JP2010037368A - Organic-inorganic composite material, preparation method thereof and optical component - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide: an organic-inorganic composite material which has high light transmittance, high refractive index and improved heat resistance; a preparation method thereof; and an optical component using the organic-inorganic composite material. <P>SOLUTION: The organic-inorganic composite material comprises a thermoplastic resin having at least one unit structure represented by formula (1) or (2) and inorganic particulates. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to an organic-inorganic composite material having high light transmittance and refractive index and improved heat resistance, and a lens base material comprising the same (for example, spectacle lens, lens for optical equipment, optoelectronics) Lens, laser lens, pickup lens, in-vehicle camera lens, portable camera lens, digital camera lens, OHP lens, and the like.

  In recent years, research on optical materials has been actively conducted, and particularly in the field of lens materials, development of materials excellent in high refraction, transparency, lightness, easy moldability, releasability, etc. is strongly desired. Yes.

  Plastic lenses are lighter and harder to break than inorganic materials such as glass and can be processed into various shapes, so in recent years they are rapidly spreading not only to spectacle lenses but also to optical materials such as portable camera lenses and pickup lenses. .

  Along with this, it has been required to increase the refractive index of the material itself in order to reduce the thickness of the lens. For example, a technique for introducing a sulfur atom into a polymer (see Patent Document 1 and Patent Document 2) In addition, a technique for introducing a halogen atom or an aromatic ring into a polymer (see Patent Document 3), a technique using a copolymer of an indene derivative and a vinyl monomer (see Patent Document 4), and the like have been actively studied. . However, a plastic material that has a sufficiently large refractive index and has good transparency and can be used as a substitute for glass has not yet been developed.

  Since it is difficult to increase the refractive index with only an organic substance, attempts have been made to produce a high refractive index material by dispersing an inorganic substance having a high refractive index in a resin matrix (see Patent Documents 5 and 6). In order to reduce attenuation of transmitted light due to Rayleigh scattering, it is preferable to uniformly disperse inorganic fine particles having a particle diameter of 15 nm or less in the resin matrix. However, since primary particles having a particle diameter of 15 nm or less are very likely to aggregate, it is extremely difficult to uniformly disperse them in the resin matrix. In addition, when the attenuation of transmitted light in the optical path length corresponding to the lens thickness is taken into consideration, the amount of inorganic fine particles added must be limited. For this reason, it has been required to disperse the fine particles in the resin matrix at a high concentration without reducing the transparency of the resin.

  In order to meet such a demand, an organic-inorganic composite material in which inorganic fine particles are dispersed in a thermoplastic resin having a functional group capable of forming a chemical bond with inorganic fine particles has been proposed (see Patent Document 7). This organic-inorganic composite material contains a practically inexpensive polystyrene-based resin as a copolymerization component, has good dispersibility of inorganic fine particles, and has achieved a refractive index of 1.60 or more.

  However, for example, when inorganic fine particles are dispersed in a thermoplastic resin containing a polystyrene-based resin of Patent Document 7 as a copolymerization component, it is known that the heat resistance of the organic-inorganic composite material is reduced. Has been. In response to such problems, it has been studied to improve heat resistance by using a thermoplastic resin having a cyclic structure introduced into the main chain.

Thus, an organic-inorganic composite material having good dispersibility of inorganic fine particles without decreasing transparency, a high refractive index, and high heat resistance has not been known.
JP 2002-131502 A Japanese Patent Laid-Open No. 10-298287 JP 2004-244444 A JP 2001-89537 A JP 61-291650 A JP 2003-73564 A JP 2007-238929 A

  As a result of the inventors further studying a thermoplastic resin in which a ring structure is introduced into the main chain, the use of a thermoplastic resin having a specific structure makes it possible to disperse inorganic fine particles without lowering transparency and refraction. It was found that an organic-inorganic composite material having a high rate and high heat resistance can be obtained. Furthermore, when a polystyrene resin copolymer, which is inexpensive and preferably used practically, was also examined, it was found that a high molecular weight polymer can be obtained with good polymerizability and the above performance can be obtained.

  The present invention has been made in view of the above circumstances, and an object of the present invention is to provide an organic-inorganic composite material having high light transmittance and refractive index, improved heat resistance, a method for producing the same, and the organic-inorganic composite material. It is to provide an optical component used.

  As a result of intensive studies to achieve the above object, the inventors of the present invention include a thermoplastic resin having a specific functional group and inorganic fine particles, and an organic-inorganic composite material satisfying a specific condition is highly refractive. The inventors found that heat resistance was improved while having excellent transparency, and led to completion of the present invention described below.

〔一般式（１）中、環αは単環式または多環式の環を表し、Ｒ¹〜Ｒ⁴はそれぞれ独立に水素原子、ハロゲン原子、置換もしくは無置換のアルキル基、置換もしくは無置換のアリール基、置換もしくは無置換のアルコキシ基、置換もしくは無置換のオキシカルボニル基、またはシアノ基を表す。〕

〔一般式（２）中、環βは単環式または多環式の環を表し、Ｒ⁵〜Ｒ⁸はそれぞれ独立に水素原子、ハロゲン原子、置換もしくは無置換のアルキル基、置換もしくは無置換のアリール基、置換もしくは無置換のアルコキシ基、置換もしくは無置換のオキシカルボニル基、またはシアノ基を表す。〕
［２］ 前記熱可塑性樹脂が、前記一般式（１）または一般式（２）で表される単位構造と、主鎖に環構造を有さず側鎖に芳香環構造を有する単位構造との共重合体であることを特徴とする請求項１に記載の有機無機複合材料。
［３］ 前記一般式（１）または一般式（２）で表される単位構造が、下記一般式（３）もしくは一般式（４）、または、下記一般式（５）もしくは一般式（６）で表される単位構造であることを特徴とする［１］または［２］に記載の有機無機複合材料。

〔一般式（３）中、各Ｒ⁹はそれぞれ独立に、水素原子、ハロゲン原子、置換もしくは無置換のアルキル基、置換もしくは無置換のアリール基、置換もしくは無置換のアルコキシ基、ヒドロキシル基を表し、Ｘ¹およびＸ²はそれぞれ独立に、酸素原子または硫黄原子を表す。〕

〔一般式（４）中、各Ｒ¹⁰はそれぞれ独立に、水素原子、ハロゲン原子、置換もしくは無置換のアルキル基、置換もしくは無置換のアリール基、置換もしくは無置換のアルコキシ基を表し、Ｘ³は、酸素原子、硫黄原子、−ＣＨ₂−、−ＮＲ−を表し、該Ｒは水素原子、置換もしくは無置換のアルキル基、置換もしくは無置換のアリール基を表す。〕

〔一般式（５）中、各Ｒ⁹はそれぞれ独立に、水素原子、ハロゲン原子、置換もしくは無置換のアルキル基、置換もしくは無置換のアリール基、置換もしくは無置換のアルコキシ基、ヒドロキシル基を表し、Ｘ¹およびＸ²はそれぞれ独立に、酸素原子または硫黄原子を表す。〕

〔一般式（６）中、各Ｒ¹⁰はそれぞれ独立に、水素原子、ハロゲン原子、置換もしくは無置換のアルキル基、置換もしくは無置換のアリール基、置換もしくは無置換のアルコキシ基を表し、Ｘ³は、酸素原子、硫黄原子、−ＣＨ₂−、−ＮＲ−を表し、該Ｒは水素原子、置換もしくは無置換のアルキル基、置換もしくは無置換のアリール基を表す。〕
［４］ 下記一般式（７）または一般式（８）で表されるモノマーの少なくとも一種を環化重合して熱可塑性樹脂を得る工程と、前記熱可塑性樹脂に無機微粒子を分散させる工程を含むことを特徴とする有機無機複合材料の製造方法。

〔一般式（７）中、Ｒ³¹〜Ｒ³⁴はそれぞれ独立に水素原子、ハロゲン原子、置換もしくは無置換のアルキル基、置換もしくは無置換のアリール基、置換もしくは無置換のアルコキシ基、置換もしくは無置換のオキシカルボニル基、またはシアノ基を表し、Ｘ³¹およびＸ³²はそれぞれ独立に酸素原子または硫黄原子を表し、Ｌ¹は単結合または２価の有機連結基を表す。〕

〔一般式（８）中、Ｒ³⁵〜Ｒ³⁸はそれぞれ独立に水素原子、ハロゲン原子、置換もしくは無置換のアルキル基、置換もしくは無置換のアリール基、置換もしくは無置換のアルコキシ基、置換もしくは無置換のオキシカルボニル基、またはシアノ基を表し、Ｘ³³は、酸素原子、硫黄原子、−ＣＨ₂−、−ＮＲ−を表し、該Ｒは水素原子、置換もしくは無置換のアルキル基、置換もしくは無置換のアリール基を表し、Ｌ²およびＬ³はそれぞれ独立に単結合または２価の有機連結基を表す。〕
［５］ 前記一般式（７）または一般式（８）で表されるモノマーと、重合した際に主鎖に環構造を有さず側鎖に芳香環構造を有する構造を形成しうるモノマーとを共重合体させて熱可塑性樹脂を得る工程を含むことを特徴とする［４］に記載の有機無機複合材料の製造方法。
［６］ 前記一般式（７）または一般式（８）で表されるモノマーが、下記一般式（９）または一般式（１０）で表されるモノマーであることを特徴とする［４］または［５］に記載の有機無機複合材料の製造方法。

〔一般式（９）中、各Ｒ³⁹は、水素原子、ハロゲン原子、置換もしくは無置換のアルキル基、置換もしくは無置換のアリール基、置換もしくは無置換のアルコキシ基、ヒドロキシル基を表し、Ｘ³¹およびＸ³²はそれぞれ独立に酸素原子または硫黄原子を表す。〕

〔一般式（１０）中、各Ｒ⁴⁰はそれぞれ独立に、水素原子、ハロゲン原子、置換もしくは無置換のアルキル基、置換もしくは無置換のアリール基、置換もしくは無置換のアルコキシ基を表し、Ｘ³³は、酸素原子、硫黄原子、−ＣＨ₂−、−ＮＲ−を表し、該Ｒは水素原子、置換もしくは無置換のアルキル基、置換もしくは無置換のアリール基を表す。〕
［７］ ［４］〜［６］のいずれか一項に記載の有機無機複合材料の製造方法により製造されたことを特徴とする有機無機複合材料。
［８］ 前記熱可塑性樹脂の波長５８９ｎｍにおける屈折率が１.５５以上であることを特徴とする［１］〜［３］および［７］のいずれか一項に記載の有機無機複合材料。
［９］ 前記熱可塑性樹脂の数平均分子量が１００００〜２０００００であることを特徴とする［１］〜［３］、［７］および［８］のいずれか一項に記載の有機無機複合材料。
［１０］ 前記熱可塑性樹脂が、前記一般式（１）または一般式（２）で表される単位構造を３〜７０質量％含むことを特徴とする［１］〜［３］および［７］〜［９］のいずれか一項に記載の有機無機複合材料。
［１１］ 前記熱可塑性樹脂が下記の群から選ばれる少なくとも１種以上の官能基を有することを特徴とする［１］〜［３］および［７］〜［１０］のいずれか１項に記載の有機無機複合材料。

［Ｒ¹¹、Ｒ¹²、Ｒ¹³、Ｒ¹⁴、Ｒ¹⁵、Ｒ¹⁶は、それぞれ独立に水素原子、置換または無置換のアルキル基、置換または無置換のアルケニル基、置換または無置換のアルキニル基、あるいは、置換または無置換のアリール基を表す。］、−ＳＯ₃Ｈ、−ＯＳＯ₃Ｈ、−ＣＯ₂Ｈ、−ＯＨ、−Ｓｉ（ＯＲ¹⁷）_nＲ¹⁸ _n［Ｒ¹⁷、Ｒ¹⁸はそれぞれ独立に水素原子、置換または無置換のアルキル基、置換または無置換のアルケニル基、置換または無置換のアルキニル基、あるいは、置換または無置換のアリール基を表し、ｎは１〜３の整数を表す。］
［１２］ 前記熱可塑性樹脂が、前記官能基を高分子鎖１本あたり平均０.１〜２０個有していることを特徴とする［１１］に記載の有機無機複合材料。
［１３］ 前記無機微粒子の数平均粒子径が１〜１５ｎｍであることを特徴とする［１］〜［３］および［７］〜［１２］のいずれか一項に記載の有機無機複合材料。
［１４］ 前記無機微粒子の波長５８９ｎｍにおける屈折率が１.９０〜３.００であることを特徴とする［１］〜［３］および［７］〜［１３］のいずれか一項に記載の有機無機複合材料。
［１５］ 前記無機微粒子が、酸化ジルコニウム、酸化亜鉛、酸化錫および酸化チタンからなる群より選ばれる少なくとも一つを含有することを特徴とする請求項１〜３および７〜１４のいずれか一項に記載の有機無機複合材料。
［１６］ 前記無機微粒子を２０〜９５質量％含むことを特徴とする［１］〜［３］および［７］〜［１５］のいずれか一項に記載の有機無機複合材料。
［１７］ 波長５８９ｎｍにおける屈折率が１.６３以上であり、かつ、波長５８９ｎｍにおける厚さ１ｍｍ換算の光線透過率が７０％以上であることを特徴とする［１］〜［３］および［７］〜［１６］のいずれか一項に記載の有機無機複合材料。
［１８］ ガラス転移温度が８５℃以上であることを特徴とする［１］〜［３］および［７］〜［１７］のいずれか一項に記載の有機無機複合材料。
［１９］ ［１］〜［３］および［７］〜［１８］のいずれか一項に記載の有機無機複合材料を含んで構成される光学部品。
［２０］ 前記光学部品がレンズであることを特徴とする、［１９］に記載の光学部品。 [1] An organic-inorganic containing a thermoplastic resin having at least one unit structure represented by the following general formula (1) or general formula (2) and inorganic fine particles Composite material.

[In general formula (1), ring α represents a monocyclic or polycyclic ring, and R ^{1 to} R ⁴ each independently represent a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted group. An aryl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted oxycarbonyl group, or a cyano group. ]

[In general formula (2), ring β represents a monocyclic or polycyclic ring, and R ^{5 to} R ⁸ each independently represents a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted group. An aryl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted oxycarbonyl group, or a cyano group. ]
[2] The thermoplastic resin includes a unit structure represented by the general formula (1) or the general formula (2) and a unit structure having no ring structure in the main chain and having an aromatic ring structure in the side chain. The organic-inorganic composite material according to claim 1, which is a copolymer.
[3] The unit structure represented by the general formula (1) or the general formula (2) has the following general formula (3) or the general formula (4), or the following general formula (5) or the general formula (6). The organic-inorganic composite material according to [1] or [2], which has a unit structure represented by:

[In General Formula (3), each R ⁹ independently represents a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted alkoxy group, or a hydroxyl group. , X ¹ and X ² each independently represents an oxygen atom or a sulfur atom. ]

[In General Formula (4), each R ¹⁰ independently represents a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted alkoxy group, and X ³ Represents an oxygen atom, a sulfur atom, —CH ₂ —, —NR—, and R represents a hydrogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group. ]

[In the general formula (5), each R ⁹ independently represents a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted alkoxy group, or a hydroxyl group. , X ¹ and X ² each independently represents an oxygen atom or a sulfur atom. ]

[In General Formula (6), each R ¹⁰ independently represents a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted alkoxy group, and X ³ Represents an oxygen atom, a sulfur atom, —CH ₂ —, —NR—, and R represents a hydrogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group. ]
[4] It includes a step of cyclopolymerizing at least one monomer represented by the following general formula (7) or general formula (8) to obtain a thermoplastic resin, and a step of dispersing inorganic fine particles in the thermoplastic resin. The manufacturing method of the organic inorganic composite material characterized by the above-mentioned.

[In General Formula (7), R ^{31 to} R ³⁴ are each independently a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted alkoxy group, substituted or unsubstituted A substituted oxycarbonyl group or a cyano group is represented, X ³¹ and X ³² each independently represent an oxygen atom or a sulfur atom, and L ¹ represents a single bond or a divalent organic linking group. ]

[In General Formula (8), R ^{35 to} R ³⁸ are each independently a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted alkoxy group, substituted or unsubstituted A substituted oxycarbonyl group or a cyano group, X ³³ represents an oxygen atom, a sulfur atom, —CH ₂ — or —NR—, wherein R represents a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted group; A substituted aryl group is represented, and L ² and L ³ each independently represent a single bond or a divalent organic linking group. ]
[5] A monomer represented by the general formula (7) or the general formula (8), and a monomer capable of forming a structure having an aromatic ring structure in the side chain without having a ring structure in the main chain when polymerized. The method for producing an organic-inorganic composite material according to [4], comprising a step of obtaining a thermoplastic resin by copolymerizing the above.
[6] The monomer represented by the general formula (7) or the general formula (8) is a monomer represented by the following general formula (9) or the general formula (10) [4] or [5] The method for producing an organic-inorganic composite material according to [5].

[In the general formula (9), each R ³⁹ represents a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted alkoxy group, a hydroxyl group, X ³¹ And X ³² each independently represents an oxygen atom or a sulfur atom. ]

[In the general formula (10), each R ⁴⁰ independently represents a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted alkoxy group, and X ³³ Represents an oxygen atom, a sulfur atom, —CH ₂ —, —NR—, and R represents a hydrogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group. ]
[7] An organic-inorganic composite material produced by the method for producing an organic-inorganic composite material according to any one of [4] to [6].
[8] The organic-inorganic composite material according to any one of [1] to [3] and [7], wherein the thermoplastic resin has a refractive index of 1.55 or more at a wavelength of 589 nm.
[9] The organic-inorganic composite material according to any one of [1] to [3], [7] and [8], wherein the thermoplastic resin has a number average molecular weight of 10,000 to 200,000.
[10] The thermoplastic resin contains 3 to 70% by mass of the unit structure represented by the general formula (1) or the general formula (2) [1] to [3] and [7] The organic-inorganic composite material according to any one of to [9].
[11] The thermoplastic resin according to any one of [1] to [3] and [7] to [10], wherein the thermoplastic resin has at least one functional group selected from the following group. Organic inorganic composite material.

[R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ and R ¹⁶ are each independently a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkynyl group, Alternatively, it represents a substituted or unsubstituted aryl group. _{], - SO 3 H, -OSO} 3 H, -CO 2 H, -OH, -Si (OR 17) n R 18 n [R 17, R 18 each independently represent a hydrogen atom, a substituted or unsubstituted alkyl group Represents a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkynyl group, or a substituted or unsubstituted aryl group, and n represents an integer of 1 to 3. ]
[12] The organic-inorganic composite material according to [11], wherein the thermoplastic resin has an average of 0.1 to 20 functional groups per polymer chain.
[13] The organic-inorganic composite material according to any one of [1] to [3] and [7] to [12], wherein the number average particle diameter of the inorganic fine particles is 1 to 15 nm.
[14] The refractive index of the inorganic fine particles at a wavelength of 589 nm is 1.90 to 3.00, according to any one of [1] to [3] and [7] to [13] Organic inorganic composite material.
[15] The inorganic fine particles contain at least one selected from the group consisting of zirconium oxide, zinc oxide, tin oxide and titanium oxide. The organic-inorganic composite material described in 1.
[16] The organic-inorganic composite material according to any one of [1] to [3] and [7] to [15], comprising 20 to 95% by mass of the inorganic fine particles.
[17] The refractive index at a wavelength of 589 nm is 1.63 or more, and the light transmittance in terms of 1 mm thickness at a wavelength of 589 nm is 70% or more, [1] to [3] and [7 ] The organic-inorganic composite material according to any one of [16] to [16].
[18] The organic-inorganic composite material according to any one of [1] to [3] and [7] to [17], wherein the glass transition temperature is 85 ° C. or higher.
[19] An optical component comprising the organic-inorganic composite material according to any one of [1] to [3] and [7] to [18].
[20] The optical component according to [19], wherein the optical component is a lens.

  The organic-inorganic composite material of the present invention has high light transmittance and refractive index, and improved heat resistance. Moreover, the optical component of the present invention has excellent transparency and a high refractive index, and further has high heat resistance.

  Hereinafter, the organic-inorganic composite material of the present invention and its utilization form will be described in detail. The description of the constituent elements described below may be made based on typical embodiments of the present invention, but the present invention is not limited to such embodiments. In the present specification, a numerical range represented by using “to” means a range including numerical values described before and after “to” as a lower limit value and an upper limit value.

[Thermoplastic resin]
The thermoplastic resin used in the present invention is characterized by having at least one unit structure represented by the general formula (1) or the general formula (2). By having such a unit structure, the heat resistance of the organic-inorganic composite material of the present invention, that is, the glass transition temperature (hereinafter also referred to as Tg) is improved.
Hereinafter, the thermoplastic resin used in the present invention will be described in detail.

(Unit structure represented by general formula (1) or general formula (2))
The unit structure represented by the general formula (1) or the general formula (2) will be described.

In the general formula (1), the ring α represents a monocyclic or polycyclic ring. The ring α is preferably a monocyclic ring.
R ^{1 to} R ⁴ are each independently a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted oxycarbonyl group, or Represents a cyano group.
R ^{1 to} R ⁴ are each independently preferably a methyl group, an ethyl group, a chlorine atom, a bromine atom, a cyano group, a phenyl group or a hydrogen atom, and a methyl group, a chlorine atom, a cyano group, a phenyl group, or A hydrogen atom is more preferable, and a phenyl group or a hydrogen atom is particularly preferable.
R ^{1 to} R ⁴ may further have a substituent, and such a substituent is not particularly limited. For example, a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted And aryl groups and substituted or unsubstituted alkoxy groups.
Two R ^{1 s} and two R ^{3 s} may be the same or different.

In the general formula (2), ring β represents a monocyclic or polycyclic ring. The ring β is preferably a monocyclic ring.
R ^{5 to} R ⁸ are each independently a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted oxycarbonyl group, or Represents a cyano group.
R ^{5 to} R ⁸ are each independently preferably a methyl group, an ethyl group, a chlorine atom, a bromine atom, a cyano group, a phenyl group or a hydrogen atom, and a methyl group, a chlorine atom, a cyano group, a phenyl group or A hydrogen atom is more preferable, and a phenyl group or a hydrogen atom is particularly preferable.
R ^{5 to} R ⁸ may further have a substituent, and such a substituent is not particularly limited. For example, a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted And aryl groups and substituted or unsubstituted alkoxy groups.
Two R ^{5 s} and two R ^{8 s} may be the same or different.

  The unit structure represented by the general formula (1) or the general formula (2) is represented by the following general formula (3) or general formula (4), or the following general formula (5) or general formula (6), respectively. It is preferable that it is a structure represented.

In the general formula (3), each R ⁹ independently represents a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted alkoxy group, or a hydroxyl group. . R ⁹ is preferably a hydrogen atom, a halogen atom or a hydroxyl group, more preferably a hydrogen atom or a halogen atom, and particularly preferably at least one R ⁹ is a halogen atom.
X ¹ and X ² each independently represents an oxygen atom or a sulfur atom. X ¹ and X ² are preferably oxygen atoms.

In the general formula (4), each R ¹⁰ independently represents a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted alkoxy group. R ¹⁰ is preferably a hydrogen atom or a halogen atom, particularly preferably at least one R ¹⁰ is a halogen atom, and more preferably at least one R ¹⁰ is a chlorine atom.
X ³ represents an oxygen atom, a sulfur atom, —CH ₂ —, or —NR—, and R represents a hydrogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group.
X ³ is preferably —CH ₂ —, an oxygen atom or a sulfur atom, and more preferably an oxygen atom or a sulfur atom.

In the general formula (5), each R ^9, X ¹ and X ^2, the general formula (3) has the same meaning as the R ^9, X ¹ and X ² in the preferred range is also the same.

In Formula (6), each of R ¹⁰ and X ³ has the same meaning as the R ¹⁰ and X ³ in the general formula (4), and preferred ranges are also the same.

(Monomer capable of forming a unit structure represented by general formula (1) or general formula (2))
The unit structure represented by the general formula (1) or (2) can be formed by cyclopolymerizing a monomer having a specific structure. In addition, there is no restriction | limiting in particular about the radical generator used for superposition | polymerization, A well-known thing can be used. Moreover, the example of the reaction route shown below is only an example, and another ring structure may be formed depending on the radical attack position.
Examples of reaction pathways for cyclopolymerizing a polymer having a structural unit represented by the general formula (1) are shown below.

  Moreover, the example of the reaction route which cyclopolymerizes the polymer which has a structural unit represented by typical general formula (2) below is shown.

  Examples of the monomer capable of forming the unit structure represented by the general formula (1) or the general formula (2) include monomers represented by the following general formula (7) or the general formula (8).

In the general formula (7), R ^{31 to} R ³⁴ are each independently a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted alkoxy group, substituted or unsubstituted. It represents a substituted oxycarbonyl group or a cyano group. The preferred range of R ^{31 to} R ^{34 is the same as} the preferred range of R ^{1 to} R ⁴ .
X ³¹ and X ³² each independently represent an oxygen atom or a sulfur atom, preferably an oxygen atom.
L ¹ represents a single bond or a divalent organic linking group, preferably an alkylene group, a carbonyl group or a single bond, more preferably a single bond. When L ¹ is an organic linking group, the chain length is preferably 1 to 4, more preferably 1 to 3, and particularly preferably 1 to 2.
Two R ^{31 s} and two R ^{33 s} may be the same or different.

In the general formula (8), R ^{35 to} R ³⁸ are each independently a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted alkoxy group, substituted or unsubstituted. It represents a substituted oxycarbonyl group or a cyano group. The preferred range of R ^{35 to} R ^{38 is the same as} the preferred range of R ^{5 to} R ⁸ .
X ³³ represents an oxygen atom, a sulfur atom, —CH ₂ —, or —NR—, and R represents a hydrogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group. X ³³ is
It is preferably —CH ₂ —, an oxygen atom or a sulfur atom, and more preferably an oxygen atom or a sulfur atom.
L ² and L ³ each independently represents a single bond or a divalent organic linking group, an alkylene group,
A carbonyl group or a single bond is preferable, and a single bond is more preferable. When L ¹ is an organic linking group, the chain length is preferably 1 to 4, more preferably 1 to 2, and particularly preferably 1.
Two R ^{35 s} and two R ^{38 s} may be the same or different.

  The monomer represented by the general formula (7) or the general formula (8) is preferably a monomer represented by the following general formula (9) or the general formula (10).

In the general formula (9), each R ³⁹ represents a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted alkoxy group, or a hydroxyl group. Same as R ⁹ .
X ³¹ and X ³² have the same meanings as X ³¹ and X ³² in the general formula (7), and preferred ranges are also the same.

In the general formula (10), each R ⁴⁰ independently represents a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted alkoxy group, and a preferred range is Same as R ¹⁰ .
X ³³ has the same meaning as X ³³ in formula (8), and the preferred range is also the same.

Hereinafter, specific examples of the monomer capable of forming the unit structure represented by the general formula (1) or the general formula (2), that is, the monomer represented by the general formula (7) or (8) will be described below. Listed as A-1 to A-16. The monomers that can be employed in the present invention are not limited to these specific examples.
First, specific examples of the monomers A-1 to A-7 represented by the general formula (7) are shown below. A unit structure represented by the general formula (1) or the general formula (2) is obtained by cyclopolymerizing these monomers.

  Specific examples of the monomer represented by the general formula (8) are shown below. A unit structure represented by the general formula (1) or the general formula (2) is obtained by cyclopolymerizing these monomers.

  The monomer capable of forming the unit structure represented by the general formula (1) or the general formula (2) can be synthesized by a known method or can be obtained commercially. is there.

  As the kind of the main chain of the thermoplastic resin containing the unit structure represented by the general formula (1) or the general formula (2), a vinyl polymer obtained by polymerization of a vinyl monomer, a polyether, a ring-opening metathesis polymer, and a condensation A polymer (polycarbonate, polyester, polyamide, polyetherketone, polyethersulfone, etc.) can be selected from any conventionally known polymers, but vinyl polymers, ring-opening metathesis polymerization polymers, polycarbonates, and polyesters are preferred and are suitable for production. From the viewpoint, a vinyl polymer is more preferable.

  Further, the thermoplastic resin used in the present invention may be a homopolymer having a unit structure represented by the general formula (1) or the general formula (2), or a copolymer with other copolymer components. May be. Further, when it is a copolymer, it may be a block copolymer or a random copolymer, but it may be a random copolymer with a copolymer component having a carboxyl group in the side chain. preferable.

  When the thermoplastic resin used in the present invention is synthesized by copolymerization, a monomer capable of forming a unit structure represented by the general formula (1) or the general formula (2) is added to the monomer composition in an amount of 3 to 3. It is preferable to use 70% by mass, more preferably 5 to 60% by mass, and even more preferably 10 to 50% by mass. When a monomer that can form a unit structure represented by general formula (1) or general formula (2) contains 70% by mass or less in the monomer composition, there is a tendency that thermoforming tends to be easy, preferable. As the monomer capable of forming the unit structure represented by the general formula (1) or the general formula (2), only one type may be used, or two or more types may be used in combination.

<Copolymerizable monomer>
The thermoplastic resin used in the present invention is preferably copolymerized with another monomer together with the monomer capable of forming the unit structure represented by the general formula (1) or the general formula (2). As such other monomers, those described in Polymer Handbook 2nd ed., J. Brandrup, Wiley lnterscience (1975) Chapter 2 Page 1 to 483 can be used.

  Specifically, for example, styrene derivatives, 1-vinylnaphthalene, 2-vinylnaphthalene, vinylcarbazole, acrylic acid, methacrylic acid, acrylic esters, methacrylic esters, acrylamides, methacrylamides, allyl compounds, vinyl ethers , Vinyl esters, dialkyl itaconates, dialkyl esters of the above fumaric acid, monoalkyl esters, and the like.

  Examples of the styrene derivative include styrene, 2,4,6-tribromostyrene, 2-phenylstyrene, 4-chlorostyrene and the like.

  Examples of the acrylic esters include methyl acrylate, ethyl acrylate, propyl acrylate, n-butyl acrylate, tert-butyl acrylate, chloroethyl acrylate, 2-hydroxyethyl acrylate, trimethylolpropane monoacrylate, and benzyl acrylate. , Benzyl methacrylate, methoxybenzyl acrylate, furfuryl acrylate, tetrahydrofurfuryl acrylate, and the like.

  Examples of the methacrylic acid esters include methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, tert-butyl methacrylate, chloroethyl methacrylate, 2-hydroxyethyl methacrylate, trimethylolpropane monomethacrylate, benzyl methacrylate, and methoxy. Examples include benzyl methacrylate, furfuryl methacrylate, and tetrahydrofurfuryl methacrylate.

  Examples of the acrylamides include acrylamide, N-alkylacrylamide (alkyl group having 1 to 3 carbon atoms, such as methyl group, ethyl group, propyl group), N, N-dialkylacrylamide (alkyl group having 1 carbon atom). ~ 6), N-hydroxyethyl-N-methylacrylamide, N-2-acetamidoethyl-N-acetylacrylamide and the like.

  Examples of the methacrylamides include methacrylamide, N-alkyl methacrylamide (alkyl groups having 1 to 3 carbon atoms, such as methyl, ethyl, propyl), N, N-dialkyl methacrylamide (as alkyl groups). Are those having 1 to 6 carbon atoms), N-hydroxyethyl-N-methylmethacrylamide, N-2-acetamidoethyl-N-acetylmethacrylamide and the like.

  Examples of the allyl compound include allyl esters (eg, allyl acetate, allyl caproate, allyl caprylate, allyl laurate, allyl palmitate, allyl stearate, allyl benzoate, allyl acetoacetate, allyl lactate), allyloxyethanol Etc.

  Examples of the vinyl ethers include alkyl vinyl ethers (alkyl groups having 1 to 10 carbon atoms, such as hexyl vinyl ether, octyl vinyl ether, decyl vinyl ether, ethylhexyl vinyl ether, methoxyethyl vinyl ether, ethoxyethyl vinyl ether, chloroethyl vinyl ether, 1-methyl Examples include -2,2-dimethylpropyl vinyl ether, 2-ethylbutyl vinyl ether, hydroxyethyl vinyl ether, diethylene glycol vinyl ether, dimethylaminoethyl vinyl ether, diethylaminoethyl vinyl ether, butylaminoethyl vinyl ether, benzyl vinyl ether, and tetrahydrofurfuryl vinyl ether.

  Examples of the vinyl esters include vinyl butyrate, vinyl isobutyrate, vinyl trimethyl acetate, vinyl diethyl acetate, vinyl valate, vinyl caproate, vinyl chloroacetate, vinyl dichloroacetate, vinyl methoxyacetate, vinyl butoxyacetate, vinyl lactate Vinyl-β-phenylbutyrate, vinylcyclohexylcarboxylate, and the like.

  Examples of the dialkyl itaconates include dimethyl itaconate, diethyl itaconate, and dibutyl itaconate. Examples of the dialkyl esters or monoalkyl esters of the fumaric acid include dibutyl fumarate.

  Other examples include crotonic acid and itaconic acid.

  Examples of the monomer that can be copolymerized with the monomer that can form the unit structure represented by the general formula (1) or the general formula (2) include the following, but may be employed in the present invention. Monomers that can be produced are not limited to these specific examples. In the following, n represents an integer of 1 or more.

(Unit structure having no ring structure in the main chain and aromatic ring structure in the side chain)
Among the monomers that can be copolymerized with the monomer that can form the unit structure represented by the general formula (1) or the general formula (2), the main chain has no ring structure when polymerized. It is preferable to use a monomer having an aromatic ring structure in the chain. That is, in the present invention, when polymerized with the monomer represented by the general formula (7) or (8), a structure having an aromatic ring structure in the side chain and no ring structure in the main chain is formed. It is preferable to use a thermoplastic resin which is a copolymer with a monomer that can be obtained. The monomer having no ring structure in the main chain and having an aromatic ring structure in the side chain when polymerized is more preferably styrene or a styrene derivative.

The thermoplastic resin used in the present invention preferably has at least one unit structure having no ring structure in the main chain and having an aromatic ring structure in the side chain, and is a unit composed of styrene or a styrene derivative. It is particularly preferred to have at least one structure.
The thermoplastic resin used in the present invention preferably contains 1 to 97% by mass, more preferably 5 to 95% by mass of a unit structure having no ring structure in the main chain and having an aromatic ring structure in the side chain. The content is preferably 10 to 90% by mass.

(Monomer having a functional group capable of forming a chemical bond with inorganic fine particles)
In the present invention, it is preferable to use a monomer having a functional group capable of forming a chemical bond with inorganic fine particles as a monomer that can be copolymerized. Examples of the functional group capable of forming a chemical bond with the inorganic fine particles include a functional group having the following structure.

［Ｒ¹¹、Ｒ¹²、Ｒ¹³、Ｒ¹⁴、Ｒ¹⁵、Ｒ¹⁶は、それぞれ独立に水素原子、置換または無置換のアルキル基、置換または無置換のアルケニル基、置換または無置換のアルキニル基、置換または無置換のアリール基、あるいは、塩を形成しうる原子または基を表す。］、−ＳＯ₃Ｈまたはその塩、−ＯＳＯ₃Ｈまたはその塩、−ＣＯ₂Ｈまたはその塩、−ＯＨまたはその塩、−Ｓｉ（ＯＲ¹⁷）_nＲ¹⁸ _n［Ｒ¹⁷、Ｒ¹⁸はそれぞれ独立に水素原子、置換または無置換のアルキル基、置換または無置換のアルケニル基、置換または無置換のアルキニル基、置換または無置換のアリール基、あるいは、塩を形成しうる原子または基を表し、ｎは１〜３の整数を表す。］

[R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ and R ¹⁶ are each independently a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkynyl group, A substituted or unsubstituted aryl group, or an atom or group capable of forming a salt. ], - SO ₃ H or salts thereof, -OSO ₃ H or a salt thereof, -CO ₂ H or a salt thereof, -OH or a salt _{^{thereof, -Si (OR 17) n R}} 18 n [R 17, R 18 are each Independently represents a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkynyl group, a substituted or unsubstituted aryl group, or an atom or group capable of forming a salt; n represents an integer of 1 to 3. ]

The preferred ranges of R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ are the following ranges.
The alkyl group preferably has 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, and examples thereof include a methyl group, an ethyl group, and an n-propyl group. Substituted alkyl groups include, for example, aralkyl groups. The aralkyl group preferably has 7 to 30 carbon atoms, more preferably 7 to 20 carbon atoms, and examples thereof include a benzyl group and a p-methoxybenzyl group. The alkenyl group preferably has 2 to 30 carbon atoms, more preferably 2 to 20 carbon atoms, and examples thereof include a vinyl group and a 2-phenylethenyl group. The alkynyl group preferably has 2 to 20 carbon atoms, more preferably 2 to 10 carbon atoms, and examples thereof include an ethynyl group and a 2-phenylethynyl group. The aryl group preferably has 6 to 30 carbon atoms, more preferably 6 to 20 carbon atoms, and examples thereof include a phenyl group, a 2,4,6-tribromophenyl group, and a 1-naphthyl group. The aryl group herein includes a heteroaryl group. As substituents for alkyl groups, alkenyl groups, alkynyl groups, and aryl groups, in addition to these alkyl groups, alkenyl groups, alkynyl groups, and aryl groups, halogen atoms (eg, fluorine atoms, chlorine atoms, bromine atoms, iodine atoms) And alkoxy groups (for example, methoxy group, ethoxy group). R ¹¹ , R ¹² , R ¹³ , and R ¹⁴ are particularly preferably a hydrogen atom or an alkyl group, and more preferably a hydrogen atom.
Preferable ranges of R ¹⁷ and R ¹⁸ are the same as those of R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ and R ¹⁶ . n is preferably 3.

、−ＳＯ₃Ｈまたはその塩、−ＣＯ₂Ｈまたはその塩、−Ｓｉ（ＯＲ¹⁵）_m1Ｒ¹⁶ _3-m1であり、より好ましくは、

または−ＣＯ₂Ｈまたはその塩である。 Among these functional groups, preferably

, -SO ₃ H or a salt thereof, -CO ₂ H or a salt thereof, -Si a ^{_{(OR 15) m1 R 16 3}} -m1, more preferably,

Or —CO ₂ H or a salt thereof.

  In order to introduce a functional group capable of forming a chemical bond with inorganic particles into a thermoplastic resin, a method of performing a polymerization reaction using a polymerizable monomer having the functional group or a precursor thereof, or reacting the resin with a reactant And a method of introducing the functional group or a precursor thereof. In view of easy control of the amount of functional group introduced, it is preferable to employ a method of obtaining a resin by performing a polymerization reaction using a polymerization monomer having the functional group or a precursor thereof.

  When a resin is obtained by a polymerization reaction, a monomer capable of undergoing a polymerization reaction with other monomers used in the present invention, such as a diol compound, a dithiol compound, or a dicarboxylic acid compound, is employed as a monomer having a functional group capable of forming a chemical bond with inorganic particles. be able to.

  The thermoplastic resin used in the present invention preferably contains 0.1 to 5% by mass, more preferably 0.3 to 3% by mass of a structural unit derived from the vinyl monomer having the functional group. It is more preferable to contain -2.5 mass%. In the thermoplastic resin used in the present invention, the average number of functional groups is preferably 0.1 to 20, more preferably 0.5 to 10, more preferably 1 to 5 per polymer chain. It is particularly preferred that

  Examples of the monomer having a functional group capable of forming a chemical bond with inorganic fine particles that can be copolymerized with the monomer that can form the unit structure represented by the general formula (1) or (2) include the following: Specific examples can be given, but the present invention is not limited to these specific examples.

(Properties of thermoplastic resin)
The number average molecular weight of the thermoplastic resin used in the present invention is preferably 10,000 to 200,000, more preferably 20,000 to 200,000, and even more preferably 50,000 to 200,000. When the number average molecular weight of the thermoplastic resin (1) is 200000 or less, the moldability tends to be improved, and when it is 10000 or more, the mechanical strength tends to be improved.

Here, the above-mentioned number average molecular weight can be measured by the following method.
It can be determined by GPC measurement using polystyrene as a solvent using GPC (HLC-8220 GPC manufactured by Tosoh Corporation) in comparison with a molecular weight standard product of polystyrene.

  In the thermoplastic resin used in the present invention, the average number of the functional groups bonded to the inorganic fine particles is preferably 0.1 to 20 per polymer chain, more preferably 0.5 to 10; It is particularly preferable that the number is 1 to 5. If the content of the functional group is 20 or less on average per polymer chain, the thermoplastic resin tends to prevent the increase in viscosity and gelation in the solution state due to coordination with a plurality of inorganic fine particles. is there. Moreover, if the number of average functional groups per polymer chain is 0.1 or more, the inorganic fine particles tend to be dispersed stably.

  The glass transition temperature (Tg) of the thermoplastic resin used in the present invention is preferably 100 to 400 ° C, more preferably 110 to 380 ° C, and more preferably 120 to 300, from the viewpoints of heat resistance and moldability. It is particularly preferable that the temperature is C. If a resin having a glass transition temperature of 100 ° C. or higher is used, an optical component having sufficient heat resistance can be easily obtained, and if a resin having a glass transition temperature of 400 ° C. or lower is used, molding tends to be easily performed.

When the difference between the refractive index of the thermoplastic resin and the refractive index of the inorganic fine particles is large, Rayleigh scattering is likely to occur, so that the amount of fine particles that can be combined while maintaining transparency is reduced. In general, when the thermoplastic resin has a refractive index of about 1.48, a transparent molded article having a refractive index of 1.60 can be provided.
The refractive index of the thermoplastic resin used in the present invention is not particularly limited. However, when the organic-inorganic composite material of the present invention is used in an optical component that requires a high refractive index, the thermoplastic resin has a high refractive index characteristic. It is preferable to have In the present invention, from the viewpoint of providing a transparent molded article having a refractive index of 1.63 or more, the refractive index of the thermoplastic resin used in the present invention is preferably 1.55 or more, and preferably 1.58 or more. Is more preferable. These refractive indexes are values at 22 ° C. and a wavelength of 589 nm.

  The thermoplastic resin used in the present invention preferably has a light transmittance in terms of 1 mm thickness at a wavelength of 589 nm of 70% or more, more preferably 80% or more, and even more preferably 85% or more, It is especially preferable that it is 88% or more.

(Specific example of thermoplastic resin)
The following table lists preferred specific examples of thermoplastic resins that can be used in the present invention. A thermoplastic resin can be produced by mixing and copolymerizing the types of monomers described in the table at a mass ratio described in the table. However, the thermoplastic resin that can be used in the present invention is not limited to these.

  These thermoplastic resins may be used alone or in combination of two or more.

[Additive]
In the present invention, in addition to the thermoplastic resin and the inorganic fine particles, various additives may be appropriately blended from the viewpoint of uniform dispersibility, flowability during molding, mold release, weather resistance, and the like. For example, a surface treatment agent, a plasticizer, an antistatic agent, a dispersant, a release agent, and the like can be given. In addition to the thermoplastic resin, a resin having no functional group may be added, and there is no particular limitation on the type of such a resin. However, the optical properties, thermophysical properties, and molecular weights of the thermoplastic resin are the same. What has is preferable.
Although the blending ratio of these additives varies depending on the purpose, it is preferably 0 to 50% by mass and preferably 0 to 30% by mass with respect to the total amount of the inorganic fine particles and the thermoplastic resin. More preferably, it is particularly preferably 0 to 20% by mass.

(Plasticizer)
When the glass transition temperature of the thermoplastic resin is high, molding may not always be easy. For this reason, a plasticizer may be used to lower the molding temperature. As a plasticizer used by this invention, what has a structure represented by General formula (11) is preferable.

（式中、Ｂ¹ およびＢ² は炭素数６〜１８のアルキル基またはアリールアルキル基、ｍは０または１、Ｘは

(Wherein B ¹ and B ² are alkyl or arylalkyl groups having 6 to 18 carbon atoms, m is 0 or 1, and X is

のうちのいずれかであり、Ｒ²¹およびＲ²²は水素原子または炭素数４以下のアルキル基を示す。）

R ²¹ and R ^{22 each} represent a hydrogen atom or an alkyl group having 4 or less carbon atoms. )

In the compound represented by the general formula (11), B ¹ and B ² may be any alkyl group or arylalkyl group within the range of 6 to 18 carbon atoms. If the number of carbon atoms is less than 6, the molecular weight may be too low to boil at the melting temperature of the polymer and generate bubbles. On the other hand, when the number of carbon atoms exceeds 18, the compatibility with the polymer is deteriorated, so that the effect of addition is insufficient.
Specific examples of the groups B ¹ and B ² include n-hexyl group, n-octyl group, n-decyl group, n-dodecyl group, n-tetradecyl group, n-hexadecyl group, n-octadecyl group and the like. Straight alkyl groups, branched alkyl groups such as 2-hexyldecyl group and methyl-branched octadecyl group, and arylalkyl groups such as benzyl group and 2-phenylethyl group. Specific examples of the compound represented by the general formula (11) used in the present invention include the following compounds, among which W-1 (trade name [KP-L155] manufactured by Kao Corporation) is preferable.

[Inorganic fine particles]
There are no particular limitations on the inorganic fine particles used in the organic-inorganic composite material of the present invention. For example, the fine particles described in JP-A Nos. 2002-241612, 2005-298717, 2006-70069, etc. are used. be able to.

  Specifically, fine oxide particles (aluminum oxide, titanium oxide, niobium oxide, zirconium oxide, magnesium oxide, tellurium oxide, yttrium oxide, indium oxide, tantalum oxide, hafnium oxide, bismuth oxide, tin oxide, etc.), double oxide Fine particles (such as lithium niobate, potassium niobate, lithium tantalate, potassium tantalate, barium titanate, strontium titanate, lead titanate, barium zirconate, barium stannate, zircon) IIb-VIb group semiconductors (Zn, Cd chalcogen (S, Se, Te) or oxide) can be used. Of these, compounds of zirconium, zinc, tin or titanium are preferable, and specifically, it is preferable to use at least one selected from the group consisting of zirconium oxide, zinc oxide, tin oxide and titanium oxide.

  Two or more kinds of inorganic fine particles may be used in combination.

The inorganic fine particles used in the present invention may be a composite of a plurality of components from the viewpoints of refractive index, transparency, stability, and the like. Also, inorganic fine particles can be doped with different elements for various purposes such as photocatalytic activity reduction and water absorption reduction, the surface layer is coated with different metal oxides such as silica and alumina, silane coupling agents, titanate couplings. The surface may be modified with an agent, an aluminate coupling agent, an organic acid (carboxylic acid, sulfonic acid, phosphoric acid, phosphonic acid, etc.) or a dispersant having an organic acid group. Furthermore, these two or more types may be used in combination depending on the purpose.
Particularly preferred fine particles in the present invention are fine particles obtained by coating tin-containing rutile titanium oxide with zirconium oxide.

  The refractive index of the inorganic fine particles used in the present invention is not particularly limited. However, when the organic-inorganic composite material of the present invention is used in an optical component that requires a high refractive index, the inorganic fine particles have a high refractive index characteristic. It is preferable. In this case, the refractive index of the inorganic fine particles used is preferably 1.90 to 3.00 at 22 ° C. and a wavelength of 589 nm, more preferably 2.00 to 2.70, and particularly preferably 2.10. ~ 2.50. If the refractive index of the fine particles is 3.0 or less, the difference in refractive index from the resin is relatively small, so that Rayleigh scattering tends to be easily suppressed. If the refractive index is 1.9 or more, the effect of increasing the refractive index tends to be easily obtained.

  The refractive index of the inorganic fine particles is obtained by, for example, molding a composite compounded with the thermoplastic resin used in the present invention into a transparent film, and measuring the refractive index with an Abbe refractometer (for example, “DM-M4” manufactured by Atago Co., Ltd.). It can be estimated by a method of calculating from the refractive index of only the resin component separately measured or a method of calculating the refractive index of the fine particles by measuring the refractive index of the fine particle dispersion having different concentrations. Further, a refractive index can also be obtained by preparing a thin film on a substrate such as a silicon wafer or the like by spin coating, for example, and drying it sufficiently, and then fitting an interference pattern with an ellipsometer.

  If the number average primary particle size of the inorganic fine particles used in the present invention is too small, the characteristics unique to the substance constituting the fine particles may change. Conversely, if the number average primary particle size is too large, Rayleigh scattering is used. May become noticeable, and the transparency of the organic-inorganic composite material may be extremely reduced. Therefore, the lower limit value of the number average primary particle size of the inorganic fine particles used in the present invention is preferably 1 nm or more, more preferably 2 nm or more, further preferably 3 nm or more, and the upper limit value is preferably 15 nm or less, more preferably. Is 10 nm or less, more preferably 7 nm or less. That is, the number average primary particle size of the inorganic fine particles in the present invention is preferably 1 nm to 15 nm, more preferably 2 nm to 10 nm, and particularly preferably 3 nm to 7 nm.

The inorganic fine particles used in the present invention desirably satisfy the above average particle size and have a narrow particle size distribution. There are various ways of defining such monodisperse particles. For example, the numerical value ranges described in JP-A-2006-160992 also apply to the preferable particle size distribution range of the fine particles used in the present invention. .
Here, the above-mentioned number average primary particle size can be measured by, for example, an X-ray diffraction (XRD) apparatus or a transmission electron microscope (TEM).

The method for producing inorganic fine particles used in the present invention is not particularly limited, and any known method can be used.
For example, desired oxide fine particles can be obtained by using a metal salt or an alkoxy metal as a raw material and hydrolyzing in a reaction system containing water. Details of this method are described in, for example, Japanese Journal of Applied Physics, 37, 4603-4608 (1998), or Langmuir, 16: 1, 241-246 (2000). ing.
When applying inorganic fine particles synthesized in a reaction system containing these moisture, the moisture may have an adverse effect. In such a case, it can be replaced with another appropriate organic solvent after the synthesis of the inorganic fine particles. Uniform dispersion is possible without impairing dispersibility by using an appropriate dispersant as required.

Further, as a method other than the method of hydrolyzing in water, a method of preparing inorganic fine particles in an organic solvent or an organic solvent in which the thermoplastic resin in the present invention is dissolved may be employed. In this case, various surface treatment agents (silane coupling agents, aluminate coupling agents, titanate coupling agents, organic acids (carboxylic acids, sulfones, phosphonic acids, etc.)) may be allowed to coexist as necessary. Good.
Examples of the solvent used in these methods include acetone, 2-butanone, dichloromethane, chloroform, toluene, ethyl acetate, cyclohexanone, anisole and the like. These may be used alone or as a mixture of two or more.
When preparing inorganic particles in a solution, it is important to obtain appropriate conditions that vary depending on the temperature at the time of synthesis, such as the properties of the inorganic particles, the particle size, and the aggregation state. However, it is impossible to synthesize at a temperature higher than the boiling point of the solution under normal pressure. When synthesis at a higher temperature is required, the necessary characteristics can be obtained by synthesis under high pressure using a high-pressure kettle such as an autoclave.

As a method for synthesizing the inorganic fine particles, in addition to the case of performing only in the liquid phase as described above, a firing step may be used for further high-temperature treatment. Such a firing method is performed to increase the crystallinity after forming fine particles in the liquid phase, when the raw materials are directly reacted and synthesized in the baking step, or after the precursor of the fine particles is formed in the liquid phase. In some cases, desired fine particles are synthesized in the firing step. As an example of the firing method, Japanese Patent Application Laid-Open No. 2003-19427 discloses a method in which a solution in which an inorganic fine particle raw material component and other inorganic compounds are dissolved is spray pyrolyzed to synthesize particles, and then washed with water to remove the inorganic fine particles. A method of obtaining only highly crystalline particles by removing the inorganic compound is disclosed.
Alternatively, Japanese Patent Application Laid-Open No. 2006-16236 discloses a method in which a particle precursor is formed in a liquid phase and then crystallized by firing while preventing aggregation of particles with an inorganic salt.
Furthermore, various general fine particle synthesis methods described in, for example, Japanese Patent Application Laid-Open No. 2006-70069 and the like, such as a method of producing by a vapor phase method using a vacuum process such as a molecular beam epitaxy method or a CVD method can be mentioned. it can.
The crystallinity of the inorganic fine particles varies depending on the conditions for synthesis, but inorganic particles having any crystallinity can be used depending on the situation. It may be crystalline having a clear peak when measured with an XRD apparatus or amorphous having a broad halo. In general, inorganic fine particles having a high degree of crystallinity have a higher refractive index than those having a low degree of crystallinity, which is advantageous for application to high refractive materials. However, in the case of a material having a high photocatalytic activity such as titanium oxide, it is known that the photocatalytic activity can be suppressed by lowering the crystallinity. The photocatalytic activity of the inorganic fine particles may cause a serious problem of resin degradation when the organic-inorganic composite material is irradiated with light. In such a case, it is also possible to suppress the photocatalytic activity using inorganic nanoparticles having a low crystallinity.
When the inorganic fine particles have a core-shell structure, the crystallinity of the core portion and the shell portion may be the same or completely different. These combinations may be physically determined by the crystal structure of the core portion and the shell portion, the lattice constant, and the like, but may be intentionally created depending on the synthesis conditions. A combination of core and shell that takes advantage of each characteristic is required.

  The content of the inorganic fine particles in the organic-inorganic composite material of the present invention is preferably 20 to 95% by mass, more preferably 25 to 70% by mass, particularly 30 to 60% by mass from the viewpoint of transparency and high refractive index. preferable.

[Method for producing organic-inorganic composite material]
The organic-inorganic composite material of the present invention can be produced by mixing components such as a thermoplastic resin and inorganic fine particles.
Since the inorganic fine particles used in the present invention have a relatively small particle size and high surface energy, it is difficult to re-disperse when isolated as a solid. Therefore, the inorganic fine particles are preferably mixed with the thermoplastic resin in a state of being dispersed in a solution to form a stable dispersion. As a preferable production method of the composite composition, (1) inorganic particles are surface-treated in the presence of the surface treatment agent, the surface-treated inorganic fine particles are extracted in an organic solvent, and the extracted inorganic fine particles are A method of producing a composite composition of inorganic fine particles and a thermoplastic resin by uniformly mixing with a thermoplastic resin, (2) Mixing both uniformly using a solvent capable of uniformly dispersing or dissolving both the inorganic fine particles and the thermoplastic resin. And a method for producing a composite composition of inorganic fine particles and a thermoplastic resin.

When a composite composition of inorganic fine particles and a thermoplastic resin is produced by the method of (1) above, water-insoluble water such as toluene, ethyl acetate, methyl isobutyl ketone, chloroform, dichloroethane, dichloroethane, chlorobenzene, methoxybenzene, etc. is used as the organic solvent. Sex solvents are used. The surface treatment agent used for extraction of the fine particles into the organic solvent and the thermoplastic resin may be the same or different, but the surface treatment agent preferably used is described above Those described in the section of> are mentioned.
When mixing the inorganic fine particles extracted into the organic solvent and the thermoplastic resin, additives such as a plasticizer, a release agent, or another type of polymer may be added as necessary.

  In the case of the above (2), the solvent is hydrophilic such as dimethylacetamide, dimethylformamide, dimethylsulfoxide, benzyl alcohol, cyclohexanol, ethylene glycol monomethyl ether, 1-methoxy-2-propanol, t-butanol, acetic acid, propionic acid, etc. Preferably, a polar solvent alone or mixed solvent, or a mixed solvent of chloroform, dichloroethane, dichloromethane, ethyl acetate, methyl ethyl ketone, methyl isobutyl ketone, toluene, chlorobenzene, methoxybenzene or the like and a polar solvent mentioned above is preferably used. . At this time, a dispersing agent, a plasticizer, a release agent, or another type of polymer may be added as necessary in addition to the above-described thermoplastic resin. When using fine particles dispersed in water / methanol, add a hydrophilic solvent that has a higher boiling point than water / methanol and dissolve the thermoplastic resin, and then concentrate the water / methanol to disperse the fine particles. After replacing the liquid with a polar organic solvent, it is preferable to mix with the resin. At this time, the surface treatment agent may be added.

The solution of the organic-inorganic composite material obtained by the above methods (1) and (2) can be cast as it is to obtain a transparent molded body. In the present invention, the solution is particularly concentrated, freeze-dried, Alternatively, after removing the solvent by a method such as reprecipitation from a suitable poor solvent, the powdered solid is preferably molded by a known method such as injection molding or compression molding. At this time, the powdered organic-inorganic composite material of the present invention can be processed into a molded article such as a lens by directly heating, melting, or compressing, but once a certain weight and shape are obtained by a method such as an extrusion method. After producing the preform (precursor) having the same, the preform can be deformed by compression molding to produce an optical component such as a lens.
In the present invention, when an inorganic fine particle and a thermoplastic resin solution are mixed to prepare a solution of an organic-inorganic composite material, the preform can be obtained by casting in a solution state. Further, after removing the solvent from the solution by a method such as concentration, lyophilization, or reprecipitation from an appropriate poor solvent, the powdered solid content is injection molded, compression molded, extruded, etc. It is also possible to form a preform having a constant weight and shape by a known method.
When the molded body is an optical component such as a lens, an appropriate curvature can be imparted to the preform in order to efficiently create a desired shape. You may heat at the time of processing of a preform.

  The organic-inorganic composite material may be used as a master batch by mixing with other resins.

In the method for producing an organic-inorganic composite material of the present invention, a step of obtaining a thermoplastic resin by cyclopolymerizing at least one of the monomers represented by the general formula (7) or the general formula (8), and the thermoplastic resin And a step of dispersing inorganic fine particles.
Preferably, the monomer represented by the general formula (7) or the general formula (8) is co-polymerized with the monomer having no ring structure in the main chain and having an aromatic ring structure in the side chain when polymerized. A step of combining to obtain a thermoplastic resin.
Furthermore, it is more preferable that the monomer represented by the general formula (7) or the general formula (8) is a monomer represented by the general formula (9) or the general formula (10).

[Organic inorganic composite materials]
The glass transition temperature (Tg) of the organic-inorganic composite material of the present invention is preferably 85 ° C. or higher, more preferably 90 to 400 ° C., and particularly preferably 95 to 300 ° C. If an organic-inorganic composite material having a glass transition temperature of 85 ° C. or higher is used, an optical component having sufficient heat resistance can be obtained.

  When the organic-inorganic composite material of the present invention is used for an optical component that requires a high refractive index, the thermoplastic resin preferably has a high refractive index characteristic. In the present invention, the organic-inorganic composite material preferably has a refractive index of 1.63 or more, more preferably 1.64 or more, and particularly preferably 1.65 or more. These refractive indexes are values at 22 ° C. and a wavelength of 589 nm.

  In the organic-inorganic composite material of the present invention, the light transmittance in terms of 1 mm thickness at a wavelength of 589 nm is preferably 70% or more, more preferably 80% or more, further preferably 85% or more, 88 % Or more is particularly preferable.

[Optical parts]
The optical component of the present invention can be manufactured by molding the organic-inorganic composite material of the present invention described above. As the optical component of the present invention, those showing the above-described refractive index and optical characteristics in the description of the organic-inorganic composite material are useful.
In addition, as the optical component of the present invention, a high refractive index optical component having a thickness of at most 0.1 mm is particularly useful. It is preferably applied to an optical component having a thickness of 0.1 to 5 mm, and particularly preferably applied to a transparent article having a thickness of 1 to 3 mm.
These thick molded bodies are usually difficult to remove in the solution casting method because the solvent is difficult to remove, but by using the organic-inorganic composite material of the present invention, molding is easy and complex shapes such as aspherical surfaces can be easily formed. Therefore, an optical component having good transparency can be obtained using the high refractive index characteristics of the fine particles.

  The optical component using the organic-inorganic composite material of the present invention is not particularly limited as long as it is an optical component using the excellent optical characteristics of the organic-inorganic composite material of the present invention. It can also be used for optical components that transmit light (so-called passive optical components). Functional devices including such optical components include various display devices (liquid crystal display, plasma display, etc.), various projector devices (OHP, liquid crystal projector, etc.), optical fiber communication devices (optical waveguide, optical amplifier, etc.), cameras, videos, etc. The imaging device is exemplified. Examples of the passive optical component in such an optical functional device include a lens, a prism, a prism sheet, a panel, a film, an optical waveguide, an optical disc, an LED sealing agent, and the like.

The optical component using the organic-inorganic composite material of the present invention is particularly suitable for a lens substrate. The lens substrate manufactured using the organic-inorganic composite material of the present invention has both light transmittance and light weight, and is excellent in optical properties. Further, the refractive index of the lens substrate can be arbitrarily adjusted by appropriately adjusting the type of monomer constituting the organic-inorganic composite material and the amount of inorganic fine particles to be dispersed.
The “lens substrate” in the present invention means a single member capable of exhibiting a lens function. A film or a member can be provided on the surface or the periphery of the lens substrate according to the use environment or application of the lens. For example, a protective film, an antireflection film, a hard coat film, or the like can be formed on the surface of the lens substrate. Further, the periphery of the lens base material can be fitted and fixed to a base material holding frame or the like. However, these films and frames are members added to the lens base material referred to in the present invention, and are distinguished from the lens base material itself referred to in the present invention.

  When the lens substrate in the present invention is used as a lens, the lens substrate itself of the present invention may be used alone as a lens, or may be used as a lens with a film or a frame added as described above. . The type and shape of the lens using the lens substrate of the present invention are not particularly limited. The lens substrate of the present invention is, for example, an eyeglass lens, an optical device lens, an optoelectronic lens, a laser lens, a pickup lens, an imaging lens (an in-vehicle camera lens, a portable camera lens, a digital camera lens, etc .; (Including various known imaging lenses such as zoom lenses and positive / negative power lenses), OHP lenses, microlens arrays, and the like).

  The features of the present invention will be described more specifically with reference to the following examples. The materials, amounts used, ratios, processing details, processing procedures, and the like shown in the following examples can be changed as appropriate without departing from the spirit of the present invention. Therefore, the scope of the present invention should not be construed as being limited by the specific examples shown below.

[Analysis and Evaluation Method]
(1) Observation with Transmission Electron Microscope (TEM) It was carried out with an H-9000UHR transmission electron microscope (acceleration voltage 200 kV, degree of vacuum at the time of observation of about 7.6 × 10 ⁻⁹ Pa) manufactured by Hitachi, Ltd. .

(2) Measurement of light transmittance A resin having a thickness of 1.0 mm was prepared by molding a resin to be measured, and light having a wavelength of 589 nm was measured with a UV-visible absorption spectrum measuring apparatus UV-3100 (manufactured by Shimadzu Corporation).

(3) Refractive index measurement Light having a wavelength of 589 nm was measured with an Abbe refractometer (DR-M4 manufactured by Atago Co., Ltd.).

(4) Heat resistance (glass transition temperature)
It measured with the differential scanning calorimeter DSC7200 (made by SII nanotechnology Co., Ltd.).

[Preparation of materials]
(1) Synthesis of titania fine particles While stirring a 0.1 mol / L titanyl sulfate aqueous solution, a 1.5 mol / L sodium carbonate aqueous solution having the same volume was added dropwise at room temperature over 10 minutes. The white ultrafine particle suspension thus obtained was centrifuged at 3500 rpm and purified by repeating the steps of removing the supernatant by decantation and washing with water. The white precipitate thus obtained was heated at 50 ° C. for about 1 hour with stirring and dispersing in 0.3 mol / L of dilute hydrochloric acid to obtain a transparent acidic hydrosol. This acidic hydrosol was ice-cooled, and an aqueous solution of sodium dodecylbenzenesulfonate was added to form a white precipitate, which was then extracted with toluene, dried and concentrated. From the XRD and TEM of this concentrated residue, it was confirmed that anatase-type titania fine particles (number average particle size was about 5 nm) were formed.

(2) Synthesis of zirconia fine particles A zirconium oxychloride solution having a concentration of 50 g / L was neutralized with a 48% aqueous sodium hydroxide solution to obtain a hydrated zirconium suspension. The suspension was filtered and then washed with ion exchanged water to obtain a hydrated zirconium cake. The cake was adjusted to a concentration of 15% by mass in terms of zirconia using ion-exchanged water as a solvent, placed in an autoclave, and hydrothermally treated at 150 ° C. and 150 ° C. for 24 hours to obtain a zirconia fine particle suspension. Formation of zirconia fine particles having a number average particle diameter of 5 nm was confirmed by TEM.

(3) Preparation of zirconia fine particle toluene dispersion The zirconia fine particle suspension synthesized in (2) above and a toluene solution in which p-propylbenzoic acid manufactured by Tokyo Kasei was dissolved were mixed and stirred at 50 ° C. for 8 hours. The toluene solution was extracted to prepare a zirconia fine particle toluene dispersion.
When other dispersants are used, they can be prepared by the same method.

(4) Synthesis of resin In a 500 ml three-necked flask equipped with a reflux condenser and a gas introduction cock, 80.0 g of vinyl cinnamate (A-1), 118.0 g of styrene (B-1), 2-carboxyethyl acrylate ( C-3) After adding 2.0 g of ethyl acetate and 22.2 g of ethyl acetate and substituting with nitrogen twice, 0.2 g of V-601 (trade name) manufactured by Wako Pure Chemical Industries, Ltd. was added as an initiator, and 2 After nitrogen substitution, the mixture was heated at 80 ° C. for 3 hours under a nitrogen stream. After returning to room temperature, 300 ml of ethyl acetate was added, stirred for 10 minutes, poured into 5 L of methanol, and reprecipitated. The precipitate was collected by filtration, washed with a large amount of methanol, and vacuum-dried at 80 ° C. for 3 hours to obtain P-3 (yield 18%, number average molecular weight 131,000, weight average molecular weight 259,000). .
Other exemplified polymers can be prepared in a similar manner.

(5) Preparation of organic-inorganic composite material Toluene dispersion of zirconia fine particles synthesized in (3) (zirconia: p-propylbenzoic acid = 10: 1) was used as resin P-3 and S-3103 manufactured by Matsumura Oil Research Co., Ltd. The product was added dropwise to a toluene solution in which (trade name) was dissolved over 5 minutes, stirred for 1 hour, and then the solvent was removed to obtain an organic-inorganic composite material as powder.
Other organic-inorganic composite materials were prepared in the same manner.

[Manufacture of optical components by thermoforming]
Each lens of Examples 1-14 and Comparative Examples 1-5 was manufactured by the following procedure. The types of inorganic fine particles used and the amounts used as inorganic components were as shown in Table 2. However, p-propylbenzoic acid is contained in an amount of 8.3% by mass and S-3103 is contained in an amount of 4.2% by mass, and the remainder is occupied by the resin. In Comparative Example 1, polymethyl methacrylate (manufactured by Aldrich, product number 44, 574-6) was used as the resin, and in Comparative Examples 2 to 4, Q-1 to Q- of the compositions described in Table 2 below were used as the thermoplastic resins, respectively. In Comparative Example 5, polystyrene (manufactured by Aldrich, product number 18, 242-7) was used.
Each manufactured organic-inorganic composite material was heat-molded at 180 ° C. to prepare a molded article for a lens having a thickness of 1 mm. The obtained molded body was cut and the cross section was observed with a TEM to confirm whether or not the inorganic fine particles were uniformly dispersed in the thermoplastic resin. Further, light transmittance measurement, refractive index measurement, and heat resistance (glass transition point) measurement were performed. These results are listed in Table 2 below. Thereafter, the lens molding was molded into a lens shape to obtain a lens as an optical component.

As is clear from Table 2, in Examples 1 to 14 of the present invention, the refractive index was larger than 1.63, the dispersibility and light transmittance of the inorganic fine particles were good, and an optical component having high heat resistance was obtained. . On the other hand, in Comparative Example 1 using polymethyl methacrylate, the inorganic fine particles cannot be uniformly dispersed because of low dispersibility, and the fine particles are aggregated, and the light transmittance is low. The refractive index could not be measured. In Comparative Examples 2 to 4 using the comparative thermoplastic resins Q-1 to Q-3, the heat resistance was insufficient. Further, in Comparative Example 5 using polystyrene as the resin, the inorganic fine particles cannot be uniformly dispersed due to low dispersibility, and the fine particles are aggregated, and the light transmittance is low. The refractive index could not be measured.
In Examples 8, 9 and 14, the monomers A-2, A-4 and A-13 having a structure in which a halogen atom is substituted with a side chain aromatic ring are used, and the heat resistance is further improved. I found out.

  In addition, as for the organic inorganic composite material of Examples 1-14, withstand voltage is all in the range of -1.0-7.0kV, and the volatile component at the time of hold | maintaining at 250 degreeC for 2 hours is 2 mass% or less. The saturated water absorption was 2% by mass or less. In addition, the organic-inorganic composite materials of Examples 1 to 14 were able to form the concave-convex lens shape accurately with good productivity and in accordance with the shape of the mold.

Claims (20)

An organic-inorganic composite material comprising a thermoplastic resin having at least one unit structure represented by the following general formula (1) or general formula (2) and inorganic fine particles.

[In general formula (1), ring α represents a monocyclic or polycyclic ring, and R ^{1 to} R ⁴ each independently represent a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted group. An aryl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted oxycarbonyl group, or a cyano group. ]

[In general formula (2), ring β represents a monocyclic or polycyclic ring, and R ^{5 to} R ⁸ each independently represents a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted group. An aryl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted oxycarbonyl group, or a cyano group. ]   The thermoplastic resin is a copolymer of the unit structure represented by the general formula (1) or the general formula (2) and a unit structure having no ring structure in the main chain and having an aromatic ring structure in the side chain. The organic-inorganic composite material according to claim 1, wherein The unit structure represented by the general formula (1) or the general formula (2) is represented by the following general formula (3) or the general formula (4), or the following general formula (5) or the general formula (6). The organic-inorganic composite material according to claim 1, wherein the organic-inorganic composite material has a unit structure.

[In General Formula (3), each R ⁹ independently represents a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted alkoxy group, or a hydroxyl group. , X ¹ and X ² each independently represents an oxygen atom or a sulfur atom. ]

[In General Formula (4), each R ¹⁰ independently represents a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted alkoxy group, and X ³ Represents an oxygen atom, a sulfur atom, —CH ₂ —, —NR—, and R represents a hydrogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group. ]

[In the general formula (5), each R ⁹ independently represents a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted alkoxy group, or a hydroxyl group. , X ¹ and X ² each independently represents an oxygen atom or a sulfur atom. ]

[In General Formula (6), each R ¹⁰ independently represents a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted alkoxy group, and X ³ Represents an oxygen atom, a sulfur atom, —CH ₂ —, —NR—, and R represents a hydrogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group. ] It includes a step of cyclopolymerizing at least one monomer represented by the following general formula (7) or general formula (8) to obtain a thermoplastic resin, and a step of dispersing inorganic fine particles in the thermoplastic resin. A method for producing an organic-inorganic composite material.

[In General Formula (7), R ^{31 to} R ³⁴ are each independently a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted alkoxy group, substituted or unsubstituted A substituted oxycarbonyl group or a cyano group is represented, X ³¹ and X ³² each independently represent an oxygen atom or a sulfur atom, and L ¹ represents a single bond or a divalent organic linking group. ]

[In General Formula (8), R ^{35 to} R ³⁸ are each independently a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted alkoxy group, substituted or unsubstituted A substituted oxycarbonyl group or a cyano group, X ³³ represents an oxygen atom, a sulfur atom, —CH ₂ — or —NR—, wherein R represents a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted group; A substituted aryl group is represented, and L ² and L ³ each independently represent a single bond or a divalent organic linking group. ]   The monomer represented by the general formula (7) or the general formula (8) is co-polymerized with the monomer capable of forming a structure having an aromatic ring structure in the side chain without having a ring structure in the main chain when polymerized. The method for producing an organic-inorganic composite material according to claim 4, further comprising a step of obtaining a thermoplastic resin by combining them. The monomer represented by the general formula (7) or the general formula (8) is a monomer represented by the following general formula (9) or the general formula (10). The manufacturing method of organic-inorganic composite material.

[In the general formula (9), each R ³⁹ represents a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted alkoxy group, a hydroxyl group, X ³¹ And X ³² each independently represents an oxygen atom or a sulfur atom. ]

[In the general formula (10), respectively each R ⁴⁰ is independently, represent a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted alkoxy group, X ³³ Represents an oxygen atom, a sulfur atom, —CH ₂ —, —NR—, and R represents a hydrogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group. ]   An organic-inorganic composite material produced by the method for producing an organic-inorganic composite material according to any one of claims 4 to 6.   The organic-inorganic composite material according to any one of claims 1 to 3, wherein the thermoplastic resin has a refractive index of 1.55 or more at a wavelength of 589 nm.   The number average molecular weight of the said thermoplastic resin is 10,000-200000, The organic-inorganic composite material as described in any one of Claims 1-3, 7 and 8 characterized by the above-mentioned.   The thermoplastic resin contains 3 to 70% by mass of the unit structure represented by the general formula (1) or the general formula (2), according to any one of claims 1 to 3 and 7 to 9. The organic-inorganic composite material described in 1. The organic-inorganic composite material according to any one of claims 1 to 3 and 7 to 10, wherein the thermoplastic resin has at least one functional group selected from the following group.

[R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ and R ¹⁶ are each independently a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkynyl group, Alternatively, it represents a substituted or unsubstituted aryl group. _{], - SO 3 H, -OSO} 3 H, -CO 2 H, -OH, -Si (OR 17) n R 18 n [R 17, R 18 each independently represent a hydrogen atom, a substituted or unsubstituted alkyl group Represents a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkynyl group, or a substituted or unsubstituted aryl group, and n represents an integer of 1 to 3. ]   The organic-inorganic composite material according to claim 11, wherein the thermoplastic resin has an average of 0.1 to 20 functional groups per polymer chain.   The organic-inorganic composite material according to any one of claims 1 to 3 and 7 to 12, wherein the number average particle diameter of the inorganic fine particles is 1 to 15 nm.   The organic-inorganic composite material according to any one of claims 1 to 3, and 7 to 13, wherein the inorganic fine particles have a refractive index of 1.90 to 3.00 at a wavelength of 589 nm.   The inorganic fine particle contains at least one selected from the group consisting of zirconium oxide, zinc oxide, tin oxide, and titanium oxide, according to any one of claims 1 to 3 and 7 to 14. Organic inorganic composite material.   The organic-inorganic composite material according to any one of claims 1 to 3 and 7 to 15, comprising 20 to 95% by mass of the inorganic fine particles.   The refractive index at a wavelength of 589 nm is 1.63 or more, and the light transmittance in terms of 1 mm thickness at a wavelength of 589 nm is 70% or more, and any one of claims 1 to 3 and 7 to 16 The organic-inorganic composite material according to Item.   Glass-transition temperature is 85 degreeC or more, The organic inorganic composite material as described in any one of Claims 1-3 and 7-17 characterized by the above-mentioned.   The optical component comprised including the organic inorganic composite material as described in any one of Claims 1-3 and 7-18.   The optical component according to claim 19, wherein the optical component is a lens.