented by the above formula [4] and the alkoxysilicon compound B represented by the above formula [5] The polycondensation reaction of the silicon 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 a solvent described later, and can be appropriately selected and used as necessary.
Examples of catalysts that can be used include acidic compounds such as inorganic acids such as hydrochloric acid, nitric acid and sulfuric acid, organic acids such as acetic acid and oxalic acid; basic compounds such as alkali metal hydroxides and alkaline earth metal hydroxides. Products, ammonium hydroxide, quaternary ammonium salts, amines; examples of fluoride salts include NH ₄ F and NR ₄ F. 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.
These catalysts can be used alone or in combination of two or more.

  Examples of the acidic compound include hydrochloric acid, nitric acid, sulfuric acid, acetic acid, oxalic acid, and boric acid.

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

  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 hydrochloric acid, acetic acid, potassium hydroxide, calcium hydroxide, barium hydroxide and tetraethylammonium hydroxide are preferably used.
The usage-amount of a catalyst is 0.01-10 mass% with respect to the total mass of the said 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 polysiloxane (polycondensate) is characterized by the structure of the alkoxysilicon compound A, and the reactive group (polymerizable double bond) contained in the alkoxysilicon compound A is a radical or a cation. The polymer is easily polymerized, and exhibits high heat resistance after polymerization (after curing).
The hydrolysis polycondensation reaction of the alkoxysilicon compound A or the hydrolysis polycondensation reaction of the alkoxysilicon compound A and the alkoxysilicon compound B can be carried out in the absence of a solvent. However, tetrahydrofuran (THF) described later, It is also possible to use a solvent inert to the alkoxysilicon compound to be used as the reaction solvent. When a reaction solvent is used, there is an advantage that the reaction system can be easily made uniform and a more stable polycondensation reaction can be performed.

The synthesis reaction of the reactive polysiloxane may be performed without a solvent as described above, but there is no problem even if a solvent is used to make the reaction more uniform. The solvent is not particularly limited as long as it does not react with the alkoxysilicon compound to be used and dissolves the polycondensate 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; tetrahydrofuran (THF), 1,4-dioxane, diisopropyl ether, and cyclopentylmethyl. Ethers such as ether (CPME); glycols such as ethylene glycol, propylene glycol and hexylene glycol; glycol ethers such as ethyl cellosolve, butyl cellosolve, ethyl carbitol, butyl carbitol, diethyl cellosolve and diethyl carbitol; N- Amides such as methyl-2-pyrrolidone (NMP) and N, N-dimethylformamide (DMF) can be mentioned. These solvents may be used alone or in combination of two or more.

The reactive polysiloxane used in the present invention is an alkoxysilicon compound A represented by the formula [4], or an alkoxysilicon compound A represented by the formula [4] and an alkoxysilicon compound represented by the formula [5]. It can be obtained by subjecting an alkoxysilicon compound containing B to hydrolysis polycondensation in the presence of an acid or a basic catalyst. The reaction temperature for hydrolysis polycondensation 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 polysiloxane is preferably recovered by any method such as filtration and solvent distillation, and appropriately subjected to purification treatment as necessary.

As an example of the method for producing the reactive polysiloxane used in the present invention, an alkoxysilicon compound A represented by the formula [4] is used, or alternatively, an alkoxysilicon compound A represented by the formula [4] and the formula [5]. Examples include a method in which an alkoxysilicon compound containing the represented alkoxysilicon compound B is polycondensed in the presence of a base and the base is removed using a cation exchange resin.
The base and the amount used thereof may be one or more compounds selected from the group consisting of the basic compounds and fluoride salts described above, and the amount used may be employed, preferably potassium hydroxide, calcium hydroxide, hydroxide One or more selected from the group consisting of barium and tetraethylammonium hydroxide can be used as the base.
The reaction conditions and the like used for the polycondensation reaction, the reaction solvent, and the like can be those described above.
And after completion | finish of reaction, as a cation exchange resin used for removal of a base, the ion exchange resin which has a sulfo group as an ionic group is used preferably.

As said cation exchange resin, the thing of the base structure generally used, such as a styrene type (styrene-divinylbenzene copolymer), an acryl type, can be used. Moreover, any of strong acid cation exchange resin which has a sulfo group as an ionic group, and weak acid cation exchange resin which has a carboxy group as an ionic group may be sufficient. Furthermore, as a form of a cation exchange resin, various things, such as granular form, fibrous form, and film form, can be used. As these cation exchange resins, commercially available ones can be suitably used.
Among these, a strongly acidic cation exchange resin having a sulfo group as an ionic group is preferably used.

  Examples of commercially available strong acid cation exchange resins include Amberlite (registered trademark) 15, 200, 200C, 200CT, 252, 1200H, IR120B, IR120H, IR122Na, IR124, IRC50, IRC86, IRN77, IRP77, IRP-64, IRP-69, CG-50, CG-120, Amberjet (registered trademark) 1020, 1024, 1060, 1200, 1220, Amberlist (registered trademark) 15, 15 DRY, 15 JWET, 16, 16 WET, 31 WET, 35 WET, 36, Dowex (registered trademark) 50Wx2, 50Wx4, 50Wx8, DR-2030, DR-G8, HCR-W2, 650C UPW, G-26 88, M-31, N-406, Dowex (registered trademark) Monosphere (registered trademark) 650C, 88, M-31, 99K / 320, 99K / 350, 99Ca / 320, Dowex Marathon (registered trademark) MSC, C [above, manufactured by Dow Chemical Company]; Diaion (registered trademark) EXC04, HPK25, PK208, PK212, PK216, PK220, PK228L, RCP160M, Same SK1B, Same SK1BS, Same SK104, Same SK110, Same SK112, Same SK116, Same UBK510L, Same UBK555 [Mitsubishi Chemical Co., Ltd.]; Is mentioned.

  Examples of commercially available weak acid cation exchange resins include Amberlite (registered trademark) CG-50, FPC3500, IRC50, IRC76, IRC86, IRP-64, and Dowex (registered trademark). MAC-3 [above, manufactured by Dow Chemical Co., Ltd.]; Diaion (registered trademark) CWK30 / S, WK10, WK11, WK40, WK100, WT01S [above, manufactured by Mitsubishi Chemical Corporation] .

The polycondensation compound obtained by such a reaction has a weight average molecular weight Mw measured in terms of polystyrene by GPC of 500 to 100,000, preferably 500 to 30,000, and dispersity: Mw (weight average molecular weight ) / Mn (number average molecular weight) is 1.0-10.
Incidentally, the reactive polysiloxane is a ^[X (Ar 1) SiO] is a compound having at least a siloxane unit represented by, for example, ^[X (Ar 1) SiO] and ^[Ar _{2 SiO 3/2]} A compound having at least a siloxane unit and having a crosslinked structure.

上記式［６］中、Ｒ^５及びＲ^６はそれぞれ独立して、水素原子又はメチル基を表し、Ｌ^１及びＬ^２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、Ｌ^３及びＬ^４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、より好ましくは炭素原子数２又は３のアルキレン基を表し、ｍ及びｎはそれぞれ独立して、０≦ｍ＋ｎ≦４０を満たす０又は正の整数を表す。<Fluorene compound>
The fluorene compound is a compound represented by the following formula [6].

In the above formula [6], R ⁵ and R ⁶ each independently represent a hydrogen atom or a methyl group, and L ¹ and L ² each independently represent a phenylene group optionally having a substituent, or Represents an optionally substituted naphthalenediyl group, and L ³ and L ⁴ each independently represent an alkylene group having 1 to 6 carbon atoms, more preferably an alkylene group having 2 or 3 carbon atoms. , M and n each independently represent 0 or a positive integer satisfying 0 ≦ m + n ≦ 40.

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, Examples include 2-aminobenzene-1,4-diyl group, 2,4-dibromobenzene-1,3-diyl group, and 2,6-dibromobenzene-1,4-diyl group.
Examples of the naphthalenediyl group optionally having a substituent represented by L ¹ and L ² include 1,2-naphthalenediyl group, 1,4-naphthalenediyl group, 1,5-naphthalenediyl group, Examples include 1,8-naphthalenediyl group, 2,3-naphthalenediyl group, and 2,6-naphthalenediyl group.

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 1-methylethylene group, a tetramethylene group, a 1-methyltrimethylene group, and 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-trimethyltrimethylene group , 1,2,2-methyltrimethylene group, 1-ethyl-1-methyltrimethylene group, and a 1-ethyl-2-methyltrimethylene group. Among these, a group corresponding to an alkylene group having 2 or 3 carbon atoms is more preferable as L ³ and L ⁴ .

  In the compound represented by the formula [6], m and n each independently preferably satisfy 0 ≦ m + n ≦ 30, and more preferably satisfy 2 ≦ m + n ≦ 20.

  Specific examples of the compound represented by the formula [6] include, for example, 9,9-bis (4- (2- (meth) acryloyloxyethoxy) phenyl) -9H-fluorene, Ogsol (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 [New Nakamura Chemical Co., Ltd.], but is not limited thereto (in the present invention, (meth) acryloyl group means both acryloyl group and methacryloyl group).

式［７−１］中、２つのＱはそれぞれ同一の基であって、ビニルオキシ基、アリルオキシ基及び（メタ）アクリロイルオキシ基からなる群から選択される基を表し、２つのｐはそれぞれ同一に０乃至３の整数を示す。

式［７−２］及び［７−３］中、Ａｒ^５及びＡｒ^６は、それぞれ独立して、フェニル基、ナフチル基、又はフェナントリル基を表す。Moreover, the compound suitable as a high refractive index polymeric compound is a compound represented by the following formula [7-1], a compound having a structural unit represented by the formula [7-2], and a formula [7-2]. And a structural unit represented by the formula [7-3].

In the formula [7-1], two Q's are the same group and each represents a group selected from the group consisting of a vinyloxy group, an allyloxy group and a (meth) acryloyloxy group, and two p's are the same An integer of 0 to 3 is shown.

In formulas [7-2] and [7-3], Ar ⁵ and Ar ⁶ each independently represent a phenyl group, a naphthyl group, or a phenanthryl group.

Particularly suitable compounds as the high refractive index polymerizable compound include a compound represented by the following formula [7-1-1], a compound having a structural unit represented by the formula [7-2-1], and the formula [7 -2-1] and a compound having a structural unit represented by the formula [7-3-1].

  The said high refractive index polymeric compound can be used individually by 1 type or in combination of 2 or more types.

<< Polymerizable composition >>
The present invention is also directed to a polymerizable composition comprising (a) 100 parts by mass of the high refractive index polymerizable compound and (b) 10 to 500 parts by mass of the viscosity reducing agent.
In the polymerizable composition, any one of (a) a high refractive index polymerizable compound and (b) a viscosity reducing agent can be used alone or in combination of two or more.
The polymerizable composition may further contain (c) a polymerizable diluent whose substance at 23 ° C. is liquid under 1013.25 hPa, and (d) a polymerization initiator.

<(C) Polymerizable diluent>
The polymerizable diluent that can be used in the polymerizable composition of the present invention is a compound in which the state of a substance at 23 ° C. is 1013.25 hPa and is also called a liquid diluent. The polymerizable diluent can be used for the purpose of 1) adjusting the viscosity of the polymerizable composition and 2) adjusting the cross-linking density when the polymerizable composition is cured. Use of the polymerizable diluent can further enhance the effect of reducing and maintaining the viscosity of the above-described viscosity reducing agent.

Examples of the polymerizable diluent include 1,3-butanediol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, 1,6-hexanediol di ( (Meth) acrylate, 1,9-nonanediol di (meth) acrylate, 2-methyl-1,8-octanediol di (meth) acrylate, 1,10-decanediol di (meth) acrylate, tricyclo [5.2. 1.0 ^2,6 ] decanedimethanol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate , 2-hydroxy-3- Acryloyloxypropyl methacrylate, glycerin di (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, bis ((meth) acryloyloxyethyl) hydroxyethyl isocyanurate, benzyl (meth) acrylate, 2-phenoxyethyl (meth) acrylate, 2-phenoxybenzyl (meth) acrylate, 3-phenoxybenzyl (meth) acrylate, 4-phenoxybenzyl (meth) acrylate, 2- (2-biphenylyloxy) ethyl (meth) acrylate 2- (3-biphenylyloxy) ethyl (meth) acrylate, 2- (4-biphenylyloxy) ethyl (meth) acrylate, ethoxylated o-phenylphenol (meth) acrylate , Diethylene glycol monophenyl ether (meth) acrylate, polyethylene glycol monophenyl ether (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, neopentyl glycol benzoate (meth) acrylate, and divinylbenzene.

  The polymerizable diluent is available as a commercial product. Specific examples thereof include NK ester 701A, A-DCP, A-DON-N, A-HD-N, A-NOD-. N, DCP, DOD-N, HD-N, NOD-N, NPG, A-TMM-3, A-TMM-3L, A-TMM-3LMN, A-TMPT, TMPT, A-TMMT, AD-TMP, A-DPH, A-9550, A-9530, ADP-51EH, ATM-31EH, UA-7100, A-LEN-10 Nakamura Chemical Co., Ltd.], KAYARAD (registered trademark) T-1420, D-330, D-320, D-310, DPCA-20, DPCA-30, DPCA-60, DPCA -120, TMPTA, P T-30, the DPHA, the DPHA-2C [manufactured by Nippon Kayaku Co., Ltd.], and.

  When a polymerizable diluent is used, the polymerizable diluent may be used alone or in combination of two or more. Moreover, as the addition amount, it is 0.1-40 mass parts when the whole polymerizable composition is 100 mass parts at 10-500 mass parts with respect to 100 mass parts of (a) component. It is preferably 5 to 30 parts by mass. If the amount exceeds 30 parts by mass, the refractive index may drop, and the high refractive index that is the main purpose of the present invention may not be maintained.

<(D) Polymerization initiator>
The polymerizable composition of the present invention may further contain a polymerization initiator. As the polymerization initiator, any of a photopolymerization initiator and a thermal polymerization initiator can be used.

Examples of the photopolymerization initiator include alkylphenones, benzophenones, Michler's ketones, acylphosphine oxides, benzoylbenzoates, oxime esters, tetramethylthiuram monosulfides, and thioxanthones.
In particular, photocleavable photoradical polymerization initiators are preferred.
Examples of commercially available radical photopolymerization initiators include IRGACURE (registered trademark) 184, 369, 651, 500, 819, 907, 784, 2959, CGI 1700, CGI 1750, and CGI 1850. CG24-61, TPO, Darocur (registered trademark) 1116, 1173 [above, manufactured by BASF Japan Ltd.], ESACURE KIP150, KIP65LT, KIP100F, KT37, KT55, KTO46, KIP75 [ As described above, manufactured by Lamberti Co.] can be mentioned.

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.] Can be mentioned.
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 (manufactured by NOF Corporation), but are not limited thereto.

  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 total amounts of a polymeric component, ie, said (a) component and (b) component (the (c) component further if desired), More preferably Is 0.3 to 10 parts by mass.

<Other additives>
Furthermore, the polymerizable composition of the present invention is, for example, a chain transfer agent, an antioxidant, an ultraviolet absorber, a light stabilizer, a leveling agent, and a rheology modifier as long as the effects of the present invention are not impaired. Further, it can contain an adhesion aid such as a silane coupling agent, a pigment, a dye, and an antifoaming agent.

  Examples of the chain transfer agent include, as thiol compounds, methyl mercaptoacetate, methyl 3-mercaptopropionate, 2-ethylhexyl 3-mercaptopropionate, 3-methoxybutyl 3-mercaptopropionate, n-mercaptopropionate n- Octyl, 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 tetrakis (3-merca) Topropionate), pentaerythritol tetrakis (3-mercaptobutyrate), dipentaerythritol hexakis (3-mercaptopropionate), dipentaerythritol hexakis (3-mercaptobutyrate), tris [2- (3-mercaptopropionyl) Mercaptocarboxylic esters such as oxy) ethyl] isocyanurate, tris [2- (3-mercaptobutyryloxy) ethyl] isocyanurate; ethanethiol, 2-methylpropane-2-thiol, n-dodecanethiol, 2, Alkylthiols such as 3,3,4,4,5-hexamethylhexane-2-thiol (tert-dodecanethiol), ethane-1,2-dithiol, propane-1,3-dithiol, benzylthiol; benzenethiol , -Aromatic thiols such as methylbenzenethiol, 4-methylbenzenethiol, naphthalene-2-thiol, pyridine-2-thiol, benzimidazol-2-thiol, benzothiazole-2-thiol; 2-mercaptoethanol, 4- Mercapto alcohols such as mercapto-1-butanol; silane-containing thiols such as 3- (trimethoxysilyl) propane-1-thiol and 3- (triethoxysilyl) propane-1-thiol; , Dipropyl disulfide, diisopropyl disulfide, dibutyl disulfide, di-tert-butyl disulfide, dipentyl disulfide, diisopentyl disulfide, dihexyl disulfide, dicyclohexyl disulfide, di Decyl disulfide, bis (2,3,3,4,4,5-hexamethylhexane-2-yl) disulfide (di-tert-dodecyl disulfide), bis (2,2-diethoxyethyl) disulfide, bis (2 Alkyl disulfides such as -hydroxyethyl) disulfide and dibenzyldisulfide; diphenyl disulfide, di-p-tolyl disulfide, di (pyridin-2-yl) pyridyl disulfide, di (benzimidazol-2-yl) disulfide, di (benzo Aromatic disulfides such as thiazol-2-yl) disulfide; thiuram disulfides such as tetramethylthiuram disulfide, tetraethylthiuram disulfide, tetrabutylthiuram disulfide, bis (pentamethylene) thiuram disulfide, α-me Le dimer and the like.

  When adding a chain transfer agent, you may use a chain transfer agent individually by 1 type or in mixture of 2 or more types. Moreover, as the addition amount, 0.01-20 mass parts with respect to 100 mass parts of total amounts of a polymeric component, ie, said (a) component and (b) component (the (c) component further if desired), More preferably Is 0.1 to 10 parts by mass.

Examples of the antioxidant include phenol-based antioxidants, phosphoric acid-based antioxidants, sulfide-based antioxidants, etc. Among them, phenol-based antioxidants are preferable.
Examples of phenolic antioxidants 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, AO-60, AO-80, AO-330 [above, manufactured by ADEKA Corporation].

  When adding antioxidant, you may use antioxidant individually by 1 type or in mixture of 2 or more types. Moreover, as the addition amount, 0.01-20 mass parts with respect to 100 mass parts of total amounts of a polymeric component, ie, said (a) component and (b) component (the (c) component further if desired), More preferably Is 0.1 to 10 parts by mass.

<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) and (b) and, if necessary, the components (c) and (d) are mixed at a predetermined ratio, and other additives are further added as necessary. A method of making a uniform solution, among these components, for example, after mixing a part of component (a) and component (b) to make a uniform solution, add the remaining components, and add others as desired Examples thereof include a method in which an agent is further added and mixed to form a uniform solution, or a method in which a conventional solvent is used in addition to these components.

  When using a solvent, the ratio of the solid content in the present polymerizable composition is not particularly limited as long as each component is uniformly dissolved in the solvent. For example, it is 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 0.1 to 5 μm.

<< cured product >>
The polymerizable composition can be exposed (photocured) or heated (thermally cured) to obtain a cured product, and the present invention is also directed to a cured product of the polymerizable compound.
Examples of light rays to be exposed include ultraviolet rays, electron beams, and X-rays. As a light source used for ultraviolet irradiation, for example, sunlight, chemical lamp, low-pressure mercury lamp, high-pressure mercury lamp, metal halide lamp, xenon lamp, or UV-LED can be used. Moreover, you may post-bake in order to stabilize the physical property of hardened | cured material after exposure. Although it does not specifically limit as a method of post-baking, Usually, it is carried out in the range of 50-260 degreeC and 1-120 minutes using a hotplate, oven, etc.
Although it does not specifically limit as heating conditions in thermosetting, 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 and oven are mentioned.

  A cured product obtained by curing the polymerizable composition of the present invention has a refractive index as high as 1.620 or more at a wavelength of 589.3 nm (D-line), and further has a Abbe number of 23 or less. It is also possible to produce a product, and since it can be expected to have dimensional stability by suppressing generation of cracks and peeling from the support by heating, it is suitable as a material for high refractive index resin lenses. Can be used for

<< 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. The molded body 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 polymerizable composition of the present invention into a space between a supporting substrate and a mold that are in contact with each other or a space inside a mold that can be divided, the filled composition A step of exposing and photopolymerizing the obtained photopolymerized product from the space filled with the mold, and a step of heating the photopolymerized product before, during or after the mold release. The method of including is mentioned.
The exposure and photopolymerization step can be carried out by applying the conditions shown in the above << cured product >>.
Although it does not specifically limit as conditions of the said heating process, Usually, it selects suitably from the range of 50-260 degreeC and 1-120 minutes. Moreover, it does not specifically limit as a heating means, For example, a hotplate, oven, etc. are mentioned.
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) Spin coater: Crew (registered trademark) 200X manufactured by Brewer Science
(2) UV exposure system: Batch type UV irradiation system (high pressure mercury lamp 2kW x 1 lamp) manufactured by Eye Graphics Co., Ltd.
(3) ¹ H NMR spectrum apparatus: AVANCE III HD manufactured by Bruker
Measurement frequency: 500 MHz
Solvent: CDCl ₃
Internal standard: Tetramethylsilane (δ = 0.00ppm)
(4) Gel permeation chromatography (GPC)
Apparatus: Prominence (registered trademark) GPC system manufactured by Shimadzu Corporation Column: Shodex (registered trademark) GPC KF-804L and GPC KF-803L manufactured by Showa Denko K.K.
Column temperature: 40 ° C
Solvent: Tetrahydrofuran Detector: RI
Calibration curve: standard polystyrene (5) Abbe number ν _D , refractive index n _D
Apparatus A (at the time of cured film measurement): Multi-angle of incidence spectroscopic ellipsometer VASE manufactured by JA Woollam Japan
Apparatus B (when measuring compact): Prismatic coupler model 2010 / M manufactured by Metricon
Measurement temperature: room temperature (approximately 23 ° C)
(6) Melting point Observation device: Nikon Corporation polarizing microscope ECLIPSE (registered trademark) E600 POL
Heating device: Tokai Hit Co., Ltd. Microscope stage automatic temperature control system ThermoPlate (registered trademark)
Temperature rising rate: 0.5 ° C./second Measuring method: The temperature at which a part of the sample started to melt visually was taken as the melting point (7) Viscosity Device: EMS-1000 manufactured by Kyoto Electronics Industry Co., Ltd.
(8) Transmittance Device: UV-Vis Near-Infrared Spectrophotometer V-670 manufactured by JASCO Corporation
Reference: Air

Abbreviations represent the following meanings.
NMA: Naphthalen-2-ylmethyl acrylate VN: 2-vinylnaphthalene [manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.]
SPeDMS: Dimethoxy (phenanthren-9-yl) (4-vinylphenyl) silane BPOEA: 2-([1,1′-biphenyl] -2-yloxy) ethyl acrylate [NK Nakano Chemical Co., Ltd., NK Ester A- LEN-10]
BnA: benzyl acrylate [Osaka Organic Chemical Co., Ltd. Viscoat # 160, BZA]
DVB: Divinylbenzene [DVB-810 manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.]
FDA: 9,9-bis (4- (2-acryloyloxyethoxy) phenyl) fluorene [NK ester A-BPEF manufactured by Shin-Nakamura Chemical Co., Ltd.]
PheTMS: Trimethoxy (9-phenanthryl) silane STMS: Trimethoxy (4-vinylphenyl) silane [Shin-Etsu Silicone (registered trademark) KBM-1403, manufactured by Shin-Etsu Chemical Co., Ltd.]
TMOS: Tetramethoxysilane [manufactured by Tokyo Chemical Industry Co., Ltd.]
TEAH: 35% by mass tetraethylammonium hydroxide aqueous solution [manufactured by Aldrich]
DDT: n-dodecanethiol [Kio Co., Ltd. Thiocalcol 20]
I184: 1-hydroxycyclohexyl phenyl ketone [IRGACURE (registered trademark) 184, manufactured by BASF Japan Ltd.]
TPO: Diphenyl (2,4,6-trimethylbenzoyl) phosphine oxide [IRGACURE (registered trademark) TPO manufactured by BASF Japan Ltd.]
PGMEA: Propylene glycol monomethyl ether acetate THF: Tetrahydrofuran

[Production Example 1] Production of dimethoxy (phenanthren-9-yl) (4-vinylphenyl) silane (SPeDMS) Into a 1 L reaction flask equipped with a condenser, a magnesium cutting piece [manufactured by Kanto Chemical Co., Ltd.] 15.7 g (0.65 mol) was charged, and the air in the flask was replaced with nitrogen using a nitrogen balloon. A mixture of 151.2 g (0.58 mol) of 9-bromophenanthrene [manufactured by Tokyo Chemical Industry Co., Ltd.] and 518 g of THF was added dropwise at room temperature (approximately 23 ° C.) over 1 hour, and the mixture was further stirred for 1 hour. Thus, a Grignard reagent was prepared.
In a 2 L reaction flask, 131.9 g (0.58 mol) of STMS and 259 g of THF were charged, and the air in the flask was replaced with nitrogen using a nitrogen balloon. The above Grignard reagent was added dropwise over 30 minutes under reflux (approximately 66 ° C.), and the mixture was further refluxed for 24 hours. From this reaction mixture, THF was distilled off under reduced pressure using an evaporator. After adding 1,000 g of hexane to the obtained residue and refluxing for 1 hour to dissolve the soluble matter, the insoluble matter was filtered off. 750 g of hexane was added to the insoluble material again, and the soluble material was similarly dissolved, and then the insoluble material was filtered off. The respective filtrates were mixed, and hexane was distilled off under reduced pressure using an evaporator to obtain a crude product. The crude product was recrystallized with 150 g of hexane to obtain 102.4 g of target SPeDMS (yield 47%).
The ¹ H NMR spectrum of the obtained compound is shown in FIG.

[Production Example 2] Production of naphthalen-2-ylmethyl acrylate (NMA) In a 200 mL reaction flask, 25.0 g (0.158 mol) of 2-naphthalenemethanol [manufactured by Tokyo Chemical Industry Co., Ltd.] and 158 g of THF were charged, and nitrogen was added. The air in the flask was replaced with nitrogen using a balloon, and then cooled to 0 ° C. Triethylamine [manufactured by Tokyo Chemical Industry Co., Ltd.] 17.58 g (0.174 mol) and acryloyl chloride [manufactured by Tokyo Chemical Industry Co., Ltd.] 15.73 g (0.174 mol) were added thereto, and room temperature (approximately 23 ° C.). ) For 1 hour. 158 g of water was added to the reaction mixture, and the product was extracted with 158 g of ethyl acetate. The crude product was obtained by distilling off the solvent from the organic layer under reduced pressure using an evaporator. The crude product is purified by silica gel chromatography (hexane / ethyl acetate = 9/1 (mass ratio)) to obtain 21.5 g (yield: 64%) of naphthalen-2-ylmethyl acrylate, which is the target product. It was.
From the ¹ H NMR spectrum of the obtained compound, it was confirmed to be the target structure.

[Production Example 3] Production of trimethoxy (9-phenanthryl) silane (PheTMS) A 500 mL reaction flask equipped with a condenser was charged with 10.4 g (0.43 mol) of a magnesium cutting piece [manufactured by Kanto Chemical Co., Ltd.] The air in the flask was replaced with nitrogen using a nitrogen balloon. A mixture of 9-bromophenanthrene [manufactured by Tokyo Chemical Industry Co., Ltd.] 100.3 g (0.39 mol) and THF 346 g was added dropwise at room temperature (approximately 23 ° C.) over 1 hour, and the mixture was further stirred for 30 minutes. Thus, a Grignard reagent was prepared.
A 1 L reaction flask was charged with 178.0 g (1.17 mol) of TMOS and 346 g of THF, and the air in the flask was replaced with nitrogen using a nitrogen balloon. The Grignard reagent was added dropwise at room temperature (approximately 23 ° C.) over 30 minutes, and the mixture was further stirred for 2 hours. From this reaction mixture, THF was distilled off under reduced pressure using an evaporator. To the resulting residue, 1,000 g of hexane was added to dissolve the soluble material, and then the insoluble material was filtered off. To this insoluble material, 500 g of hexane was added again, and the insoluble material was similarly filtered off. The respective filtrates were mixed, and hexane was distilled off under reduced pressure using an evaporator to obtain a crude product. The crude product was distilled under reduced pressure (1 mmHg, 120 to 150 ° C.) and then recrystallized with 389 g of methanol to obtain 74.6 g of the intended PheTMS (yield 64%).
The ¹ H NMR spectrum of the obtained compound is shown in FIG.

[Production Example 4] Production of High Refractive Index Polymerizable Compound 1 (PSeDMS) A 50 mL reaction flask equipped with a condenser was charged with 1.36 g (3.23 mmol) of TEAH and 12 g of THF. Air was replaced with nitrogen. A mixture of 29.9 g (80.7 mmol) of SPeDMS prepared according to Preparation Example 1 and 24 g of THF was added dropwise at room temperature (approximately 23 ° C.) over 10 minutes, and the mixture was stirred at 40 ° C. for 16 hours. This was cooled to room temperature (approximately 23 ° C.). Next, 6.0 g of a cation exchange resin [Amberlyst (registered trademark) 15JWET] manufactured by Dow Chemical Co., Ltd.] preliminarily washed with THF and a filter aid [KC Flock W-100GK manufactured by Nippon Paper Industries Co., Ltd.] were added to this reaction mixture. 1.2 g was added and the reaction was stopped by stirring for 1 hour. Thereafter, the cation exchange resin and the filter aid were filtered through a membrane filter having a pore size of 0.5 μm, and further washed with 30 g of ethyl acetate. The filtrate and washing solution were combined and added to 897 g of methanol to precipitate the polymer. The precipitate was filtered and dried to obtain 18.9 g of the target high refractive index polymerizable compound 1 (hereinafter sometimes abbreviated as PSPeDMS).
The weight average molecular weight Mw of the obtained compound measured in terms of polystyrene by GPC was 610, and the degree of dispersion: Mw (weight average molecular weight) / Mn (number average molecular weight) was 1.2.

[Production Example 5] Production of high refractive index polymerizable compound 2 (XPe55) In a 50 mL reaction flask equipped with a condenser, TEAH 0.90 g (2.14 mmol), ion-exchanged water 0.86 g (47.7 mmol), and 7 g of THF was charged, and the air in the flask was replaced with nitrogen using a nitrogen balloon. Here, a mixture of 9.9 g (26.8 mmol) of SPeDMS prepared according to Preparation Example 1, 8.0 g (26.8 mmol) of PheTMS prepared according to Preparation Example 3, and 14 g of THF was added at room temperature (approximately 23 ° C.) for 10 minutes. The solution was added dropwise and stirred at 40 ° C. for 16 hours. This was cooled to room temperature (approximately 23 ° C.). Subsequently, 3.6 g of a cation exchange resin [Amberlyst (registered trademark) 15JWET manufactured by Dow Chemical Co., Ltd.] 3.6 g previously washed with THF and a filter aid [KC Flock W-100GK manufactured by Nippon Paper Industries Co., Ltd.] were added to the reaction mixture. ] 0.72g was added and it stirred for 1 hour, and reaction was stopped. Thereafter, the cation exchange resin and the filter aid were filtered through a membrane filter having a pore size of 0.5 μm, and further washed with 18 g of ethyl acetate. The filtrate and the washing solution were combined and added to 538 g of methanol to precipitate the polymer. The precipitate was filtered and dried to obtain 14.8 g of a target high refractive index polymerizable compound 2 (hereinafter sometimes abbreviated as XPe55).
The weight average molecular weight Mw of the obtained compound measured in terms of polystyrene by GPC was 1,000, and the degree of dispersion: Mw / Mn was 1.0.

  With respect to SPeDMS and NMA produced according to Production Examples 1 and 2, and VN and BPOEA, the state and viscosity of substances at 23 ° C. and 100 ° C. under atmospheric pressure were measured. The results are shown in Table 1.

The SPeDMS, NMA, VN, or BPOEA 100 parts by mass, I184 1 part by mass, and PGMEA 233 parts by mass were mixed. This solution was filtered with a PTFE syringe filter having a pore size of 0.2 μm to obtain a varnish with a solid content concentration of 30% by mass.
Each varnish was spin-coated (1,500 rpm × 30 seconds) on a silicon wafer and dried by heating on a hot plate at 80 ° C. for 1 minute. This coating film was exposed to UV at 20 mW / cm ² for 250 seconds under a nitrogen atmosphere, and further heated on a hot plate at 150 ° C. for 20 minutes to produce a cured film having a thickness of 1.0 μm. The Abbe number ν _D at a wavelength of 589 nm (D line) of the obtained cured film was measured. The results are also shown in Table 1.

[Example 1] Preparation of polymerizable composition 1 2 parts by mass of VN as a viscosity reducing agent for component (b), 6 parts by mass of FDA as a high refractive index polymerizable compound for component (a), and polymerizability for component (c) As a diluent, 2 parts by mass of BnA was blended and stirred at 40 ° C. for 2 hours. To this, 0.1 part by mass of I184 and 0.07 part by mass of TPO were added as a polymerization initiator for the component (d), and the mixture was stirred at 40 ° C. for 1 hour. Furthermore, 0.3 mass part of DDT was added here as a chain transfer agent (reaction accelerator), and the polymerizable composition 1 was obtained as a uniform transparent varnish by stirring at room temperature (approximately 23 ° C.) for 2 hours.

[Examples 2 to 9, Comparative Examples 1 to 7] Preparation of polymerizable compositions 2 to 16 The polymerizable composition 2 was operated in the same manner as in Example 1 except that each formulation was changed as shown in Table 2. ~ 16 were prepared respectively. In Table 2, “part” represents “part by mass”.

  Table 3 shows the viscosity at 25 ° C. of each polymerizable composition.

[Production of cured product and evaluation of optical properties]
Each polymerizable composition was sandwiched between two release-treated glass substrates together with a 1 mm thick silicone rubber spacer. The sandwiched polymerizable composition was exposed to UV at 20 mW / cm ² for 250 seconds. After the cured product was peeled off from the glass substrate, the molded product having a diameter of 30 mm and a thickness of 1 mm was produced by heating for 20 minutes on a 150 ° C. hot plate.
The Abbe number ν _{D at} a wavelength of 589 nm (D line), the refractive index n _D , and the average transmittance at a wavelength of 400 to 800 nm of the obtained molded product were measured. The results are also shown in Table 3.

As shown in Tables 2 and 3, by blending the low-viscosity agent of the present invention, a lower viscosity and a lower Abbe number ν _D are realized, and the refractive index n _D and transmission are compared with the case of not blending the lower viscosity agent. The results were also obtained that the rate could be improved to the same or higher value (see Examples 1 and 3 and Comparative Example 1, Example 4 and Comparative Example 2, Example 5 and Comparative Example 3). In Example 2, low viscosity and high refractive index and high transmittance were realized by blending the low viscosity agent, but the ratio of the high refractive index polymerizable compound in the polymerizable composition was reduced. As a result, the Abbe number increased.
In addition, BPOEA, which is a conventional liquid diluent, was able to maintain a reduced viscosity or a viscosity of 10,000 mPa · s or less as in the case of the present invention, but the Abbe number increased (Examples). 5 and Comparative Example 5, Example 7 and Comparative Example 6, Example 9 and Comparative Example 7). In addition, compared with the example without a viscosity reducing agent, BPOEA resulted in an increase in Abbe number on the contrary (see Comparative Examples 3 and 5 and Comparative Examples 4 and 7).

[(A) Optical characteristics of high refractive index polymerizable compound]
100 parts by mass of the FDA, PSPeDMS, XPe55 or BPOEA, 1 part by mass of I184, and 233 parts by mass of PGMEA were mixed. This solution was filtered with a PTFE syringe filter having a pore size of 0.2 μm to obtain a varnish with a solid content concentration of 30% by mass.
Each varnish was spin-coated (1,500 rpm × 30 seconds) on a silicon wafer and dried by heating on a hot plate at 80 ° C. for 1 minute. This coating film was exposed to UV at 20 mW / cm ² for 250 seconds under a nitrogen atmosphere, and further heated on a hot plate at 150 ° C. for 20 minutes to produce a cured film having a thickness of 1.0 μm. The refractive index and Abbe number ν _D at a wavelength of 589 nm (D line) of the obtained cured film were measured. The results are shown in Table 4.

Claims (17)

A compound having a solid state at 1013.25 hPa at 23 ° C. and having a melting point of less than 100 ° C., having a viscosity at 100 ° C. of 10 mPa · s or less, and a D line (589.3 nm) of the cured product A compound having an Abbe number of 23 or less in
A method of using as a viscosity reducing agent for a high refractive index polymerizable compound having at least one polymerizable double bond, and having a refractive index of the cured product at D-line (589.3 nm) of 1.60 or more. The viscosity reducing agent is a phenyl group or phenylene group which may be substituted with an alkyl group having 1 to 6 carbon atoms, or a monovalent or divalent condensed ring hydrocarbon group having a plurality of benzene ring structures (carbon atoms). And a monovalent or divalent hydrocarbon ring assembly group (having 1 to 6 carbon atoms) in which a plurality of aromatic rings are directly bonded with a single bond. At least one aromatic group selected from the group consisting of (optionally substituted with an alkyl group), and
A compound having at least one group having a polymerizable double bond selected from the group consisting of a vinyl group, an allyl group, a (meth) allyloxy group and a (meth) acryloyl group,
The method of claim 1. The method according to claim 2, wherein the viscosity reducing agent is a compound represented by the following formula [1].

(Wherein X represents a phenyl group having at least one substituent having a polymerizable double bond, a naphthyl group having at least one substituent having a polymerizable double bond, and a substituent having a polymerizable double bond. Represents a biphenyl group having at least one or a phenanthryl group having at least one substituent having a polymerizable double bond, and Ar ¹ represents a condensed ring hydrocarbon group having a plurality of benzene ring structures (having 1 to 6 carbon atoms). Or a hydrocarbon ring assembly group (which may be substituted with an alkyl group having 1 to 6 carbon atoms) in which a plurality of aromatic rings are directly bonded with a single bond. R ¹ represents a methyl group, an ethyl group, or an isopropyl group.) The method according to claim 2, wherein the viscosity reducing agent is a compound represented by the following formula [2].

(In the formula, Ar ² represents a q-valent aromatic hydrocarbon residue, q represents 1 or 2,
Y represents a single bond, —O—C (═O) — group, or —O— group, and R ² represents a hydrogen atom or a methyl group. ) The method according to claim 2, wherein the viscosity reducing agent is a compound represented by the following formula [3-1] or formula [3-2].

(In the formula, R ¹ represents a methyl group, an ethyl group, or an isopropyl group.) A low-viscosity agent for a high-refractive index polymerizable compound having at least one polymerizable double bond and a refractive index of the cured product at the D-line (589.3 nm) of 1.60 or more,
A compound having a solid state at 1013.25 hPa at 23 ° C. and having a melting point of less than 100 ° C., having a viscosity at 100 ° C. of 10 mPa · s or less, and a D line (589.3 nm) of the cured product ), A viscosity reducing agent comprising a compound having an Abbe number of 23 or less. (A) 100 parts by mass of a high-refractive-index polymerizable compound having at least one polymerizable double bond and a refractive index of the cured product at D-line (589.3 nm) of 1.60 or more, and (b) A compound having a solid state at 1013.25 hPa at 23 ° C. and having a melting point of less than 100 ° C., having a viscosity at 100 ° C. of 10 mPa · s or less, and a D line (589.3 nm) of the cured product The polymerizable composition comprising 10 to 500 parts by mass of a viscosity reducing agent, comprising a compound having an Abbe number of 23 or less. The (a) high refractive index polymerizable compound is represented by the polycondensate of the alkoxysilicon compound A represented by the formula [4], the alkoxysilicon compound A represented by the formula [4], and the formula [5]. The polymerizable composition according to claim 7, comprising a reactive polysiloxane containing at least one of a polycondensate with an alkoxysilicon compound B.

(Wherein X represents a phenyl group having at least one substituent having a polymerizable double bond, a naphthyl group having at least one substituent having a polymerizable double bond, and a substituent having a polymerizable double bond. Represents a biphenyl group having at least one, or a phenanthryl group having at least one substituent having a polymerizable double bond, and Ar ³ represents a phenyl group which may be substituted with an alkyl group having 1 to 6 carbon atoms, a plurality of A condensed ring hydrocarbon group having a benzene ring structure (which may be substituted with an alkyl group having 1 to 6 carbon atoms), or a hydrocarbon ring assembly group in which a plurality of aromatic rings are directly bonded by a single bond ( And optionally substituted with an alkyl group having 1 to 6 carbon atoms, and R ³ represents a methyl group, an ethyl group, or an isopropyl group.)

(In the formula, Ar ⁴ is a phenyl group which may be substituted with an alkyl group having 1 to 6 carbon atoms, or a condensed ring hydrocarbon group having a plurality of benzene ring structures (substituted with an alkyl group having 1 to 6 carbon atoms). Or a hydrocarbon ring assembly group in which a plurality of aromatic rings are directly bonded with a single bond (which may be substituted with an alkyl group having 1 to 6 carbon atoms), and R ⁴ is Represents a methyl group, an ethyl group, or an isopropyl group.) The polymerizable composition according to claim 7, wherein the high refractive index polymerizable compound (a) includes a fluorene compound represented by the formula [6].

(In the formula, R ⁵ and R ⁶ 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 represent an alkylene group having 1 to 6 carbon atoms, and m and n each independently represents 0 ≦ m + n ≦ 40. Represents 0 or a positive integer to satisfy.) The (a) high refractive index polymerizable compound is a compound represented by the following formula [7-1], a compound having a structural unit represented by the formula [7-2], and a formula [7-2]. The polymerizable composition according to claim 7, wherein the polymerizable composition is selected from the group consisting of a structural unit and a compound having a structural unit represented by the formula [7-3].

(In the formula, two Q's are the same group, and each represents a group selected from the group consisting of a vinyloxy group, an allyloxy group and a (meth) acryloyloxy group, and two p's are each independently 0 to 3) Indicates an integer.)

(In the formula, Ar ⁵ and Ar ⁶ each independently represent a phenyl group, a naphthyl group, or a phenanthryl group.) (C) The polymerizable composition according to any one of claims 7 to 10, further comprising a polymerizable diluent having a liquid state at 23 ° C under 1013.25 hPa. A cured product of the polymerizable composition according to any one of claims 7 to 11. A high refractive index resin lens material comprising the polymerizable composition according to any one of claims 7 to 11. The resin lens produced from the polymeric composition as described in any one of Claims 7 thru | or 11. A step of filling the polymerizable composition according to any one of claims 7 to 11 into a space between a supporting support and a mold, or a space inside a mold that can be divided, and the filling. A method for producing a molded body comprising the step of exposing and photopolymerizing the prepared composition. 16. The method according to claim 15, further comprising a step of taking out and releasing the obtained photopolymer from the filled space, and a step of heating the photopolymer before, during or after the release. Manufacturing method. The manufacturing method according to claim 15 or 16, wherein the molded body is a camera module lens.

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