JP2009029937A - Organic-inorganic composite composition and its molded article and optical part - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an optical part which has excellent transparency and a high refractive index and is excellent in temporal stability. <P>SOLUTION: This organic-inorganic composite composition is characterized by comprising a compound represented by general formula (1) and fine inorganic particles. In the formula, Ra, Rb and Rc are each a substituent; Q is an atom group or a single bond for forming a five to eight-membered ring; (l) and (m) are each an integer of 0 to 5; (n) is 0 or 1, provided that (n1+n3) and (n2+n3) do not each exceed 5. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to an organic-inorganic composite composition excellent in high refraction, transparency, lightness, and processability, and a lens substrate (for example, spectacle lens, optical device lens, optoelectronics) comprising the same. The present invention relates to an optical component such as a lens, a lens for laser, a lens for pickup, a lens for vehicle camera, a lens for portable camera, a lens for digital camera, a lens for OHP, a microlens array, and the like.

Resin has advantages such as lightness, impact resistance, moldability, and economy compared to glass, and in recent years, replacement of optical glass with resin is also progressing in optical components such as lenses. .
As resin molding methods, injection molding methods, extrusion molding methods, compression molding methods, etc., which are poured into a mold in a molten state and molded, are widely used. Yes. In recent years, in particular, development of a material in which inorganic nanoparticles are finely dispersed in a resin has been carried out for the purpose of higher functionality such as higher refractive index and higher heat resistance (see, for example, Patent Documents 1 and 2). Dispersing the nanoparticles in the resin may deteriorate the fluidity, which is a big problem in terms of imparting moldability.

Conventionally, as a means for improving the gold fluidity of a resin, a method using a plasticizer has been known, and phthalate ester plasticizer, phosphate ester plasticizer, adipic acid, citric acid and other polyvalent carboxylic acids such as Esters are widely used. The most common plasticizer is DOP (di-2-ethylhexyl phthalate) (see Patent Document 3), but because the D-line refractive index is as low as 1.486, the refractive index is 1.6 or higher. Application to a refractive index material is difficult because it reduces the refractive index of the material.
JP 61-291650 A JP 2003-73564 A JP-A-61-73754

A material composition that has both high refractive properties, transparency, and processability, and that can arbitrarily control the refractive index, and an optical component that includes the material composition have not yet been found, and the development thereof is desired. It was.
The present invention has been made in view of the above-mentioned circumstances, and an object thereof is an organic-inorganic composite in which fine particles are uniformly dispersed in a resin matrix, has excellent transparency and a high refractive index, and has excellent temporal stability. The object is to provide a composition and an optical component such as a lens substrate using the composition.

  As a result of intensive studies to achieve the above object, the present inventors have obtained an organic-inorganic composite composition using inorganic fine particles having a specific refractive index and a specific resin as raw materials due to the uniform dispersion effect of the fine particles, The present inventors have found that it has high refractive properties and excellent transparency, and have completed the present invention described below.

[1] An organic-inorganic composite composition comprising a compound represented by the following general formula (1) having a molecular weight of less than 2000 and inorganic fine particles.
General formula (1)

［一般式（１）中、Ｒａ、ＲｂおよびＲｃはそれぞれ独立に置換基を表す。Ｑは５〜８員環を形成する原子群または単結合を表す。ｎ１およびｎ２はそれぞれ独立に０〜５の整数を表す。ｎ３は０または１を表す。ただし、（ｎ１＋ｎ３）と（ｎ２＋ｎ３）は、それぞれ５を超えることはない。］
［２］ 前記無機微粒子が屈折率が１．９０〜３．００の金属酸化物微粒子であることを特徴とする［１］に記載の有機無機複合組成物。
［３］ 前記無機微粒子が酸化ジルコニウム、酸化亜鉛、または酸化チタンを含有する微粒子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組成物。
［４］ 前記無機微粒子の数平均粒子サイズが１〜１５ｎｍであることを特徴とする［１］〜［３］のいずれか一項に記載の有機無機複合組成物。
［５］ 前記無機微粒子を２０質量％以上含むことを特徴とする［１］〜［４］のいずれか一項に記載の有機無機複合組成物。
［６］ 前記一般式（１）で表される化合物の分子量が１０００未満であることを特徴とする［１］〜［５］のいずれか一項に記載の有機無機複合組成物。

[In General Formula (1), Ra, Rb and Rc each independently represent a substituent. Q represents an atomic group or a single bond forming a 5- to 8-membered ring. n1 and n2 each independently represents an integer of 0 to 5. n3 represents 0 or 1. However, (n1 + n3) and (n2 + n3) do not exceed 5. ]
[2] The organic-inorganic composite composition according to [1], wherein the inorganic fine particles are metal oxide fine particles having a refractive index of 1.90 to 3.00.
[3] The organic-inorganic composite composition according to [1] or [2], wherein the inorganic fine particles are fine particles containing zirconium oxide, zinc oxide, or titanium oxide.
[4] The organic-inorganic composite composition according to any one of [1] to [3], wherein the number average particle size of the inorganic fine particles is 1 to 15 nm.
[5] The organic-inorganic composite composition according to any one of [1] to [4], comprising 20% by mass or more of the inorganic fine particles.
[6] The organic-inorganic composite composition according to any one of [1] to [5], wherein the compound represented by the general formula (1) has a molecular weight of less than 1000.

[7] The thermoplastic resin according to any one of [1] to [6], including a thermoplastic resin having a functional group capable of forming an arbitrary chemical bond with the inorganic fine particles at a polymer terminal or a side chain. Organic-inorganic composite composition.
[8] The organic-inorganic composite composition according to [7], wherein the thermoplastic resin is a thermoplastic resin having a functional group selected from the following in the side chain.

［Ｒ¹¹、Ｒ¹²、Ｒ¹³、Ｒ¹⁴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、または−Ｓｉ（ＯＲ¹⁵）_m1Ｒ¹⁶ _3-m1［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し、ｍ１は１〜３の整数を表す。］
［９］ 前記官能基がポリマー鎖1本あたりに平均０．１〜２０個の範囲で含まれていることを特徴とする［８］に記載の有機無機複合組成物。
［１０］ 前記熱可塑性樹脂が一般式（２）で表されるモノマーを重合単位として含むコポリマーであることを特徴とする［８］または［９］に記載の有機無機複合組成物。

[R ¹¹ , R ¹² , R ¹³ and R ¹⁴ are each independently a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkynyl group, or a substituted or unsubstituted group. Represents an aryl group. _{], - SO 3 H, -OSO} 3 H, -CO 2 H or _{^{-Si (OR 15) m1 R 16}} 3-m1 [R 15, R 16 are each independently 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 m1 represents an integer of 1 to 3. ]
[9] The organic-inorganic composite composition according to [8], wherein the functional group is contained in an average range of 0.1 to 20 per polymer chain.
[10] The organic-inorganic composite composition as described in [8] or [9], wherein the thermoplastic resin is a copolymer containing a monomer represented by the general formula (2) as a polymerization unit.

〔一般式（１）中、Ｒは、水素原子、ハロゲン原子またはメチル基を表し、Ｘは−ＣＯ₂−、−ＯＣＯ−、−ＣＯＮＨ−、−ＯＣＯＮＨ−、−ＯＣＯＯ−、−Ｏ−、−Ｓ−、−ＮＨ−、置換または無置換のアリーレン基から選ばれる２価の連結基を表す。Yは炭素原子数が１〜３０である２価の連結基を表し、ｑは０〜１８の整数を表す。Ｚは下記から選ばれる官能基を表す。］

[In General Formula (1), R represents a hydrogen atom, a halogen atom or a methyl group, and X represents —CO ₂ —, —OCO—, —CONH—, —OCONH—, —OCOO—, —O—, — Represents a divalent linking group selected from S-, -NH-, a substituted or unsubstituted arylene group. Y represents a divalent linking group having 1 to 30 carbon atoms, and q represents an integer of 0 to 18. Z represents a functional group selected from the following. ]

［Ｒ¹¹、Ｒ¹²、Ｒ¹³、Ｒ¹⁴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、または−Ｓｉ（ＯＲ¹⁵）_m1Ｒ¹⁶ _3-m1［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し、ｍ１は１〜３の整数を表す。］

[R ¹¹ , R ¹² , R ¹³ and R ¹⁴ are each independently a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkynyl group, or a substituted or unsubstituted group. Represents an aryl group. _{], - SO 3 H, -OSO} 3 H, -CO 2 H or _{^{-Si (OR 15) m1 R 16}} 3-m1 [R 15, R 16 are each independently 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 m1 represents an integer of 1 to 3. ]

[11] The organic-inorganic composite composition as described in [7], wherein the thermoplastic resin is a thermoplastic resin having a functional group selected from the following at least at one position of a polymer terminal.

〔Ｒ²¹、Ｒ²²、Ｒ²³、Ｒ²⁴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、および、−Ｓｉ（ＯＲ²⁵）_m2Ｒ²⁶ _3-m2〔Ｒ²⁵、Ｒ²⁶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。ｍ２は１〜３の整数を表す。〕

[R ²¹ , R ²² , R ²³ and R ²⁴ are each independently a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkynyl group, or a substituted or unsubstituted group. Represents an aryl group. _{], -SO 3 H, -OSO 3 H} , -CO 2 H, _{^{and, -Si (OR 25) m2 R}} 26 3-m2 [R ^25, R ²⁶ are each independently a hydrogen atom, a substituted or unsubstituted An alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkynyl group, or a substituted or unsubstituted aryl group is represented. m2 represents an integer of 1 to 3. ]

[12] The organic-inorganic composite composition according to [7], wherein the thermoplastic resin is a block copolymer composed of a hydrophobic segment and a hydrophilic segment.

[13] A molded article obtained by molding the organic-inorganic composite composition according to any one of [1] to [12].
[14] The molded article according to [13], wherein the light transmittance in terms of 1 mm thickness is 70% or more at a wavelength of 589 nm.
[15] The molded article according to [13] or [14], wherein a refractive index at a wavelength of 589 nm is 1.60 or more.
[16] The molded body according to any one of [13] to [15], wherein the maximum thickness is 0.1 mm or more.

[17] An optical component comprising the molded body according to any one of [13] to [16].
[18] The optical component according to [17], which is a lens base material.

  According to the present invention, it is possible to provide an organic-inorganic composite composition having excellent transparency and high refractive index and excellent in temporal stability, and an optical component using the same. Further, according to the present invention, the refractive index can be arbitrarily controlled.

  Hereinafter, the organic-inorganic composite composition of the present invention and optical components such as a lens base material including the composition 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.

[Compound represented by general formula (1)]
The organic-inorganic composite composition of the present invention includes an inorganic fine particle and a compound represented by the following general formula (1) having a molecular weight of less than 2000.

  In general formula (1), Ra, Rb and Rc each independently represent a substituent. Q represents an atomic group or a single bond forming a 5- to 8-membered ring. n1 and n2 each independently represents an integer of 0 to 5. n3 represents 0 or 1. However, (n1 + n3) and (n2 + n3) do not exceed 5.

  In general formula (1), Ra, Rb, and Rc represent a substituent. The substituent is not particularly limited. For example, a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom), an alkyl group (for example, a methyl group, an ethyl group), an aryl group (for example, a phenyl group, a naphthyl group) Alkenyl group, alkynyl group, cyano group, carboxyl group, alkoxycarbonyl group (eg methoxycarbonyl group), aryloxycarbonyl group (eg phenoxycarbonyl group), substituted or unsubstituted carbamoyl group (eg carbamoyl group, N-phenylcarbamoyl) Group, N, N-dimethylcarbamoyl group), alkylcarbonyl group (for example, acetyl group), arylcarbonyl group (for example, benzoyl group), nitro group, acylamino group (for example, acetamido group, ethoxycarbonylamino group), sulfonamide group (for example, Meta Sulfonamide group), imide group (eg succinimide group, phthalimide group), imino group (eg benzylideneamino group), alkoxy group (eg methoxy group), aryloxy group (eg phenoxy group), acyloxy group (eg acetoxy group), Alkylsulfonyloxy group (for example, methanesulfonyloxy group), arylsulfonyloxy group (for example, benzenesulfonyloxy group), sulfo group, substituted or unsubstituted sulfamoyl group (for example, sulfamoyl group, N-phenylsulfamoyl group), alkylthio A group (for example, methylthio group), an arylthio group (for example, phenylthio group), an alkylsulfonyl group (for example, methanesulfonyl group), an arylsulfonyl group (for example, benzenesulfonyl group), a formyl group, a heterocyclic group, etc. It is possible. Further, the substituent may be further substituted, and when there are a plurality of substituents, they may be the same or different. The substituent for Ra and Rb is preferably a halogen atom, an alkyl group, an aryl group, an aryloxycarbonyl group, a substituted or unsubstituted carbamoyl group, an alkylcarbonyl group, an arylcarbonyl group, an acylamino group, an aryloxy group, or an acyloxy group. More preferably a halogen atom, an alkyl group, an aryl group, an arylcarbonyl group, an acylamino group, an aryloxy group or an acyloxy group, and still more preferably a halogen atom, an alkyl group, an aryl group or an arylcarbonyl group. The substituent for Rc is preferably an alkyl group, an aryl group, an aryloxycarbonyl group, a substituted or unsubstituted carbamoyl group or an arylcarbonyl group, more preferably an alkyl group or an aryl group, still more preferably an aryl group. is there.

  In general formula (1), Q represents an atomic group that forms a 5- to 8-membered ring, preferably an atomic group that forms a 5- to 7-membered ring or a single bond, and more preferably a 5- to 6-membered ring. Or a single bond. Q is preferably a single bond, an oxy group, a thio group, a substituted or unsubstituted alkylene group, a substituted or unsubstituted alkenylene group, or a substituted or unsubstituted imino group, more preferably a single bond, an oxy group, A thio group, a substituted or unsubstituted alkylene group, a substituted or unsubstituted alkenylene group; Details and preferred ranges of substituents that can be taken by the alkylene group, alkenylene group, and imino group are the same as details and preferred ranges of substituents that can be taken by Ra and Rb in the above general formula (1). The substituent which the alkylene group and the alkenylene group can take may form a condensed ring structure with these alkylene group or alkenylene group. Q is particularly preferably a single bond or the following linking group.

  The ring structure formed by Q is most preferably a carbazole ring.

  In general formula (1), n1 and n2 represent the integer of 0-5 each independently. n1 and n2 are preferably 0 to 3, more preferably 0 to 2, and even more preferably 0 to 1. n3 represents 0 or 1. Only when n3 is 0, n1 and n2 can each be 5.

  The molecular weight of the compound represented by the general formula (1) is less than 2000, preferably less than 1000, and more preferably less than 700. The lower limit of the molecular weight is preferably 181, more preferably 195, and even more preferably 209.

  Although the specific example of a compound represented by General formula (1) below is shown, the compound of General formula (1) which can be used by this invention is not limited to these.

  The compound represented by the general formula (1) may be synthesized according to a method well known to those skilled in the art or may be obtained from the market.

  The amount of the compound represented by the general formula (1) added to the organic-inorganic composite composition is preferably 0.1 to 30% by mass, more preferably 0.3 to 25% by mass, and further preferably It is 0.5-20 mass%. If the addition amount is 30% by mass or less, there is a tendency to prevent crying during molding or storage, and if the addition amount is 0.1% by mass or more, the effect of adding tends to be easily obtained. is there. In addition, crying out here means the phenomenon in which the added compound oozes out on the surface of a molded object.

[Inorganic fine particles]
The organic-inorganic composite composition of the present invention contains inorganic fine particles together with the compound represented by the general formula (1). The inorganic fine particles used in the present invention are not particularly limited, and for example, fine particles described in JP-A Nos. 2002-241612, 2005-298717, 2006-70069 and the like can be used.

Specifically, fine oxide particles (aluminum oxide, titanium oxide, niobium oxide, zirconium oxide, zinc oxide, magnesium oxide, tellurium oxide, yttrium oxide, indium oxide, tin oxide, etc.), double oxide fine particles (lithium niobate, Potassium niobate, lithium tantalate, etc.), sulfide fine particles (zinc sulfide, cadmium sulfide, etc.), other semiconductor crystal fine particles (zinc selenide, cadmium selenide, zinc telluride, cadmium telluride, etc.), or LiAlSiO ₄ , PbTiO ₃ , Sc ₂ W ₃ O ₁₂ , ZrW ₂ O ₈ , AlPO ₄ , Nb ₂ O ₅ , LiNO ₃ or the like can be used.

  Among these, metal oxide fine particles are particularly preferable, and among these, any one selected from the group consisting of zirconium oxide, zinc oxide, tin oxide, and titanium oxide is preferable, and includes zirconium oxide, zinc oxide, and titanium oxide. More preferably, it is any one selected from the group, and it is particularly preferable to use zirconium oxide fine particles having good visible range transparency and low photocatalytic activity.

  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. In addition, for various purposes such as reducing photocatalytic activity and water absorption, the inorganic fine particles are doped with different elements, the surface layer is coated with different metal oxides such as silica and alumina, silane coupling agents, titanate cups. The surface may be modified with a ring agent, an aluminate coupling agent, an organic acid (such as a carboxylic acid, a sulfonic acid, a phosphoric acid, or a phosphonic acid). Furthermore, these two or more types may be used in combination depending on the purpose.

  The refractive index of the inorganic fine particles used in the present invention is not particularly limited. However, when the organic-inorganic composite composition of the present invention is used for an optical member that requires a high refractive index, the inorganic fine particles have the above-described temperature dependency. In addition, it is preferable to have a high refractive index characteristic. In this case, the refractive index of the inorganic fine particles used is preferably 1.9 to 3.0 at 22 ° C. and a wavelength of 589 nm, more preferably 2.0 to 2.7, and particularly preferably 2.1. It is the case of ~ 2.5. 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 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 measured separately 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.

  If the number average particle size of the inorganic fine particles used in the present invention is too small, the characteristics specific to the substance constituting the fine particles may change. Conversely, if the number average particle size is too large, the influence of Rayleigh scattering is significant. Thus, the transparency of the organic-inorganic composite composition may be extremely reduced. Therefore, the lower limit of the number average 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 is preferably 15 nm or less, more preferably 10 nm. Hereinafter, it is more preferably 7 nm or less. That is, the number average 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 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 halide 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.

In addition to the method of hydrolyzing in water, the inorganic fine particles may be produced in an organic solvent or an organic solvent in which the thermoplastic resin in the present invention is dissolved. At this time, various surface treatment agents (silane coupling agents, aluminate coupling agents, titanate coupling agents, organic acids (carboxylic acids, sulfones, phosphonic acids, etc.)) may coexist as necessary. .
Examples of the solvent used in these methods include acetone, 2-butanone, dichloromethane, chloroform, toluene, ethyl acetate, cyclohexanone, anisole and the like. One of these may be used alone, or a plurality of these may be mixed and used.

  As a fine particle synthesis method, other than the above methods, various general fine particle synthesis methods described in, for example, Japanese Patent Application Laid-Open No. 2006-70069 are used, such as a method of manufacturing by a vacuum process such as a molecular beam epitaxy method or a CVD method. It may be adopted.

  The content of the inorganic fine particles in the organic-inorganic composite composition of the present invention is preferably 20 to 95% by mass, more preferably 25 to 70% by mass, and 30 to 60% by mass from the viewpoint of transparency and high refractive index. Particularly preferred. In addition, the mass ratio of the inorganic fine particles and the thermoplastic resin (dispersed polymer) in the present invention is preferably 1: 0.01 to 1: 100, more preferably 1: 0.05 to 1:10, from the viewpoint of dispersibility. A ratio of 1: 0.05 to 1: 5 is particularly preferable.

[Thermoplastic resin]
The organic-inorganic composite composition of the present invention preferably contains a thermoplastic resin. In particular, the organic-inorganic composite composition of the present invention preferably contains a thermoplastic resin having a functional group capable of forming an arbitrary chemical bond with inorganic fine particles at least at the polymer chain terminal or side chain. The chemical bond here is defined to include a covalent bond, an ionic bond, a hydrogen bond, and a coordination bond. Preferred examples of such thermoplastic resins include the following three types of thermoplastic resins.

(1) Thermoplastic resin having a functional group selected from the following in the side chain

［Ｒ¹¹、Ｒ¹²、Ｒ¹³、Ｒ¹⁴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、または−Ｓｉ（ＯＲ¹⁵）_m1Ｒ¹⁶ _3-m1［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し、ｍ１は１〜３の整数を表す。］；
（２）高分子末端の少なくとも１箇所に、下記から選ばれる官能基を有する熱可塑性樹脂

[R ¹¹ , R ¹² , R ¹³ and R ¹⁴ are each independently a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkynyl group, or a substituted or unsubstituted group. Represents an aryl group. _{], - SO 3 H, -OSO} 3 H, -CO 2 H or _{^{-Si (OR 15) m1 R 16}} 3-m1 [R 15, R 16 are each independently 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 m1 represents an integer of 1 to 3. ];
(2) A thermoplastic resin having a functional group selected from the following at least at one end of the polymer end

〔Ｒ²¹、Ｒ²²、Ｒ²³、Ｒ²⁴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、および、−Ｓｉ（ＯＲ²⁵）_m2Ｒ²⁶ _3-m2〔Ｒ²⁵、Ｒ²⁶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。ｍ２は１〜３の整数を表す。〕；
（３）疎水性セグメントおよび親水性セグメントで構成されるブロック共重合体
以下、これらの熱可塑性樹脂（１）〜（３）について、詳細に説明する。

[R ²¹ , R ²² , R ²³ and R ²⁴ are each independently a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkynyl group, or a substituted or unsubstituted group. Represents an aryl group. _{], -SO 3 H, -OSO 3 H} , -CO 2 H, _{^{and, -Si (OR 25) m2 R}} 26 3-m2 [R ^25, R ²⁶ are each independently a hydrogen atom, a substituted or unsubstituted An alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkynyl group, or a substituted or unsubstituted aryl group is represented. m2 represents an integer of 1 to 3. ];
(3) Block copolymer composed of hydrophobic segment and hydrophilic segment Hereinafter, these thermoplastic resins (1) to (3) will be described in detail.

<Thermoplastic resin (1)>
The thermoplastic resin (1) used in the present invention has a functional group capable of forming a chemical bond with inorganic fine particles in the side chain. Here, the “chemical bond” includes, for example, a covalent bond, an ionic bond, a coordination bond, a hydrogen bond, and the like, and when there are a plurality of functional groups, each can form a chemical bond different from the inorganic fine particles. It may be. Whether or not a chemical bond can be formed is determined by whether or not the functional group of the thermoplastic resin can form a chemical bond with the inorganic fine particle when the thermoplastic resin and the inorganic fine particle are mixed in an organic solvent. All of the functional groups of the thermoplastic resin may form chemical bonds with the inorganic fine particles, or some of them may form chemical bonds with the inorganic fine particles.

  The functional group capable of binding to the inorganic fine particles has a function of stably dispersing the inorganic fine particles in the thermoplastic resin by forming a chemical bond with the inorganic fine particles. Functional groups that can form chemical bonds with inorganic fine particles

［Ｒ¹¹、Ｒ¹²、Ｒ¹³、Ｒ¹⁴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、または−Ｓｉ（ＯＲ¹⁵）_m1Ｒ¹⁶ _3-m1［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し、ｍ１は１〜３の整数を表す。］から選ばれる官能基である。

[R ¹¹ , R ¹² , R ¹³ and R ¹⁴ are each independently a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkynyl group, or a substituted or unsubstituted group. Represents an aryl group. _{], - SO 3 H, -OSO} 3 H, -CO 2 H or _{^{-Si (OR 15) m1 R 16}} 3-m1 [R 15, R 16 are each independently 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 m1 represents an integer of 1 to 3. ] Is a functional group selected from

The preferred ranges of R ¹¹ , R ¹² , R ¹³ and R ¹⁴ 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, 2,4,6-tribromophenyl group, and 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 preferably a hydrogen atom or an alkyl group, and particularly preferably a hydrogen atom.
The preferred ranges of R ¹⁵ and R ¹⁶ are the same as those for R ¹¹ , R ¹² , R ¹³ and R ¹⁴ . m1 is preferably 3.

  Among these functional groups, preferably

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

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

または−ＣＯ₂Ｈであり、特に好ましくは、

Or —CO ₂ H, particularly preferably

である。

It is.

  The thermoplastic resin used in the present invention is particularly preferably a copolymer having a repeating unit represented by the following general formula (3). Such a copolymer can be obtained by copolymerizing a vinyl monomer represented by the following general formula (2).

In the general formulas (2) and (3), R represents a hydrogen atom, a halogen atom or a methyl group, and X represents —CO ₂ —, —OCO—, —CONH—, —OCONH—, —OCOO—, It represents a divalent linking group selected from the group consisting of —O—, —S—, —NH—, and a substituted or unsubstituted arylene group, more preferably —CO ₂ — or a p-phenylene group.

  Y represents a divalent linking group having 1 to 30 carbon atoms. 1-20 are preferable, as for carbon number, 2-10 are more preferable, and 2-5 are more preferable. Specific examples include an alkylene group, an alkyleneoxy group, an alkyleneoxycarbonyl group, an arylene group, an aryleneoxy group, an aryleneoxycarbonyl group, and a combination thereof, and an alkylene group is preferable.

q represents the integer of 0-18. More preferably, it is an integer of 0-10, More preferably, it is an integer of 0-5, Most preferably, it is an integer of 0-1.
Z is

、−ＳＯ₃Ｈ、−ＯＳＯ₃Ｈ、−ＣＯ₂Ｈ、または−Ｓｉ（ＯＲ¹⁵）_m1Ｒ¹⁶ _3-m1からなる群より選ばれる官能基を表し、好ましくは

Represents _{-SO 3 H, -OSO 3 H,} -CO 2 H or -Si (OR ¹⁵⁾ _m1 functional group selected from the group consisting of R ¹⁶ _3-m1,, preferably

であり、さらに好ましくは、

And more preferably

である。
ここで、Ｒ¹¹、Ｒ¹²、Ｒ¹³、Ｒ¹⁴、Ｒ¹⁵、Ｒ¹⁶およびｍ１の定義、好ましい範囲および具体例は、それぞれ独立に、上述したＲ¹¹、Ｒ¹²、Ｒ¹³、Ｒ¹⁴、Ｒ¹⁵、Ｒ¹⁶およびｍ１の定義、好ましい範囲および具体例と同義である。

It is.
Here, the definitions, preferred ranges and specific examples of R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ and m1 are each independently the above-mentioned R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , definition of R ^15, R ¹⁶ and m1, is synonymous with the preferred ranges and examples.

  Specific examples of the monomer represented by the general formula (2) are given below, but the monomer that can be used in the present invention is not limited thereto.

  Other types of monomers copolymerizable with the monomer represented by the general formula (2) in the present invention include 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 and the like.

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

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

  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.

  In addition, crotonic acid, itaconic acid, acrylonitrile, methacrylonitrile, maleilonitrile, and the like can also be mentioned.

  The weight average molecular weight of the thermoplastic resin (1) used in the present invention is preferably 1,000 to 500,000, more preferably 3,000 to 300,000, and 10,000 to 100,000. It is particularly preferred that When the weight average molecular weight of the thermoplastic resin (1) is 500,000 or less, the moldability tends to be improved, and when it is 1,000 or more, the mechanical strength tends to be improved.

  Here, the above-mentioned weight average molecular weight was determined by using a GPC analyzer using a column of “TSKgel GMHxL”, “TSKgel G4000HxL”, and “TSKgel G2000HxL” (both trade names manufactured by Tosoh Corporation) with a solvent tetrahydro The molecular weight is expressed in terms of polystyrene by furan and differential refractometer detection.

  In the thermoplastic resin (1) used in the present invention, the average number of functional groups bonded to inorganic fine particles is preferably from 0.1 to 20, and preferably from 0.5 to 10, per polymer chain. More preferably, it is particularly preferably 1 to 5. If the content of the functional group is 20 or less on average per polymer chain, the thermoplastic resin (1) is coordinated with a plurality of inorganic fine particles to prevent high viscosity and gelation in solution. It tends to be easy. 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 of the thermoplastic resin (1) used in the present invention is preferably 80 ° C to 400 ° C, and more preferably 130 ° C to 380 ° C. If a resin having a glass transition temperature of 80 ° 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 (1) 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. If the thermoplastic resin (1) 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 (1) used in the invention is preferably 1.55 or more, and more preferably 1.58 or more. These refractive indexes are values at 22 ° C. and a wavelength of 589 nm.

  The thermoplastic resin (1) used in the present invention preferably has a light transmittance in terms of 1 mm thickness at a wavelength of 589 nm of 80% or more, more preferably 85% or more, and more preferably 88% or more. Particularly preferred.

  Although the preferable specific example of the thermoplastic resin which can be used by this invention is given to the following, the thermoplastic resin which can be used by this invention is not limited to these.

  These thermoplastic resins (1) may be used alone or in combination of two or more. Moreover, you may use together with a thermoplastic resin (2) and / or (3).

<Thermoplastic resin (2)>
In the thermoplastic resin (2) used in the present invention, the functional group capable of forming a chemical bond with inorganic fine particles has a functional group capable of forming a chemical bond with inorganic fine particles at least at one position on the polymer terminal. Here, the functional group may be present only at one end of the polymer chain or may be present at both ends, but is preferably present only at one end of the polymer chain. Further, a plurality of functional groups may exist at the terminal. The term “terminal” as used herein means a portion excluding a structure sandwiched between repeating units constituting a polymer chain. Here, the “chemical bond” can be considered in the same manner as the thermoplastic resin (1).

  Functional groups that can form chemical bonds with inorganic fine particles

〔Ｒ²¹、Ｒ²²、Ｒ²³、Ｒ²⁴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、および、−Ｓｉ（ＯＲ²⁵）_m2Ｒ²⁶ _3-m2〔Ｒ²⁵、Ｒ²⁶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。ｍ２は１〜３の整数を表す。〕から選ばれる官能基である。
Ｒ²¹、Ｒ²²、Ｒ²³、Ｒ²⁴、Ｒ²⁵、Ｒ²⁶が、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である場合、これらの好ましい範囲は、Ｒ¹¹、Ｒ¹²、Ｒ¹³、Ｒ¹⁴の好ましい範囲として述べたものと同様である。また、ｍ２は、３であることが好ましい。

[R ²¹ , R ²² , R ²³ and R ²⁴ are each independently a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkynyl group, or a substituted or unsubstituted group. Represents an aryl group. _{], -SO 3 H, -OSO 3 H} , -CO 2 H, _{^{and, -Si (OR 25) m2 R}} 26 3-m2 [R ^25, R ²⁶ are each independently a hydrogen atom, a substituted or unsubstituted An alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkynyl group, or a substituted or unsubstituted aryl group is represented. m2 represents an integer of 1 to 3. ] Is a functional group selected from
R ²¹ , R ²² , R ²³ , R ²⁴ , R ²⁵ , R ²⁶ are substituted or unsubstituted alkyl groups, substituted or unsubstituted alkenyl groups, substituted or unsubstituted alkynyl groups, or substituted or unsubstituted aryls. In the case of a group, these preferable ranges are the same as those described as the preferable ranges of R ¹¹ , R ¹² , R ¹³ and R ¹⁴ . M2 is preferably 3.

  Among these functional groups, preferably

、−ＳＯ₃Ｈ、−ＣＯ₂Ｈ、および、−Ｓｉ（ＯＲ²⁵）_m2Ｒ²⁶ _3-m2であり、より好ましくは、

_{, -SO 3 H, -CO 2 H} , and a ^{_{-Si (OR 25) m2 R 26}} 3-m2, more preferably,

、−ＳＯ₃Ｈ、および、−ＣＯ₂Ｈであり、特に好ましくは、

, -SO ₃ H, and a -CO ₂ H, particularly preferably,

、−ＳＯ₃Ｈである。

, A -SO ₃ H.

  The basic skeleton of the thermoplastic resin (2) used in the present invention is not particularly limited, and poly (meth) acrylic acid ester, polystyrene, polyvinylcarbazole, polyarylate, polycarbonate, polyurethane, polyimide, polyether, polyethersulfone, Known resin skeletons such as polyether ketone, polythioether, cycloolefin polymer, and cycloolefin copolymer can be employed. Preferred are vinyl polymers, polyarylate, and aromatic-containing polycarbonates, and more preferred are vinyl polymers. Specific examples thereof are the same as those described in the thermoplastic resin (1).

  If the thermoplastic resin (2) used in the present invention has a refractive index of about 1.48, a transparent molded article having a refractive index of 1.60 can be provided, but a refractive index of 1.65 or more is realized. In order to achieve this, the refractive index of the thermoplastic resin (1) used in the present invention is preferably 1.55 or more, and more preferably 1.58 or more. These refractive indexes are values at 22 ° C. and a wavelength of 589 nm.

  The thermoplastic resin (2) used in the present invention preferably has a glass transition temperature of 50 ° C to 400 ° C, and more preferably 80 ° C to 380 ° C. By setting the glass transition temperature to 50 ° C. or higher, heat resistance tends to be improved, and by setting the glass transition temperature to 400 ° C. or lower, molding processing tends to be easily performed.

  In addition, the thermoplastic resin (2) used in the present invention preferably has a light transmittance in terms of 1 mm thickness at a wavelength of 589 nm of 80% or more, and more preferably 85% or more.

  The number average molecular weight of the thermoplastic resin (2) used in the present invention is 1,000 to 500,000. The number average molecular weight of the thermoplastic resin (2) is preferably 3,000 to 300,000, more preferably 5,000 to 200,000, and particularly preferably 10,000 to 100,000. preferable. When the number average molecular weight of the thermoplastic resin (2) is 1,000 or more, the mechanical strength tends to be improved, and when the number average molecular weight is 500,000 or less, the moldability tends to be improved. is there.

  The method for introducing the functional group at the end of the polymer chain is not particularly limited. For example, New Polymer Experiments 4 Polymer Synthesis and Reaction (3) Polymer Reaction and Degradation (Edited by Polymer Society) As described in Chapter 3 “Terminal Reactive Polymer”, it may be introduced at the time of polymerization, or after polymerization, terminal functional group conversion or main chain decomposition of the once isolated polymer may be performed. A method for obtaining a polymer by polymerization using an initiator, a terminator, a chain transfer agent, etc. having a functional group and / or a protected functional group, for example, a phenol terminal portion of a polycarbonate obtained from bisphenol A, It is also possible to use a polymer reaction such as a method of modifying with a contained reactive agent. For example, the serial transfer method vinyl using the sulfur-containing chain transfer agent described in the paragraphs 110 to 112 in “New Polymer Experimental 2 Synthesis and Reaction of Polymers (1) Synthesis of Addition Polymers (Edited by Polymer Society)” Polymeric radical polymerization; functional group-containing initiators according to 255-256, “New Polymer Experiment 2, Synthesis and Reaction of Polymers (1) Synthesis of Addition Polymers” Or, living cationic polymerization using a functional group-containing terminator; ring-opening metathesis polymerization using a sulfur-containing chain transfer agent described in “Macromolecules, Vol. 36”, paragraphs 7020 to 7026 (2003).

  Preferred specific examples (exemplary compounds P-1 to P-22) of the thermoplastic resin (2) that can be used in the present invention are listed below, but the thermoplastic resin (2) that can be used in the present invention is these. It is not limited to. The structure in [] represents a repeating unit, and x and y of the repeating unit represent a copolymerization ratio (mol ratio).

  These thermoplastic resins (2) may be used alone or in combination of two or more. Further, these thermoplastic resins may contain other copolymer components.

<Thermoplastic resin (3)>
The thermoplastic resin (3) used in the present invention is a block copolymer composed of a hydrophobic segment and a hydrophilic segment.

Here, the hydrophobic segment (A) refers to a segment having a characteristic that a polymer composed only of the segment (A) does not dissolve in water or methanol, and the hydrophilic segment (B) includes only the segment (B). A segment in which the polymer has the property of being dissolved in water or methanol. The block copolymer types include AB type, B ¹ AB ² type (two hydrophilic segments B ¹ and B ² may be the same or different) and A ¹ BA ² type (two hydrophobic types). Segments A ¹ and A ² may be the same or different), and from the viewpoint of good dispersion characteristics, AB type or A ¹ BA ² type block copolymers are preferred, and from the viewpoint of production suitability, AB type or ABA type (the two hydrophobic segments of A ¹ BA ² type are the same type) is more preferred, and AB type is particularly preferred.

  The hydrophobic segment and the hydrophilic segment are each a vinyl polymer, polyether, ring-opening metathesis polymer, and condensation polymer (polycarbonate, polyester, polyamide, polyetherketone, polyethersulfone, etc.) obtained by polymerization of vinyl monomers. However, vinyl polymers, ring-opening metathesis polymerization polymers, polycarbonates, and polyesters are preferable, and vinyl polymers are more preferable from the viewpoint of production suitability.

As a vinyl monomer (A) which forms the said hydrophobic segment (A), the following are mentioned, for example.
Acrylic acid esters and methacrylic acid esters (the ester group is a substituted or unsubstituted aliphatic ester group, a substituted or unsubstituted aromatic ester group, such as a methyl group, a phenyl group, or a naphthyl group);

  Acrylamides, methacrylamides, specifically, N-monosubstituted acrylamides, N-disubstituted acrylamides, N-monosubstituted methacrylamides, N-disubstituted methacrylamides (substituents of mono- and di-substituted products are A substituted or unsubstituted aliphatic group, a substituted or unsubstituted aromatic group, and examples of the substituent include a methyl group, a phenyl group, and a naphthyl group);

  Olefins, specifically, dicyclopentadiene, norbornene derivatives, ethylene, propylene, 1-butene, 1-pentene, vinyl chloride, vinylidene chloride, isoprene, chloroprene, butadiene, 2,3-dimethylbutadiene, vinylcarbazole and the like; Styrenes, specifically styrene, methyl styrene, dimethyl styrene, trimethyl styrene, ethyl styrene, isopropyl styrene, chloromethyl styrene, methoxy styrene, acetoxy styrene, chloro styrene, dichloro styrene, bromo styrene, tribromo styrene, vinyl benzoate Acid methyl ester, etc .;

  Vinyl ethers, specifically methyl vinyl ether, butyl vinyl ether, phenyl vinyl ether, methoxyethyl vinyl ether, etc .; other monomers include butyl crotonate, hexyl crotonate, dimethyl itaconate, dibutyl itaconate, diethyl maleate, dimethyl maleate , Dibutyl maleate, diethyl fumarate, dimethyl fumarate, dibutyl fumarate, methyl vinyl ketone, phenyl vinyl ketone, methoxyethyl vinyl ketone, N-vinyl oxazolidone, N-vinyl pyrrolidone, vinylidene chloride, methylene malononitrile, vinylidene, diphenyl 2-acryloyloxyethyl phosphate, diphenyl-2-methacryloyloxyethyl phosphate, dibutyl-2-acryloyloxy Chiruhosufeto, dioctyl-2-methacryloyloxyethyl phosphate.

  Among them, acrylic esters and methacrylic esters in which the ester group is an unsubstituted aliphatic group, substituted or unsubstituted aromatic group; the substituent is an unsubstituted aliphatic group, substituted or unsubstituted aromatic group N-monosubstituted acrylamides, N-disubstituted acrylamides, N-monosubstituted methacrylamides and N-disubstituted methacrylamides; styrenes; preferred are acrylic esters and methacrylic esters in which the ester group is a substituted or unsubstituted aromatic group Acid esters; styrenes are more preferred.

As a vinyl monomer (B) which forms the said hydrophilic segment (B), the following are mentioned, for example.
Acrylic acid, methacrylic acid, acrylic acid esters and methacrylic acid esters having a hydrophilic substituent at the ester moiety; styrenes having a hydrophilic substituent at the aromatic ring portion; vinyl ethers having a hydrophilic substituent, acrylamide , Methacrylamide, N-monosubstituted acrylamide, N-disubstituted acrylamide, N-monosubstituted methacrylamide and N-disubstituted methacrylamide.

  As the hydrophilic substituent,

〔但し、Ｒ³¹、Ｒ³²、Ｒ³³、Ｒ³⁴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、および、−Ｓｉ（ＯＲ³⁵）_m3Ｒ³⁶ _3-m3〔但し、Ｒ³⁵、Ｒ³⁶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。ｍ３は１〜３の整数を表す。〕からなる群より選ばれる官能基を有するのが好ましい。

[However, R ³¹ , R ³² , R ³³ and R ³⁴ are each independently a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkynyl group, substituted or unsubstituted An unsubstituted aryl group is represented. _{], -SO 3 H, -OSO 3 H} , -CO 2 H, -OH, _{^{and, -Si (OR 35) m3 R}} 36 3-m3 [However, R ^35, R ³⁶ are each independently a hydrogen atom Represents a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkynyl group, or a substituted or unsubstituted aryl group. m3 represents an integer of 1 to 3. It preferably has a functional group selected from the group consisting of

R ³¹ , R ³² , R ³³ , R ³⁴ , R ³⁵ , and R ³⁶ are substituted or unsubstituted alkyl groups, substituted or unsubstituted alkenyl groups, substituted or unsubstituted alkynyl groups, or substituted or unsubstituted aryl groups. In the case of a group, these preferable ranges are the same as those described as the preferable ranges of R ¹¹ , R ¹² , R ¹³ and R ¹⁴ . M3 is preferably 3.
As the functional group,

、−ＣＯ₂Ｈ、もしくは、−Ｓｉ（ＯＲ³⁵）_m3Ｒ³⁶ _3-m3が好ましく、

, -CO ₂ H _{^{or,, -Si (OR 35) m3}} R 36 3-m3 is preferred,

および−ＣＯ₂Ｈがより好ましく、

And -CO ₂ H are more preferable,

が特に好ましい。

Is particularly preferred.

  In the present invention, in particular, the block copolymer is

、−ＳＯ₃Ｈ、−ＯＳＯ₃Ｈ、−ＣＯ₂Ｈ、−ＯＨ、および、−Ｓｉ（ＯＲ³⁵）_m3Ｒ³⁶ _3-m3から選ばれる官能基を有し、該官能基の含有量が０．０５ｍｍｏｌ／ｇ以上５．０ｍｍｏｌ／ｇ以下であることが好ましい。

_{, -SO 3 H, -OSO 3 H} , -CO 2 H, -OH, and has a functional group selected from ^{_{-Si (OR 35) m3 R 36}} 3-m3, the content of the functional group 0 It is preferable that it is 0.05 mmol / g or more and 5.0 mmol / g or less.

  Among them, as the hydrophilic segment (B), acrylic acid, methacrylic acid, acrylic acid esters and methacrylic acid esters having a hydrophilic substituent at the ester site, and styrenes having a hydrophilic substituent at the aromatic ring portion Is preferred.

  The vinyl monomer (A) forming the hydrophobic segment (A) may contain the vinyl monomer (B) as long as the hydrophobic properties are not hindered. The molar ratio of the vinyl monomer (A) and the vinyl monomer (B) contained in the hydrophobic segment (A) is preferably 100: 0 to 60:40.

  The vinyl monomer (B) forming the hydrophilic segment (B) may contain the vinyl monomer (A) as long as the hydrophilic property is not hindered. The molar ratio of the vinyl monomer (B) and the vinyl monomer (A) contained in the hydrophilic segment (B) is preferably 100: 0 to 60:40.

  Each of the vinyl monomer (A) and the vinyl monomer (B) may be used alone or in combination of two or more. The vinyl monomer (A) and the vinyl monomer (B) are used for various purposes (for example, adjustment of acid content, adjustment of glass transition point (Tg), adjustment of solubility in organic solvents and water, and adjustment of dispersion stability. ).

The content of the functional group is preferably 0.05 to 5.0 mmol / g, more preferably 0.1 to 4.5 mmol / g, based on the entire block copolymer. It is particularly preferably 15 to 3.5 mmol / g. If the content of the functional group is too small, the dispersibility may be reduced. If the content is too large, the water solubility may be too high, or the organic-inorganic composite composition may be gelled. In the block copolymer, the functional group may form a salt with a cationic ion such as an alkali metal ion (for example, Na ⁺ or K ⁺ ) or an ammonium ion.

  The molecular weight (Mn) of the block copolymer is preferably 1000 to 100,000, more preferably 2000 to 80000, and particularly preferably 3000 to 50000. When the molecular weight of the block copolymer is 1000 or more, a stable dispersion tends to be easily obtained, and when it is 100000 or less, the solubility in an organic solvent tends to be improved.

  If the refractive index of the block copolymer used in the present invention is about 1.48, a transparent molded article having a refractive index of 1.60 can be provided, but in order to realize a refractive index of 1.65 or more. The refractive index of the thermoplastic resin (1) used in the present invention is preferably 1.55 or more, and more preferably 1.58 or more. These refractive indexes are values at 22 ° C. and a wavelength of 589 nm.

  The block copolymer used in the present invention preferably has a glass transition temperature of 80 ° C to 400 ° C, more preferably 130 ° C to 380 ° C. When the glass transition temperature is 80 ° C. or higher, the heat resistance tends to be improved, and when the glass transition temperature is 400 ° C. or lower, the moldability tends to be improved.

  The block copolymer used in the present invention preferably has a light transmittance in terms of 1 mm thickness at a wavelength of 589 nm of 80% or more, and more preferably 85% or more.

  Specific examples of the block copolymer (Exemplary Compounds Q-1 to Q-20) are listed below. In addition, the block copolymer used for this invention is not limited to these specific examples at all.

  The block copolymer can be synthesized using living radical polymerization and living ion polymerization using a technique for protecting a carboxyl group or the like as required or introducing a functional group into the polymer. Moreover, it can synthesize | combine by the radical polymerization from a terminal functional group polymer, and the connection of terminal functional group polymers. Among them, it is preferable to use living radical polymerization and living ion polymerization from the viewpoint of molecular weight control and the yield of the block copolymer. As for the production method of the block copolymer, for example, “Synthesis and Reaction of Polymer (1) (Edited by Polymer Society, Kyoritsu Publishing Co., Ltd. (1992))”, “Precision Polymerization (Edited by Chemical Society of Japan, (Published by Academic Publishing Center (1993)) ”,“ Synthesis and Reaction of Polymers (1) (Edited by Polymer Society, Kyoritsu Publishing Co., Ltd. (1995)) ”,“ Telechelic Polymers: Synthesis, Properties, Applications (R) Jerome et al., Prog. Polym. Sci. Vol 16.837-906 (1991)), “Synthesis of block and graft copolymers by light (Y. Yagch et al., Prog. Polym. Sci. Vol 15.551-601). Page (1990)), US Pat. No. 5,085,698 and the like.

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

[Other additives]
In addition to the compound represented by the above general formula (1), the thermoplastic resin, and the inorganic fine particles, various additions are appropriately added to the organic-inorganic composite composition of the present invention from the viewpoints of uniform dispersibility, releasability, weather resistance, and the like. An agent may be blended. For example, a surface treatment agent, an antistatic agent, a dispersant, a plasticizer, a release agent, and the like can be given. In addition to the resin, a resin having no functional group may be added, and there is no particular limitation on the kind of the resin, but the resin has the same optical properties, thermophysical properties, and molecular weight as the thermoplastic resin. Is preferred.
Although the blending ratio of these additives varies depending on the purpose, it is preferably 0 to 50% by mass and more preferably 0 to 30% by mass with respect to the total amount of the inorganic fine particles and the thermoplastic resin. 0 to 20% by mass is particularly preferable.

<Surface treatment agent>
In the present invention, as described later, when inorganic fine particles dispersed in water or an alcohol solvent are mixed with a thermoplastic resin, the objective is to improve the extractability or substitution into an organic solvent, and the uniform dispersibility to the thermoplastic resin. Depending on various purposes such as increasing the water absorption, decreasing the water absorption of the fine particles, or increasing the weather resistance, a fine particle surface modifier other than the thermoplastic resin may be added. The surface treatment agent preferably has a weight average molecular weight of 50 to 50,000, more preferably 100 to 20,000, and still more preferably 200 to 10,000.

As said surface treating agent, what has a structure represented by following General formula (4) is preferable.
General formula (4)
AB

  In the general formula (4), A represents a functional group capable of forming a chemical bond with the surface of the inorganic fine particles used in the present invention, and B is compatible with a resin matrix mainly composed of the thermoplastic resin used in the present invention. Alternatively, it represents a monovalent group or polymer having 1 to 30 carbon atoms having reactivity. Here, “chemical bond” refers to, for example, a covalent bond, an ionic bond, a coordinate bond, a hydrogen bond, and the like.

Preferred examples of the group represented by A are the same as those described above as the functional group of the thermoplastic resin used in the present invention.
On the other hand, the chemical structure of the group represented by B is preferably the same as or similar to the chemical structure of the thermoplastic resin that is the main component of the resin matrix from the viewpoint of compatibility. In the present invention, particularly from the viewpoint of increasing the refractive index, it is preferable that the chemical structure of B together with the thermoplastic resin has an aromatic ring.

  Examples of the surface treatment agent preferably used in the present invention include, for example, p-octylbenzoic acid, p-propylbenzoic acid, acetic acid, propionic acid, cyclopentanecarboxylic acid, dibenzyl phosphate, monobenzyl phosphate, diphenyl phosphate, diphosphate phosphate. -Α-naphthyl, phenylphosphonic acid, phenylphosphonic acid monophenyl ester, KAYAMER PM-21 (trade name; manufactured by Nippon Kayaku Co., Ltd.), KAYAMER PM-2 (trade name; manufactured by Nippon Kayaku Co., Ltd.), benzenesulfonic acid, Naphthalenesulfonic acid, paraoctylbenzenesulfonic acid, or silane coupling agents described in JP-A-5-221640, JP-A-9-100111, JP-A-2002-187721, and the like, are limited thereto. It is not a thing.

These surface treatment agents may be used alone or in combination of two or more.
The total amount of addition of these surface treatment agents is preferably 0.01 to 2 times, more preferably 0.03 to 1 time, and more preferably 0.05 to 0. A ratio of 5 times is particularly preferable.

<Antistatic agent>
In order to adjust the charged voltage of the organic-inorganic composite composition of the present invention, an antistatic agent can be added. In the organic-inorganic composite composition of the present invention, the inorganic fine particles added for the purpose of improving optical characteristics may contribute to the antistatic effect, which is another effect. In the case of adding an antistatic agent, an anionic antistatic agent, a cationic antistatic agent, a nonionic antistatic agent, a zwitterionic antistatic agent, a polymeric antistatic agent, or a charging fine particle may be mentioned. Two or more types may be used in combination. Examples thereof include compounds described in JP2007-4131A and JP2003201396A.
The addition amount of the antistatic agent varies, but is preferably 0.001 to 50% by mass, more preferably 0.01 to 30% by mass, and particularly preferably 0.1 to 10% by mass based on the total solid content. % By mass.

<Others>
In addition to the above compounds, plant waxes such as carnauba wax, rice wax, cotton wax and tree wax, animal waxes such as beeswax and lanolin, and ozokerite for the purpose of enhancing the mold release effect and further improving the fluidity during molding. In addition to mineral waxes such as ceresin and natural waxes such as paraffin, microcrystalline, and petrolatum, synthetic hydrocarbon waxes such as Fischer-Tropsch wax and polyethylene wax, stearamide, chlorinated hydrocarbons, etc. Add synthetic waxes such as long chain aliphatic amides, esters, ketones and ethers, silicone oils such as dimethyl silicone oil and methylphenyl silicone oil, and fluorine telomers such as Zonyl FSN and Zonyl FSO manufactured by DuPont. You can also. In addition, for the purpose of improving light resistance and thermal degradation, known degradation inhibitors such as hindered phenols, amines, phosphoruss, and thioethers may be appropriately added. When these are blended, the resin composition About 0.1-5 mass% is preferable with respect to the total solid of.

[Method for producing organic-inorganic composite composition]
The organic-inorganic composite composition of the present invention is preferably produced by chemically bonding inorganic fine particles with the thermoplastic resin having the functional group and dispersing it in the resin. At this time, the compound represented by the general formula (1) is allowed to exist.
Since the inorganic fine particles used in the present invention have a small particle size and high surface energy, it is difficult to re-disperse when isolated as a solid. Therefore, it is preferable that the inorganic fine particles are mixed with the thermoplastic resin in a state dispersed in a solution to form a stable dispersion. As a preferred method for producing an organic-inorganic composite composition, [1] inorganic particles obtained by surface-treating inorganic particles in the presence of the surface treatment agent, extracting the surface-treated inorganic fine particles in an organic solvent, and extracting the inorganic fine particles. Is a method for producing a composite of inorganic fine particles and a thermoplastic resin by uniformly mixing with the thermoplastic resin and the compound represented by the general formula (1), [2] inorganic fine particles, a thermoplastic resin and the general formula (1) ) And a compound capable of uniformly dispersing or dissolving other additives, and a method of producing a composite of inorganic fine particles and a thermoplastic resin by uniformly mixing all the components.

In the case of producing a composite of inorganic fine particles and a thermoplastic resin by the method of [1] above, water-insoluble such as toluene, ethyl acetate, methyl isobutyl ketone, chloroform, dichloroethane, dichloroethane, chlorobenzene, methoxybenzene and the like as an organic solvent. These 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 column of> are mentioned.
When mixing the inorganic fine particles extracted into the organic solvent and the thermoplastic resin, the compound represented by the general formula (1) is also added, and further, a plasticizer, a release agent, or another kind of polymer is added. You may add an agent as needed.

  When the method [2] is employed, dimethylacetamide, dimethylformamide, dimethylsulfoxide, benzyl alcohol, cyclohexanol, ethylene glycol monomethyl ether, 1-methoxy-2-propanol, tert-butanol, acetic acid, propionic acid are used as the solvent. Hydrophilic polar solvents such as single or mixed solvents, or mixed solvents of non-water soluble solvents such as chloroform, dichloroethane, dichloromethane, ethyl acetate, methyl ethyl ketone, methyl isobutyl ketone, toluene, chlorobenzene, methoxybenzene and the above polar solvents Preferably used. In this case, a dispersant, a plasticizer, a mold 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, after adding a hydrophilic solvent which has a higher boiling point than water / methanol and dissolves the thermoplastic resin, the water / methanol is concentrated and distilled 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 composition obtained by the methods (1) and (2) can be cast as it is to obtain a transparent molded body. In the present invention, however, the solution is particularly concentrated and freeze-dried. Alternatively, after removing the solvent by a method such as reprecipitation from an appropriate poor solvent, the solidified powder is preferably molded by a known method such as injection molding or compression molding. At this time, the powdery organic-inorganic composite composition of the present invention can be processed into a molded article such as a lens by directly heating, melting, or compressing, but once it has a certain weight and shape by a method such as an extrusion method. After forming a preform (precursor) having, an optical component such as a lens can be formed by deforming the preform by compression molding. In this case, the preform can have an appropriate curvature in order to efficiently create the target shape.

[Organic-inorganic composite composition]
The light transmittance of the organic-inorganic composite composition of the present invention is preferably 70% or more, more preferably 75% or more, and particularly preferably 80% or more in terms of 1 mm thickness at a wavelength of 589 nm. . The light transmittance at a wavelength of 405 nm is preferably 60% or more, more preferably 65% or more, and particularly preferably 70% or more. If the light transmittance in terms of 1 mm thickness at a wavelength of 589 nm is 70% or more, it is easy to obtain a lens substrate having more preferable properties. In the present invention, the light transmittance in terms of 1 mm thickness is obtained by forming a substrate having a thickness of 1.0 mm by molding an organic-inorganic composite composition, and measuring an ultraviolet-visible absorption spectrum (UV-3100, Inc.). It is a value measured by Shimadzu Corporation.

  The organic-inorganic composite composition of the present invention preferably has a refractive index of 1.60 or more at a wavelength of 589 nm, more preferably 1.65 or more, and particularly preferably 1.67 or more.

  It is desirable that the organic-inorganic composite composition of the present invention is difficult to be charged for the purpose of preventing adhesion of dust and the like. The charged voltage is preferably −2 to 15 kV, more preferably −1.5 to 7.5 kV, and particularly preferably −1.0 to 7.0 kV.

  The organic-inorganic composite composition of the present invention preferably has a glass transition temperature of 100 ° C to 400 ° C, and more preferably 130 ° C to 380 ° C. When the glass transition temperature is 100 ° C. or higher, sufficient heat resistance is easily obtained, and when the glass transition temperature is 400 ° C. or lower, molding processing tends to be easily performed.

  In the organic-inorganic composite composition of the present invention, the volatile component when held at 200 ° C. for 2 hours is preferably 2% by mass or less, more preferably, 2% by mass when held at 230 ° C. for 2 hours. %, And particularly preferably, the volatile component when held at 250 ° C. for 2 hours is 2% by mass or less.

  The saturated water absorption of the organic-inorganic composite composition of the present invention is preferably 2% by mass or less, more preferably 1% by mass or less, and particularly preferably 0.5% by mass or less.

[Molded body]
By molding the organic-inorganic composite composition of the present invention described above, the molded article of the present invention can be produced. As the molded article of the present invention, those showing the refractive index and optical characteristics described above in the explanation of the organic-inorganic composite composition are useful.
The molded article of the present invention is particularly useful for optical components having a high refractive index having a maximum thickness of 0.1 mm or more. It is preferably applied to an optical component having a thickness of 0.1 to 5 mm, and particularly preferably applied to a transparent component having a thickness of 1 to 3 mm.
These thick molded products are difficult to remove by solvent casting and are usually not easy, but by using the organic-inorganic composite composition of the present invention, molding is easy and complex shapes such as aspherical surfaces are easy. The material having good transparency can be obtained while utilizing the high refractive index characteristics of the fine particles.

[Optical parts]
The molded article of the present invention is a molded article having both high refractive properties, light transmittance and light weight and excellent optical characteristics. The optical component of the present invention is made of such a molded body. The kind of the optical component of the present invention is not particularly limited. In particular, it can be suitably used as an optical component utilizing the excellent optical properties of the organic-inorganic composite composition, particularly as an optical component that transmits light (so-called passive optical component). Examples of the optical functional device provided with 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.), camera, etc. And an imaging device such as a video.

  Examples of the passive optical component used in the optical functional device include a lens, a prism, a prism sheet, a panel (plate-shaped molded body), a film, an optical waveguide (film-like or fiber-like), an optical disk, and an LED seal. Examples thereof include a stopper. For such passive optical components, an optional coating layer, for example, a protective layer that prevents mechanical damage to the coated surface due to friction and wear, light rays with an undesirable wavelength that causes deterioration of inorganic particles and substrates, etc. A light absorbing layer that absorbs light, a transmission shielding layer that suppresses or prevents the transmission of reactive low molecules such as moisture and oxygen gas, an antiglare layer, an antireflection layer, a low refractive index layer, etc. A multilayer structure may be used. Specific examples of such an optional coating layer include a transparent conductive film and gas barrier film made of an inorganic oxide coating layer, a gas barrier film made of an organic coating layer, a hard coat, and the like. A known coating method such as a sputtering method, a dip coating method, or a spin coating method can be used.

An optical component using the organic-inorganic composite composition of the present invention is particularly suitable for a lens substrate. The lens substrate manufactured using the organic-inorganic composite composition of the present invention has both high refractive properties, light transmittance and lightness, and is excellent in optical properties. In addition, the refractive index of the lens substrate can be arbitrarily adjusted by appropriately adjusting the type of monomer constituting the organic-inorganic composite composition 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 includes, for example, a spectacle lens, an optical device lens, an optoelectronic lens, a laser lens, a pickup lens, an in-vehicle camera lens, a portable camera lens, a digital camera lens, an OHP lens, Used for 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) “H-9000UHR Transmission Electron Microscope” manufactured by Hitachi, Ltd. (acceleration voltage 200 kV, degree of vacuum at observation about 7.6 × 10 ⁻⁹ Pa) went.

(2) Light transmittance measurement A sample to be measured is molded to produce a substrate having a thickness of 1.0 mm, and a wavelength of 589 nm is obtained using an ultraviolet-visible absorption spectrum measuring apparatus “UV-3100” (manufactured by Shimadzu Corporation). Measured with light.

(3) Refractive index measurement It measured about the light of wavelength 589nm with the Abbe refractometer ("DR-M4" by Atago Co., Ltd.).

(4) X-ray diffraction (XRD) spectrum measurement It measured at 23 degreeC using "RINT1500" (X-ray source: Copper K alpha ray, wavelength 1.5418?) By Rigaku Corporation.

(5) Molecular weight measurement The number average molecular weight and the weight average molecular weight were measured using a GPC analyzer using columns of “TSKgel GMHxL”, “TSKgel G4000HxL”, and “TSKgel G2000HxL” (both trade names manufactured by Tosoh Corporation). Measured using tetrahydrofuran as a solvent. The molecular weight was expressed in terms of polystyrene by differential refractometer detection.

[Preparation of fine particle dispersion]
(1) Preparation of Titanium Oxide Fine Particle Dispersion A dispersion of titanium oxide fine particles was prepared according to the method described in Synthesis Example 9 of JP-A-2003-73559. From XRD and TEM, it was confirmed that anatase-type titanium oxide fine particles (number average particle size was about 5 nm) were formed. The refractive index of the fine particles was 2.5.

(2) Synthesis of zirconium oxide 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. This cake was adjusted to a concentration of 15% by mass in terms of zirconium oxide 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 zirconium oxide fine particle suspension. Formation of zirconium oxide fine particles having a number average particle size of 5 nm was confirmed by TEM. The refractive index of the fine particles was 2.1.

(3) Preparation of zirconium oxide fine particle toluene dispersion The zirconium oxide fine particle suspension synthesized in (2) above was mixed with a toluene solution in which “KAYAMER PM-21” manufactured by Nippon Kayaku was dissolved. After stirring for a period of time, the toluene solution was extracted to prepare a zirconium oxide fine particle toluene dispersion.

(4) Preparation of Zirconium Oxide Dimethylacetamide Dispersion Add 500 g of N, N′-dimethylacetamide to 500 g of the zirconium oxide fine particle suspension (concentration: 15% by mass) prepared in (2) above, and reduce the pressure to about 500 g or less. After concentration and solvent replacement, the concentration was adjusted by adding N, N′-dimethylacetamide to obtain a 15 mass% zirconium oxide dimethylacetamide dispersion.

[Synthesis of thermoplastic resin]
(1) Synthesis of thermoplastic resin B-11 Styrene 246.25 g, β-carboxyethyl acrylate 3.75 g, and Wako Pure Chemical Industries, Ltd. polymerization initiator V-601 (trade name) 2.5 g were mixed with ethyl acetate. It melt | dissolved in 107.1g and superposed | polymerized at 80 degreeC under nitrogen, and synthesize | combined thermoplastic resin B-11. When measured by GPC, the weight average molecular weight was 32,000. The refractive index of the resin measured with an Abbe refractometer was 1.59.

(2) Synthesis of thermoplastic resin B-10 Methyl methacrylate 246.25 g, β-carboxyethyl acrylate 3.75 g, and Wako Pure Chemical Industries, Ltd. polymerization initiator V-601 (trade name) 2.5 g were mixed with acetic acid. Dissolved in 107.1 g of ethyl and polymerized at 80 ° C. under nitrogen to synthesize thermoplastic resin B-11. When measured by GPC, the weight average molecular weight was 35,000. The refractive index of the resin measured with an Abbe refractometer was 1.49.

(3) Synthesis of thermoplastic resin P-8 <Synthesis of living radical polymerization initiator A>
A 200 ml three-necked flask equipped with a reflux condenser and a gas introduction cock was charged with 20 g (75.8 mmol) of α, α′-dibromo-p-xylene and 70 ml of m-xylene, and heated under reflux with triisopropyl phosphine in a nitrogen stream. A solution of 16.8 g (80.7 mmol) of phyto in 20 ml of m-xylene was added dropwise. After completion of the dropwise addition, the mixture was heated to reflux for 3 hours, and the solvent was distilled off. Purification by silica gel column chromatography gave initiator A in a yield of 53%.

<Synthesis of Exemplified Compound P-8>
In a 200 ml three-necked flask equipped with a reflux condenser and a gas introduction cock, copper bromide 0.41 g (2.86 mmol), styrene 42.7 g (0.407 mol), N, N, N ′, N ′, N ″ -penta After charging 0.5 g (2.86 mmol) of methyldiethylenetriamine and 1.0 g (2.86 mmol) of initiator A, and substituting with nitrogen five times, the mixture was heated for 5 hours under a nitrogen stream at 80 ° C. After returning to room temperature, 30 g of alumina And 50 ml of toluene were added, and the mixture was stirred for 10 minutes and filtered through celite, and the filtrate was poured into a large amount of methanol for precipitation, and the precipitate was collected by filtration, washed with a large amount of methanol, and vacuum-dried at 60 ° C. for 3 hours. The yield was 38%.
A 100 ml three-necked flask equipped with a gas introduction cock was charged with 10 g of the polymer obtained above, 2.3 g (15 mmol) of trimethylsilyl bromide, and 40 ml of methylene chloride, and stirred at room temperature for 24 hours under a nitrogen stream. After adding 10 ml of water and stirring for 1 hour, the solution was poured into a large amount of methanol to cause precipitation. The precipitate was collected by filtration, washed with a large amount of methanol, and vacuum-dried at 60 ° C. for 3 hours. The yield was 97% (number average molecular weight 18,000, weight average molecular weight 20,000). The refractive index of the resin measured with an Abbe refractometer was 1.59.

(4) Synthesis of thermoplastic resin Q-1
tert-butyl acrylate 2.1 g, 2-bromopropionic acid tert-butyl ester 0.72 g, copper (I) bromide 0.46 g, N, N, N ′, N ′, N ″, N ″ -pentamethyldiethylene A liquid mixture consisting of 0.56 g of tetramine and 9 ml of methyl ethyl ketone was prepared and purged with nitrogen. The mixture was stirred for 1 hour at an oil bath temperature of 80 ° C., and 136.2 g of styrene was added under a nitrogen stream. The mixture was stirred at an oil bath temperature of 90 ° C. for 16 hours, and after returning to room temperature, 100 ml of ethyl acetate and 30 g of alumina were added and stirred for 30 minutes. The reaction solution was filtered, and the filtrate was added dropwise to excess methanol. The resulting precipitate was collected by filtration, washed with methanol, and dried to obtain 61 g of resin. This resin was dissolved in 300 ml of toluene, 6 g of p-toluenesulfonic acid monohydrate was added, and the mixture was heated to reflux for 3 hours. The reaction solution is added dropwise to excess methanol. The resulting precipitate was collected by filtration, washed with methanol, and dried to obtain 55 g of block copolymer Q-1. The number average molecular weight of the resin measured by GPC was 32,000, and the weight average molecular weight was 35,000. The refractive index of the resin measured with an Abbe refractometer was 1.59.

[Preparation of organic-inorganic composite composition and production of molded article (lens substrate)]
[Example 1]
The mass ratio of the thermoplastic resin B-11, the compound PL-1 and the surface treatment agent (n-octylbenzoic acid) to the zirconium oxide dimethylacetamide dispersion is ZrO ₂ solid content / B-11 / PL-1 / n. -Octyl benzoic acid was added to 42 / 37.8 / 11.8 / 8.4 and stirred and mixed uniformly, and then the dimethylacetamide solvent was concentrated under heating and reduced pressure. The surface of the concentrated residue was subjected to heat compression molding with a SUS mold (temperature: 180 ° C., pressure: 13.7 MPa, time 2 minutes) to obtain a molded body (lens substrate) having a thickness of 1 mm.

[Examples 2-6 and Comparative Examples 1, 2, 4]
The molded bodies (lens base materials) of Examples 2 to 5 were obtained in the same manner as in Example 1 except that the thermoplastic resin in Example 1 and the compound represented by the general formula (1) were respectively replaced as shown in Table 1. Obtained.
In the methods of Examples 1 and 5, molded bodies (lens substrates) of Comparative Examples 1 and 2 were obtained in the same manner as in Example 1 except that the compound represented by the general formula (1) was not added.
A molded article (lens substrate) of Comparative Example 4 in the same manner as in Example 2, except that di-2-ethylhexyl phthalate (DOP) was added instead of the compound represented by Formula (1) in Example 2. Got.

[Example 7 and Comparative Example 3]
The titanium oxide dispersion described above was added dropwise over 5 minutes at room temperature with stirring to a chloroform solution in which the thermoplastic resin P-8 and the surface treatment agent ((n-octylbenzoic acid) were dissolved. After the compound P-11 represented by the general formula (1) was added and dissolved, the solvent was distilled off (TiO ₂ solid content / P-8 / PL-11 / n-octylbenzoic acid = 39.5 / 44.7 / 7.9 / 7.9) The molded residue (lens substrate) of Example 7 was obtained by molding the concentrated residue in the same manner as in Example 1.
A molded body (lens substrate) of Comparative Example 3 was obtained in the same manner as in Example 1 except that Compound P-11 represented by General Formula (1) was not added in Example 7.

[Example 8 and Comparative Example 5]
A molded body (lens substrate) of Example 7 was obtained in the same manner as Example 5 except that the temperature of heat compression molding was set to 120 ° C.
A molded article of Comparative Example 5 was obtained in the same manner as Comparative Example 2 except that the temperature of heat compression molding was 120 ° C.

[Test example]
Appearance immediately after molding of each molded body (lens substrate) prepared in Examples 1 to 8 and Comparative Examples 1 to 5, and light transmittance and refraction after aging for 720 hours at room temperature, in air and at a humidity of 50% The rates are shown in Table 3.

As is apparent from Table 3, optical components having a refractive index greater than 1.60 and good transparency were obtained by the present invention even after time (Examples 1 to 8). In Comparative Examples 1 to 3, cracks occurred in the molded body over time, and the transmittance and refractive index could not be measured. In Comparative Example 4, the generation of cracks over time was suppressed by the addition of a known plasticizer, but the transmittance and refractive index were inferior. In Comparative Example 6, only a white solid powder was obtained, but a transparent molded product was not obtained.
From Table 3, the organic-inorganic composite composition of the present invention has good moldability and stability over time, and is suitable for the production of optical components having both high refractive index and 1 mm thick molded article having good transparency. I understand that.
The material compositions of Examples 1 to 8 all have a withstand voltage in the range of -1.0 to 7.0 kV, a glass transition temperature in the range of 100 to 400 ° C, and 250 ° C for 2 hours. The volatile component at the time of holding was 2% by mass or less, and the saturated water absorption was 0.5% by mass or less.
In addition, it was confirmed that the use of the organic-inorganic composite composition of the present invention enables the lens shape to be accurately formed with good productivity in accordance with the mold shape such as a concave lens and a convex lens.

  The organic-inorganic composite composition of the present invention has excellent transparency and high refractive index, and is excellent in stability over time. Moreover, according to the present invention, the refractive index can be arbitrarily adjusted. Furthermore, if the organic-inorganic composite composition of the present invention is used, it is easy to provide an optical component having good mechanical strength, heat resistance, weather resistance, and moldability. Therefore, the present invention has high industrial applicability.

Claims (18)

An organic-inorganic composite composition comprising a compound represented by the following general formula (1) having a molecular weight of less than 2000 and inorganic fine particles.
General formula (1)

[In General Formula (1), Ra, Rb and Rc each independently represent a substituent. Q represents an atomic group or a single bond forming a 5- to 8-membered ring. n1 and n2 each independently represents an integer of 0 to 5. n3 represents 0 or 1. However, (n1 + n3) and (n2 + n3) do not exceed 5. ]   The organic-inorganic composite composition according to claim 1, wherein the inorganic fine particles are metal oxide fine particles having a refractive index of 1.90 to 3.00.   3. The organic-inorganic composite composition according to claim 1, wherein the inorganic fine particles are fine particles containing zirconium oxide, zinc oxide, or titanium oxide.   The organic-inorganic composite composition according to any one of claims 1 to 3, wherein the inorganic fine particles have a number average particle size of 1 to 15 nm.   The organic-inorganic composite composition according to any one of claims 1 to 4, comprising 20% by mass or more of the inorganic fine particles.   The organic-inorganic composite composition according to any one of claims 1 to 5, wherein the compound represented by the general formula (1) has a molecular weight of less than 1000.   The organic-inorganic composite composition according to any one of claims 1 to 6, further comprising a thermoplastic resin having a functional group capable of forming an arbitrary chemical bond with the inorganic fine particles at a polymer terminal or a side chain. object. The organic-inorganic composite composition according to claim 7, wherein the thermoplastic resin is a thermoplastic resin having a functional group selected from the following in the side chain.

[R ¹¹ , R ¹² , R ¹³ and R ¹⁴ are each independently a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkynyl group, or a substituted or unsubstituted group. Represents an aryl group. _{], - SO 3 H, -OSO} 3 H, -CO 2 H or _{^{-Si (OR 15) m1 R 16}} 3-m1 [R 15, R 16 are each independently 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 m1 represents an integer of 1 to 3. ]   The organic-inorganic composite composition according to claim 8, wherein the functional group is contained in an average range of 0.1 to 20 per polymer chain. The organic-inorganic composite composition according to claim 8 or 9, wherein the thermoplastic resin is a copolymer containing a monomer represented by the general formula (2) as a polymerization unit.

[In General Formula (1), R represents a hydrogen atom, a halogen atom or a methyl group, and X represents —CO ₂ —, —OCO—, —CONH—, —OCONH—, —OCOO—, —O—, — Represents a divalent linking group selected from S-, -NH-, a substituted or unsubstituted arylene group. Y represents a divalent linking group having 1 to 30 carbon atoms, and q represents an integer of 0 to 18. Z represents a functional group selected from the following. ]

[R ¹¹ , R ¹² , R ¹³ and R ¹⁴ are each independently a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkynyl group, or a substituted or unsubstituted group. Represents an aryl group. _{], - SO 3 H, -OSO} 3 H, -CO 2 H or _{^{-Si (OR 15) m1 R 16}} 3-m1 [R 15, R 16 are each independently 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 m1 represents an integer of 1 to 3. ] 8. The organic-inorganic composite composition according to claim 7, wherein the thermoplastic resin is a thermoplastic resin having a functional group selected from the following at least at one position of a polymer terminal.

[R ²¹ , R ²² , R ²³ and R ²⁴ are each independently a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkynyl group, or a substituted or unsubstituted group. Represents an aryl group. _{], -SO 3 H, -OSO 3 H} , -CO 2 H, _{^{and, -Si (OR 25) m2 R}} 26 3-m2 [R ^25, R ²⁶ are each independently a hydrogen atom, a substituted or unsubstituted It represents an alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkynyl group, or a substituted or unsubstituted aryl group. m2 represents an integer of 1 to 3. ]   The organic-inorganic composite composition according to claim 7, wherein the thermoplastic resin is a block copolymer composed of a hydrophobic segment and a hydrophilic segment.   The molded object which shape | molded the organic inorganic composite composition as described in any one of Claims 1-12.   The molded article according to claim 13, wherein the light transmittance in terms of 1 mm thickness is 70% or more at a wavelength of 589 nm.   The molded article according to claim 13 or 14, wherein a refractive index at a wavelength of 589 nm is 1.60 or more.   The maximum thickness is 0.1 mm or more, The molded product according to any one of claims 13 to 15.   An optical component comprising the molded body according to any one of claims 13 to 16.   The optical component according to claim 17, wherein the optical component is a lens substrate.