JP5345294B2 - Organic-inorganic composite material, manufacturing method thereof, and optical component - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an organic-inorganic composite material which has inorganic micro particles uniformly dispersed in a resin matrix, and exhibits a good mold releasability, an excellent transparency and a high refractive index. <P>SOLUTION: The organic-inorganic composite material includes inorganic micro particles having a number average particle size of 1-15 nm dispersed in a thermoplastic resin having at least one kind of structure unit expressed by the general formula (1). In the formula, R<SP>1</SP>and R<SP>2</SP>each represent a hydrogen atom, a halogen atom, an alkyl group or an aryl group; A represents an oxygen atom or a sulfur atom; m is an integer of &ge;1; and n is an integer of &ge;2. <P>COPYRIGHT: (C)2009,JPO&amp;INPIT

Description

  The present invention relates to an organic-inorganic composite material excellent in high refraction, transparency, and workability (particularly releasability), and a lens substrate (for example, spectacle lens, optical device lens, opt) The present invention relates to optical components such as electronics lenses, laser lenses, pickup lenses, in-vehicle camera lenses, portable camera lenses, digital camera lenses, OHP lenses, and the like.

  In recent years, research on optical materials has been actively conducted, and particularly in the field of lens materials, high refractive index, low dispersibility (that is, high Abbe number), heat resistance, transparency, easy moldability, light weight, chemical resistance Development of materials with excellent properties and solvent resistance is strongly desired.

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

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

Since it is difficult to raise the refractive index only with an organic substance, attempts have been made to produce a high refractive index material by dispersing an inorganic substance having a high refractive index in a resin matrix (see Patent Documents 4 and 5). In order to obtain a transparent molded article having a high refractive index by such an organic-inorganic composite material, it is necessary to uniformly disperse high refractive index inorganic fine particles having a particle size of 15 nm or less in a resin at a high concentration. . However, a resin in which the above-mentioned inorganic fine particles are compounded at a high concentration has high adhesion to the mold at the time of molding, and the resin adheres to the mold surface at the time of mold release or excessive stress is applied. There are problems such as deformation and optical distortion in the molded product. In order to improve releasability, a technique for applying a release agent to a mold (see Patent Document 6) has been proposed. However, even if these methods are used, the operation is complicated, so There is a problem that the cost is increased, and an improvement is desired.
JP 2002-131502 A Japanese Patent Laid-Open No. 10-298287 JP 2004-244444 A JP 61-291650 A JP 2003-73564 A JP 2005-270801 A

Therefore, an organic / inorganic composite material having both high refractive properties, transparency, and processability, and an optical component such as a lens including the organic inorganic composite material have not yet been found, and development thereof has been desired.
The present invention has been made in view of the above-mentioned circumstances, and the object thereof is an organic-inorganic composite in which inorganic fine particles are uniformly dispersed in a resin matrix, has good releasability, and has excellent transparency and a high refractive index. The object is to provide a material and an optical component such as a lens substrate using the same.

  As a result of intensive studies to achieve the above-mentioned object, the present inventors have made the unit structure having a specific structure in the resin, thereby improving the high refractive index of the organic-inorganic composite material in which inorganic fine particles are dispersed. It has been found that the releasability from the molding die can be improved without impairing the high transparency, and the present invention has been completed.

That is, the present invention is specified in the matters described in [1] to [11] below.
[1] An organic-inorganic composite material in which inorganic fine particles having a number average particle size of 1 to 15 nm are dispersed in a thermoplastic resin having at least one unit structure represented by the following general formula (1).

〔一般式（１）中、Ｒ¹およびＲ²はそれぞれ独立に水素原子、ハロゲン原子、置換もしくは無置換のアルキル基、または置換もしくは無置換のアリール基を表し、Ａは酸素原子または硫黄原子を表し、ｍは１以上の整数を表し、ｎは２以上の整数を表す。ｍ個のＲ¹は互いに同一であっても異なっていてもよく、ｍ個のＲ²は互いに同一であっても異なっていてもよい。〕

[In General Formula (1), R ¹ and R ² each independently represents a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group, and A represents an oxygen atom or a sulfur atom. M represents an integer of 1 or more, and n represents an integer of 2 or more. The m R ^{1 s} may be the same as or different from each other, and the m R ^{2 s} may be the same as or different from each other. ]

[2] The organic-inorganic composite material according to [1], wherein the polymer constituting the thermoplastic resin has at least one unit structure represented by the general formula (1) via a chemical bond. .
[3] The thermoplastic resin is

［Ｒ¹¹〜Ｒ¹⁶はそれぞれ独立に水素原子、置換もしくは無置換のアルキル基、または置換もしくは無置換のアリール基を表わす。］、―ＳＯ₃Ｈ、―ＯＳＯ₃Ｈ、―ＣＯ₂Ｈ、―ＯＨ、および―Ｓｉ（ＯＲ¹⁷）_xＲ¹⁸ _3-x［Ｒ¹⁷およびＲ¹⁸はそれぞれ独立に水素原子、置換もしくは無置換のアルキル基、または置換もしくは無置換のアリール基を表し、ｘは１〜３の整数を表す。］からなる群より選択される官能基を有することを特徴とする［１］または［２］のいずれか一項に記載の有機無機複合材料。
［４］ 前記無機微粒子の波長５８９ｎｍにおける屈折率が１.９０〜３.００であることを特徴とする［１］〜［３］のいずれか一項に記載の有機無機複合材料。
［５］ 前記無機微粒子が、ジルコニア、酸化亜鉛、酸化錫およびチタニアからなる群より選ばれるいずれか一種であることを特徴とする［１］〜［４］のいずれか一項に記載の有機無機複合材料。
［６］ 波長５８９ｎｍにおける屈折率が１.６３以上、かつ、波長５８９ｎｍにおける厚さ１ｍｍ換算の光線透過率が８０％以上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材料。
［７］ ［１］〜［６］のいずれか一項に記載の有機無機複合材料を含んで構成される光学部品。

[R ^{11 to} R ¹⁶ each independently represents a hydrogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group. _{], - SO 3 H, -OSO} 3 H, -CO 2 H, -OH, and _{^{-Si (OR 17) x R 18}} 3-x [R 17 and R ¹⁸ each independently represent a hydrogen atom, a substituted or unsubstituted An alkyl group, or a substituted or unsubstituted aryl group, and x represents an integer of 1 to 3. The organic-inorganic composite material according to any one of [1] and [2], which has a functional group selected from the group consisting of:
[4] The organic-inorganic composite material according to any one of [1] to [3], wherein the inorganic fine particles have a refractive index of 1.90 to 3.00 at a wavelength of 589 nm.
[5] The organic and inorganic materials according to any one of [1] to [4], wherein the inorganic fine particles are any one selected from the group consisting of zirconia, zinc oxide, tin oxide, and titania. Composite material.
[6] Any one of [1] to [5], wherein the refractive index at a wavelength of 589 nm is 1.63 or more, and the light transmittance in terms of 1 mm thickness at a wavelength of 589 nm is 80% or more. The organic-inorganic composite material described in 1.
[7] An optical component comprising the organic-inorganic composite material according to any one of [1] to [6].

[8] The optical component according to [7], wherein the optical component is a lens substrate.
[9] An organic-inorganic composite material comprising a step of dispersing inorganic fine particles having a number average particle size of 1 to 15 nm in a thermoplastic resin having at least one unit structure represented by the following general formula (1) Manufacturing method.

〔一般式（１）中、Ｒ¹およびＲ²はそれぞれ独立に水素原子、ハロゲン原子、置換もしくは無置換のアルキル基、または置換もしくは無置換のアリール基を表し、Ａは酸素原子または硫黄原子を表し、ｍは１以上の整数を表し、ｎは２以上の整数を表す。ｍ個のＲ¹は互いに同一であっても異なっていてもよく、ｍ個のＲ²は互いに同一であっても異なっていてもよい。〕

[In General Formula (1), R ¹ and R ² each independently represents a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group, and A represents an oxygen atom or a sulfur atom. M represents an integer of 1 or more, and n represents an integer of 2 or more. The m R ^{1 s} may be the same as or different from each other, and the m R ^{2 s} may be the same as or different from each other. ]

[10] The method for producing an organic-inorganic composite material according to [9], wherein the inorganic fine particles are dispersed in the thermoplastic resin in the presence of a dispersant.
[11] The method for manufacturing an optical component according to [7] and [8], wherein the molding is performed using a mold.

  According to the present invention, an organic-inorganic composite material having both excellent releasability, high refraction, and transparency, and an optical component having high accuracy, high transparency, and high refraction, comprising the same. Can be provided.

  Hereinafter, the organic-inorganic composite material of the present invention, the method for producing the same, and the optical component including the same 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.

[Inorganic fine particles]
In the organic-inorganic composite material of the present invention, inorganic fine particles having a number average particle size of 1 to 15 nm are used. If the number average particle size of the inorganic fine particles is too small, the characteristics unique to the substance constituting the fine particles may change. Conversely, if the number average particle size is too large, the effect of Rayleigh scattering becomes remarkable, and the transparency of the organic-inorganic composite material is extremely high. May fall. Therefore, the number average particle size of the inorganic fine particles in the present invention needs to be 1 to 15 nm, preferably 2 to 13 nm, and more preferably 3 to 10 nm.

  Examples of the inorganic fine particles used in the present invention include oxide fine particles, sulfide fine particles, selenide fine particles, telluride fine particles and the like. More specifically, titania fine particles, zinc oxide fine particles, zirconia fine particles, tin oxide fine particles, zinc sulfide fine particles and the like can be mentioned, preferably titania fine particles, zirconia fine particles and zinc sulfide fine particles, more preferably titania fine particles. Although it is a zirconia fine particle, it is not limited to these. In the present invention, one type of inorganic fine particles may be used, or a plurality of types of inorganic fine particles may be used in combination.

  The method for producing inorganic fine particles used in the present invention is not particularly limited, and any known method may be adopted. Desired oxide fine particles can be obtained by using a metal halide or alkoxy metal as a raw material and hydrolyzing in a reaction system containing water.

  For example, titanyl sulfate is exemplified as a synthetic raw material for titania fine particles. Metal alkoxides such as titanium tetraisopropoxide can also be suitably used as a raw material. As a synthesis method, use a known method described in Japanese Journal of Applied Physics, 37, 4603-4608 or (1998) Langmuir, Vol. 16, No. 1, 241-246 (2000). Can do. In particular, in the case of synthesizing oxide fine particles by a sol production method, for example, as in the synthesis of titania fine particles using titanyl sulfate as a raw material, this is passed through a precursor such as hydroxide and then dehydrated or condensed with acid or alkali. A procedure for peptizing to form a hydrosol is also possible. In the procedure via such a precursor, it is preferable from the viewpoint of the purity of the final product that the precursor is isolated and purified by any method such as filtration or centrifugation. An appropriate surfactant such as sodium dodecylbenzenesulfonate (abbreviated as DBS) or dialkylsulfosuccinate monosodium salt (manufactured by Sanyo Chemical Industries, Ltd., trade name is Eleminol JS-2) is added to the hydrosol to obtain a sol The particles may be isolated by making them water-insoluble. For example, a known method described in Coloring Materials, Vol. 57, No. 6, 305-308 (1984) can be used.

Further, as a method other than the method of hydrolyzing in water, a method of preparing inorganic fine particles in an organic solvent can be employed.
Examples of the solvent used in this method include acetone, methyl ethyl ketone (MEK), dichloromethane, chloroform, toluene, ethyl acetate, cyclohexanone, anisole and the like. These may be used alone or as a mixture of two or more.

  The refractive index of the inorganic fine particles used in the present invention at a wavelength of 589 nm is preferably 1.90 to 3.00, more preferably 1.90 to 2.70, and 2.00 to 2.70. More preferably it is. If inorganic fine particles having a refractive index of 1.90 or more are used, it becomes easy to produce an organic-inorganic composite material having a refractive index greater than 1.65. If inorganic fine particles having a refractive index of 3.00 or less are used, the transmittance is 80%. There exists a tendency which is easy to produce the above organic inorganic composite material. In addition, the refractive index in this invention is the value measured at 25 degreeC about the light of wavelength 589nm with the Abbe refractometer (Atago DR-M4).

[Thermoplastic resin]
The thermoplastic resin used in the present invention is characterized by having at least one unit structure represented by the general formula (1). The unit structure represented by the general formula (1) may be bonded to the polymer constituting the thermoplastic resin via a chemical bond, or may be included in a compound included in the thermoplastic resin. Good. From the viewpoint of suppressing phase separation between the thermoplastic resin and the inorganic fine particles, an embodiment in which the polymer is included in the polymer constituting the thermoplastic resin through a chemical bond is preferable. Here, examples of the “chemical bond” include a covalent bond, an ionic bond, a coordination bond, and a hydrogen bond.

  The total content of the unit structure represented by the general formula (1) in the thermoplastic resin is preferably 0.01 to 10% by mass, more preferably 0.05 to 8% by mass, More preferably, it is 1-5 mass%. If the total content is 0.01% by mass or more, the effect of improving the releasability is easily obtained, and if it is 10% by mass or less, phase separation from the resin matrix is difficult to occur, so that the transmittance and refractive index of the entire resin are increased. It tends to be easy to do. Hereinafter, the unit structure represented by the general formula (1) will be described in detail.

In general formula (1), R ¹ and R ² each independently represent a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group, and A represents an oxygen atom or a sulfur atom. , M represents an integer of 1 or more, and n represents an integer of 2 or more. The m R ^{1 s} may be the same as or different from each other, and the m R ^{2 s} may be the same as or different from each other.

Examples of the halogen atom that can be selected as R ¹ and R ² include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and a fluorine atom, a chlorine atom, and a bromine atom are preferable. 1-10 are preferable, as for carbon number of an alkyl group, 1-9 are more preferable, and 1-8 are more preferable. 6-18 are preferable, as for carbon number of an aryl group, 6-16 are more preferable, and 6-12 are more preferable. The alkyl group and the aryl group may each be substituted. As the substituent, in addition to the alkyl group and the aryl group, a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom), an alkoxy group (For example, a methoxy group and an ethoxy group) can be mentioned. For example, an aralkyl group can be mentioned as a specific example of a substituted alkyl group. 7-18 are preferable, as for carbon number of an aralkyl group, 7-16 are more preferable, and 7-14 are more preferable. R ¹ and R ² are more preferably a hydrogen atom, a methyl group, an ethyl group, a propyl group, a trifluoromethyl group, a phenyl group, or a benzyl group, more preferably a hydrogen atom, a methyl group, a phenyl group, or a benzyl group. Particularly preferred are a hydrogen atom and a methyl group.

  A represents an oxygen atom or a sulfur atom, but it is preferable to select an oxygen atom from the viewpoint that coloring can be suppressed.

  m represents the number of repeating units and is an integer of 1 or more. Preferably it is 1-6, More preferably, it is 1-4, More preferably, it is 2. n represents the number of repeating units and is an integer of 2 or more. Preferably it is 2-1,000, More preferably, it is 3-500, More preferably, it is 3-300. If the number of repeating units is smaller than 2, sufficient releasability cannot be obtained. If the number of repeating units is 1,000 or less, phase separation from the resin matrix is difficult to occur, so that the transmittance and the refractive index of the entire thermoplastic resin tend not to decrease.

  As a preferred embodiment of the unit structure represented by the general formula (1), a unit structure represented by the following general formula (1a) can be exemplified.

一般式（１ａ）において、ｍ１は１以上の整数を表し、Ａ¹は酸素原子または硫黄原子を表し、ｎ１は２以上の整数を表す。ｍ１、Ａ¹およびｎ１の好ましい範囲は、一般式（１）のｍ、Ａおよびｎの好ましい範囲と同じである。

In the general formula (1a), m1 represents an integer of 1 or more, A ¹ represents an oxygen atom or a sulfur atom, and n1 represents an integer of 2 or more. The preferred ranges of m1, A ¹ and n1 are the same as the preferred ranges of m, A and n in the general formula (1).

  Another preferred embodiment of the unit structure represented by the general formula (1) includes a unit structure represented by the following general formula (1b).

一般式（１ｂ）において、ｎ２は２以上の整数を表す。ｎ２の好ましい範囲は、一般式（１）のｎの好ましい範囲と同じである。

In the general formula (1b), n2 represents an integer of 2 or more. The preferable range of n2 is the same as the preferable range of n in the general formula (1).

  In the present invention, the unit structure represented by the general formula (1) may be introduced into the polymer constituting the thermoplastic resin. The introduction site of the unit structure may be at the end of the polymer, in the main chain, or in the side chain. Moreover, you may introduce | transduce into several site | parts.

  As a method for introducing the unit structure represented by the general formula (1) into the polymer, a polymerization method using an initiator, a terminator, a chain transfer agent, a monomer or the like having the unit structure, or a general formula (1 And a method of reacting a compound having a unit structure represented by any of the above with a functional group in the polymer.

  When a polymer having these unit structures is produced by polymerization using a monomer having a unit structure represented by the general formula (1), the monomer used is selected without particular limitation as long as it has polymerizability. can do. As such a monomer, for example, a compound represented by the following general formula (2) can be exemplified.

In the general formula (2), R ¹⁰ represents a hydrogen atom or a methyl group, and R ^{11 to} R ¹⁴ each independently represents a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group. represents, a ¹¹ and a ¹² each independently represent an oxygen atom or a sulfur atom, represent an integer of 1 or more, respectively m11 and m12 independently represents an integer of 2 or more n11 and n12 each independently. When m11 is 2 or more, m11 R ¹¹ and R ¹² may be the same as or different from each other. When m12 is 2 or more, m12 R ¹³ and R ¹⁴ may be the same as each other. May be different. R ¹⁵ represents a hydrogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group.

The preferable range of R ^{11 to} R ¹⁴ in the general formula (2) is the same as the preferable range of R ¹ and R ^{2 in} the general formula (1). A preferable range of A ¹¹ and A ¹² in the general formula (2) is the same as a preferable range of A in the general formula (1). Moreover, the preferable range of m11 and m12 in General formula (2) is the same as the preferable range of m of General formula (1). Furthermore, the preferable range of n11 and n12 in General formula (2) is the same as the preferable range of n of General formula (1).

Formula (2) number of carbon atoms in the alkyl group may be selected as R ¹⁵ in is preferably 1 to 10, more preferably 1-9, 1-8 is more preferable. 6-18 are preferable, as for carbon number of an aryl group, 6-16 are more preferable, and 6-12 are more preferable. The alkyl group and the aryl group may each be substituted. As the substituent, in addition to the alkyl group and the aryl group, a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom), an alkoxy group (For example, a methoxy group and an ethoxy group) can be mentioned. R ¹⁵ is preferably a hydrogen atom, an alkyl group, an aryl group, or an alkylaryl group.

  Among the compounds represented by the general formula (2), a compound represented by the following general formula (2a) can be preferably used.

In the general formula (2a), R ²⁰ represents a hydrogen atom or a methyl group, R ²¹ and R ²² each independently represents a substituted or unsubstituted alkylene group, and n ²¹ and n ²² each independently represents an integer of 2 or more. , R ²³ represents a hydrogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group.
R ²¹ and the carbon number of the alkylene group R ²² is preferably 1 to 8, more preferably 1 to 6, 1 to 4 is more preferred. The alkylene group may be substituted, and in addition to an alkyl group and an aryl group, a halogen atom (eg, fluorine atom, chlorine atom, bromine atom, iodine atom), alkoxy group (eg, methoxy group, ethoxy group) ). Specific examples of the alkylene group include an ethylene group, a methylethylene group, a propylene group, and a butylene group.
The preferable range of n21 and n22 in the general formula (2a) is the same as the preferable range of n in the general formula (1). Further, preferred ranges of R ²³ in the general formula (2a) are the same as the preferred range of R ¹⁵ in the general formula (2).

  The thermoplastic resin used in the present invention may include a polymer having a block body including a unit structure represented by the general formula (1). As a repeating unit of such a block body, the structure represented by the following general formula (3) can be illustrated.

In the general formula (3), R ^{31 to} R ³⁴ each independently represent a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group, and A ³¹ and A ³² each independently An oxygen atom or a sulfur atom is represented, m31 and m32 each independently represent an integer of 1 or more, and n31 and n32 each independently represent an integer of 2 or more. When m31 is 2 or more, m31 R ³¹ and R ³² may be the same or different, and when m32 is 2 or more, m32 R ³³ and R ³⁴ may be the same. May be different. B ¹ and B ² each independently represents a cyano group, a carboxymethyl group or a carboxyethyl group.
The preferred range of R ^{31 to} R ³⁴ in the general formula (3) is the same as the preferred range of R ¹ and R ^{2 in} the general formula (1). The preferred range of A ³¹ and A ³² in the general formula (3) is the same as the preferred range of A in the general formula (1). Moreover, the preferable range of m31 and m32 in General formula (3) is the same as the preferable range of m of General formula (3). Furthermore, the preferable range of n31 and n32 in General formula (3) is the same as the preferable range of n of General formula (1).

  Among the repeating units represented by the general formula (3), the repeating units represented by the following general formula (3a) can be preferably used.

In the general formula (3a), R ⁴¹ and R ⁴² each independently represent a substituted or unsubstituted alkylene group, n ⁴¹ and n ⁴² each independently represent an integer of 2 or more, and B ¹ and B ² each independently represent cyano Represents a group, a carboxymethyl group or a carboxyethyl group.
The preferred range of R ⁴¹ and R ⁴² in the general formula (3a) is the same as the preferred range of R ²¹ and R ²² in the general formula (2a). The preferable range of n41 and n42 in General formula (3a) is the same as the preferable range of n of General formula (1).

  Specific examples of the monomer having the unit structure represented by the general formula (1) are listed below as S-1 to S-25 and S-31 to S-35, but these monomers can be used in the present invention. It is not limited to the specific example. Specific examples of the repeating unit of the block body having the unit structure represented by the general formula (1) are listed below as S-26 to S-30, but the repeating unit of the block body that can be employed in the present invention. Is not limited to these specific examples. In the following, n and n ′ represent an integer of 2 or more, and x represents an integer of 1 or more.

  The thermoplastic resin used in the present invention may contain a compound having a unit structure represented by the general formula (1) separately from the polymer. Such a compound may be contained in a thermoplastic resin together with a polymer having a unit structure represented by the general formula (1), or a polymer not having a unit structure represented by the general formula (1) And may be included in the thermoplastic resin.

  Examples of the compound having a unit structure represented by the general formula (1) include known compounds having these unit structures. The compound to be used can be selected without particular limitation. Specific examples of such compounds are listed below, but the compounds that can be employed in the present invention are not limited to these specific examples. In the following, n, n ′ and n ″ represent an integer of 2 or more, x and y represent an integer of 0 or more, a represents an integer of 0 or more, and b represents an integer of 1 or more. Further, the following exemplary compounds are compounds in which the atom corresponding to A in the general formula (1) is an oxygen atom, but compounds in which the atom corresponding to A is substituted with a sulfur atom can also be exemplified. .

  The compound having the unit structure represented by the general formula (1) can be introduced into the thermoplastic resin by adding and mixing into the polymer constituting the thermoplastic resin. As a method of addition, a method of dropping a compound having a unit structure represented by the general formula (1) into a polymer solution alone or in a solution state, or a place where a polymer melt is kneaded is represented by the general formula (1 And a method of dropping a compound having a unit structure represented by).

The amount of the compound having a unit structure represented by the general formula (1) in the thermoplastic resin used in the present invention is preferably 0.01 to 15% by mass,
More preferably, it is 0.05-10 mass%, and it is further more preferable that it is 0.05-5 mass%.

  The thermoplastic resin used in the present invention preferably has a refractive index at a wavelength of 589 nm of greater than 1.50, more preferably greater than 1.55, and even more preferably greater than 1.60.

  The thermoplastic resin used in the present invention preferably has a light transmittance at a wavelength of 589 nm of 75% or more, more preferably 80% or more, and further preferably 85% or more.

  The thermoplastic resin used in the present invention preferably has a glass transition temperature of 80 ° C to 400 ° C, and more preferably 100 ° 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.

  The thermoplastic resin used in the present invention preferably has a number average molecular weight of 1,000 to 500,000, more preferably 3,000 to 300,000, and 5,000 to 200,000. It is more preferable that it is 10,000 to 100,000. If the number average molecular weight is 1,000 or more, an organic-inorganic composite material having practical mechanical strength is easily obtained, and if it is 500,000 or less, molding tends to be easily performed. In addition, the polymer constituting the thermoplastic resin used in the present invention may be either an addition polymer or a condensation polymer, and the type of polymer is not limited.

  In the present invention, a thermoplastic resin containing sulfur may be used. For example, examples of the polymer having a dithian structure include those described in JP-A-11-202101, JP-A-2002-131502, JP-A-2005-29608, and the like. Examples of the resin having a urethane structure include those described in JP-A Nos. 2001-342252 and 2001-106761. Examples of the resin having a phenylene sulfide structure include those described in JP-A-7-316295, JP-A-8-92367, JP-A-8-104751, and JP-A-8-100065.

  Examples of other resins having a refractive index of 1.65 or more include those described in JP-A Nos. 5-178929 and 2002-201262.

  The resin used in the present invention is improved in compatibility with inorganic fine particles.

［Ｒ¹¹〜Ｒ¹⁶はそれぞれ独立に水素原子、ハロゲン原子または置換または無置換のアルキル基を表わす。］、−ＳＯ₃Ｈ、−ＯＳＯ₃Ｈ、−ＣＯ₂Ｈ、−ＯＨ、および―Ｓｉ（ＯＲ¹⁷）_xＲ¹⁸ _3-x［Ｒ¹⁷およびＲ¹⁸はそれぞれ独立に水素原子、置換または無置換のアルキル基、置換または無置換のアルケニル基、置換または無置換のアルキニル基、または置換または無置換のアリール基を表し、ｘは１〜３の整数を表す。］からなる群より選択される官能基を有していることが好ましい。さらに好ましくは、

[R ^{11 to} R ¹⁶ each independently represents a hydrogen atom, a halogen atom, or a substituted or unsubstituted alkyl group. _{], - SO 3 H, -OSO} 3 H, -CO 2 H, -OH, and _{^{-Si (OR 17) x R 18}} 3-x [R 17 and R ¹⁸ each independently represent 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, and x represents an integer of 1 to 3. It preferably has a functional group selected from the group consisting of More preferably,

−ＳＯ₃Ｈ、−ＯＳＯ₃Ｈ、−ＣＯ₂Ｈから選ばれる官能基を有していることであり、特に好ましくは、

Having a functional group selected from —SO ₃ H, —OSO ₃ H, —CO ₂ H, particularly preferably

−ＳＯ₃Ｈ、−ＣＯ₂Ｈから選ばれる官能基を有していることである。

It has a functional group selected from —SO ₃ H and —CO ₂ H.

  The functional group is preferably contained in a polymer constituting the thermoplastic resin via a chemical bond. The functional group introduction site may be at the end of the polymer, in the main chain, or in the side chain. Moreover, you may introduce | transduce into several site | parts.

  These functional groups are preferably contained in the resin in an amount of 0.1 to 20% by mass, more preferably 0.2 to 15% by mass, and still more preferably 0.2 to 10% by mass. . If the content in the resin is 0.1% by mass or more, the effect of improving compatibility with inorganic fine particles is easily exhibited, and if it is 20% by mass or less, the thermoplasticity tends to be maintained when an organic-inorganic composite material is formed. There is.

  The method for introducing the functional group into the main chain or side chain of the polymer is not particularly limited. Examples thereof include a method of copolymerizing a monomer having a functional group and a method of introducing a functional group into the main chain or side chain of the polymer by reaction.

  As a method for introducing a functional group into a polymer terminal, a polymer is obtained by polymerization using an initiator having a functional group, a terminator, a chain transfer agent or the like, for example, a phenol terminal part of a polycarbonate obtained from bisphenol A is functionalized. Examples thereof include a method of modifying with a reactive agent containing a group. For example, new polymer experiment 2, synthesis and reaction of polymer (1) synthesis of addition polymer (edited by Society of Polymer Science) 110-112, serial transfer method vinyl system using sulfur-containing chain transfer agent Monomer radical polymerization, new polymer experiment 2, synthesis and reaction of polymers (1) Synthesis of addition-type polymers (edited by the Society of Polymer Science) 255-256, functional group-containing initiators and / or functional groups Living cationic polymerization using a containing terminator, ring opening metathesis polymerization using a sulfur-containing chain transfer agent described in Macromolecules, Vol. 36, Item 7020 to Item 7026 (2003) can be exemplified.

  When producing the organic-inorganic composite material of the present invention, only one of the above thermoplastic resins may be used alone, or two or more of them may be mixed and used. When using 2 or more types mixed, it is preferable that the resin mixture after mixing satisfy | fills the conditions of said refractive index.

  Specific examples of monomers preferably used in producing the thermoplastic resin used in the present invention are given below. However, monomers that can be used in the present invention are not limited to these. These monomers can be copolymerized with a monomer having a unit structure represented by the general formula (1).

  Preferred specific examples of the thermoplastic resin and thermoplastic resin composition used in the present invention are exemplified in the following table as combinations of constituent monomers and initiators. However, the thermoplastic resin and the thermoplastic resin composition used in the present invention are not limited to these specific examples.

[Organic-inorganic composite material and its manufacturing method]
The organic-inorganic composite material of the present invention is characterized in that inorganic fine particles having a number average particle size of 1 to 15 nm are dispersed in a thermoplastic resin having at least one unit structure represented by the general formula (1). . The method for producing the organic-inorganic composite material of the present invention is not particularly limited. Specifically, a method of independently synthesizing a thermoplastic resin and inorganic fine particles and mixing them, a method of synthesizing a thermoplastic resin in the presence of pre-synthesized inorganic fine particles, and in the presence of a pre-synthesized thermoplastic resin And a method of synthesizing inorganic fine particles, a method of synthesizing both thermoplastic resin and inorganic fine particles at the same time, and any of these methods may be used.

  For example, when adopting a method in which a thermoplastic resin and inorganic fine particles are independently synthesized and mixed together, the inorganic fine particles may be mixed with the resin solution at once, or may be gradually dropped into the resin solution. . Further, a plasticizer may be present during the stirring and mixing. Such a plasticizer may be added in advance to the resin solution or the inorganic fine particle dispersion, or may be added when the resin solution and the inorganic fine particle dispersion are mixed.

  The content of the inorganic fine particles in the organic-inorganic composite material of the present invention is preferably 1 to 90% by mass, more preferably 5 to 80% by mass, and further preferably 10 to 70% by mass. If the content of the inorganic fine particles is 1% by mass or more, the effect of improving the refractive index is easily obtained, and if it is 90% by mass or less, the mechanical strength of the organic-inorganic composite material tends to be prevented from being lowered.

  The organic-inorganic composite material of the present invention preferably has a refractive index at a wavelength of 589 nm of 1.63 or more, more preferably 1.65 or more, and even more preferably 1.70 or more. If the refractive index at a wavelength of 589 nm is 1.63 or more, it is easy to provide an optical component such as a lens having more preferable properties.

  In the organic-inorganic composite material of the present invention, the light transmittance at a wavelength of 589 nm is preferably 80% or more, more preferably 85% or more, and further preferably 90% or more. If the light transmittance at a wavelength of 589 nm is 80% or more, it is easy to provide an optical component such as a lens having more preferable properties. The light transmittance in the present invention is a value measured with a UV-visible absorption spectrum measuring apparatus UV-3100 (Shimadzu Corporation) after molding a resin to prepare a substrate having a thickness of 1.0 mm.

[Dispersant]
When producing the organic-inorganic composite material of the present invention by dispersing inorganic fine particles in a thermoplastic resin, the inorganic fine particles may be dispersed in the thermoplastic resin using a dispersant. The molecular weight of the dispersant is usually about 100 to 1000. If the molecular weight is too large, it may be difficult to increase the refractive index of the organic-inorganic composite material.

  If an organic compound (a type of dispersant) that is compatible with a resin matrix mainly composed of thermoplastic resin is coordinated or modified to inorganic fine particles, the dispersibility of the inorganic fine particles in the resin matrix is improved. The transparency and mechanical strength of the organic-inorganic composite material of the invention may be improved. The effect of the dispersant is considered to be due to a combination of an effect of suppressing aggregation of fine particles and an effect of improving compatibility with the resin matrix.

In the present invention, it is preferable to use a dispersant having a structure represented by the following general formula (4).
General formula (4)
X-R

  In the general formula (4), X represents a functional group capable of forming an arbitrary chemical bond with the surface of the inorganic fine particles used in the present invention, and R represents a resin matrix mainly composed of the thermoplastic resin used in the present invention. Represents a monovalent group or polymer having 1 to 30 carbon atoms having compatibility or reactivity. Here, examples of the “chemical bond” include a covalent bond, an ionic bond, a coordination bond, a hydrogen bond, and the like.

  There is no limitation on the coordination method of the dispersant to the inorganic fine particles, the modification method by covalent bond, and the molecular structure of the organic substance used for this. Preferable specific examples of X coordinated to inorganic fine particles by a coordinate bond include sulfur-containing organic compounds such as thiols and sulfonic acids; phosphorus-containing organic ligands having phosphine, phosphine oxide, phosphonic acid, phosphate ester, etc. A nitrogen-containing ligand having an alkylamine, an aromatic amine or the like; a ligand having a carboxylic acid. Among these examples, phosphorus-containing organic ligands that are preferably used are, for example, “KAYAMER PM-21” manufactured by Nippon Kayaku and “dibenzyl phosphate” manufactured by Tokyo Chemical Industry.

  Further, preferred specific examples of X for modifying inorganic fine particles with a covalent bond include silane coupling agents, titanate coupling agents, and aluminum-based compounds conventionally used for surface treatment of oxides such as silica, alumina, and titania. List metal alkoxide groups that are active functional groups such as coupling agents, and phosphonic acid derivatives such as phosphonic acids and phosphonic acid esters that are known to form covalent bonds with metal oxide surfaces under relatively mild conditions. Can do. Among these, a silane coupling agent is preferable, and methods described in JP-A-5-221640, JP-A-9-100111, JP-A-2002-187721, and the like can be used.

On the other hand, when R in the general formula (4) is a group having compatibility or reactivity with the resin matrix, the chemical structure is the same as part or all of the chemical structure of the resin that is the main component of the resin matrix. Or it is preferable that they are similar.
These dispersants may be used alone or in combination of two or more.

[Plasticizer]
When the glass transition temperature of the thermoplastic resin constituting the organic-inorganic composite material of the present invention is high, molding may not always be easy. For this reason, in order to lower the molding temperature, the organic-inorganic composite material of the present invention may contain a plasticizer. As a plasticizer used by this invention, what has the structure represented by General formula (5) is preferable.

［一般式（５）中、Ｂ¹およびＢ²はそれぞれ独立に炭素数６〜１８のアルキル基またはアリールアルキル基、ｍは０または１、Ｘは

[In General Formula (5), B ¹ and B ² are each independently an alkyl group or arylalkyl group having 6 to 18 carbon atoms, m is 0 or 1, and X is

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

R ²¹ and R ²² each independently represents a hydrogen atom or an alkyl group having 4 or less carbon atoms. )

In the compound represented by the general formula (5), B ¹ and B ² can be selected from any alkyl group or arylalkyl group within the range of 6 to 18 carbon atoms. If the number of carbon atoms is less than 6, the molecular weight may be too low to boil at the melting temperature of the polymer and generate bubbles. On the other hand, if the number of carbon atoms exceeds 18, the compatibility with the polymer is deteriorated, so that the effect of addition may be insufficient.
Specific examples of the groups B ¹ and B ² include n-hexyl group, n-octyl group, n-decyl group, n-dodecyl group, n-tetradecyl group, n-hexadecyl group, n-octadecyl group and the like. Straight alkyl groups, branched alkyl groups such as 2-hexyldecyl group and methyl-branched octadecyl group, and arylalkyl groups such as benzyl group and 2-phenylethyl group. Specific examples of the compound represented by the general formula (6) include the following compounds, among which W-1 (trade name [KP-L155] manufactured by Kao Corporation) is preferable. However, the plasticizer that can be used in the present invention is not limited to these compounds.

[Molding method]
As a molding method of the organic-inorganic composite material in the present invention, a general thermoplastic resin material molding method such as injection molding, extrusion molding, compression molding, cast molding or the like can be employed. Since the fluidity of the organic-inorganic composite material is low, it is preferably molded by compression molding in the present invention.

[Optical parts]
The organic-inorganic composite material of the present invention is an organic-inorganic composite material having high refractive properties, low dispersibility (high Abbe number), light transmittance, and processability, and excellent optical properties. Further, the refractive index of the organic-inorganic composite material of the present invention can be arbitrarily adjusted by changing the mixing ratio of inorganic fine particles and resin, for example.
The optical component of the present invention includes the above organic-inorganic composite material. The kind of the optical component of the present invention is not particularly limited. In particular, it is suitably used for an optical component utilizing the excellent optical properties of the organic-inorganic composite material, particularly an optical component that transmits light (so-called passive optical component). Functional devices including such optical components include various display devices (liquid crystal display, plasma display, etc.), various projector devices (OHP, liquid crystal projector, etc.), optical fiber communication devices (optical waveguide, optical amplifier, etc.), cameras, videos, etc. The imaging device is exemplified.

  Examples of the passive optical component in such an optical functional device include a lens, a prism, a panel (plate-shaped molded body), a film, an optical waveguide (film-like or fiber-like), an optical disk, and the like. Of these exemplified optical components, the optical component of the present invention can be particularly preferably used as a lens. 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.

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

[Analysis and Evaluation Method]
(1) Observation with Transmission Electron Microscope (TEM) It was carried out with an H-9000UHR transmission electron microscope (acceleration voltage 200 kV, degree of vacuum at the time of observation of about 7.6 × 10 ⁻⁹ Pa) manufactured by Hitachi, Ltd. .
(2) Measurement of light transmittance A resin having a thickness of 1.0 mm was prepared by molding a resin to be measured, and light having a wavelength of 589 nm was measured with a UV-visible absorption spectrum measuring apparatus UV-3100 (manufactured by Shimadzu Corporation).
(3) Refractive index measurement Light having a wavelength of 589 nm was measured with an Abbe refractometer (DR-M4 manufactured by Atago Co., Ltd.).
(4) Evaluation of releasability After removing the molded product from the mold made of stainless steel after heat forming, ◎ indicates that the product is naturally released, but it requires a little force but it is easy to release. ○, excessive force is required and there is no damage, but when it is optically affected by internal distortion or deformation of the lens surface, △, when a large force is required and it is damaged, × did.

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

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

(3) Preparation of zirconia fine particle toluene dispersion The zirconia fine particle suspension synthesized in the above (2) and a toluene solution in which “KAYAMER PM-21” manufactured by Nippon Kayaku was dissolved, were stirred at 50 ° C. for 8 hours. Then, the toluene solution was extracted to prepare a zirconia fine particle toluene dispersion.
When other dispersants are used, they can be prepared by the same method.

(4) Resin Synthesis Synthesis of P-13:
To a 300 ml three-necked flask equipped with a reflux condenser and a gas introduction cock, 0.50 g of 2-carboxyethyl acrylate (M-14) manufactured by Aldrich was added, and after nitrogen substitution twice, styrene (M-5) 48. 5 g, NK ester M-230G (S-7, n = 23) 1.0 g manufactured by Shin-Nakamura Chemical Co., Ltd., 21.4 g ethyl acetate, and V-601 0.5 g manufactured by Wako Pure Chemical Industries, Ltd. as an initiator. Was added, and the mixture was further purged with nitrogen twice, and then heated at 80 ° C. for 3 hours under a nitrogen stream. After returning to room temperature, 30 ml of ethyl acetate was added, stirred for 10 minutes, poured into 2 L of methanol, and reprecipitated. The precipitate was collected by filtration, washed with a large amount of methanol, and vacuum-dried at 60 ° C. for 3 hours to obtain P-13 (yield 48%, number average molecular weight 21,400, weight average molecular weight 37,600). .
Other exemplified polymers can be prepared in a similar manner.

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 triisopropyl in a nitrogen stream while heating under reflux. A solution prepared by dissolving 16.8 g (80.7 mmol) of phosphite in 20 ml of m-xylene was added dropwise. After completion of dropping, the mixture was heated to reflux for 3 hours, and the solvent was distilled off. Purification by silica gel column chromatography gave initiator A (yield 53%).

Synthesis of P-11:
In a 200 ml three-necked flask equipped with a reflux condenser and a gas introduction cock, 0.41 g of copper bromide, 59.6 g of styrene (M-5), Bremer 30PET-800 (S-23, n = 55, n, manufactured by NOF Corporation) '= 9.7) 1.2 g, N, N, N ′, N ′, N ″ -pentamethyldiethylenetriamine 0.5 g and initiator A 1.0 g were charged, and after nitrogen substitution 5 times, under nitrogen flow 80 Heat at 5 ° C. for 5 hours. After returning to room temperature, 30 g of alumina and 50 ml of toluene were added, stirred for 10 minutes, and filtered through Celite. The filtrate was poured into a large amount of methanol and precipitated, and the precipitate was collected by filtration, washed with a large amount of methanol, and dried in vacuo at 60 ° C. for 3 hours to obtain a polymer (yield 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 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 and precipitated. The precipitate was collected by filtration, washed with a large amount of methanol, and vacuum-dried at 60 ° C. for 3 hours to obtain P-11. (Yield 96%, number average molecular weight 32,900, weight average molecular weight 38,200).
Other exemplified polymers can be prepared in a similar manner.

(5) Preparation of organic-inorganic composite material Toluene dispersion of zirconia fine particles synthesized in (3) is dropped into a toluene solution of resin P-13 over 5 minutes, and this is stirred for 1 hour, and then the solvent is removed. Thus, an organic-inorganic composite material was obtained as a powder.
Other organic-inorganic composite materials were prepared in the same manner.

[Manufacture of optical components by thermoforming]
Examples 1 to 4, 7, 9, and 10, Reference Examples 5, 6, and 8, and Comparative Examples 1 to 5 were manufactured according to the procedure described above. The types of inorganic fine particles used and the amounts used as inorganic components were as shown in Table 2. However, in Comparative Example 1, Q-3 synthesized in the same proportion as Example Compound P-3 without using monomer component S-5 was used as the resin, and in Comparative Example 2, Example Compound P-14 was used. In Comparative Example 3 and 4, only the thermoplastic resin was molded without adding inorganic fine particles, except that the monomer component S-26 was used and the other components were synthesized in the same ratio. In No. 5, polystyrene produced by Aldrich was used.
Each manufactured organic-inorganic composite material was heat-molded at 220 ° C. to prepare a molded article for a lens having a thickness of 1 mm. At this time, the releasability from the mold was evaluated. The molded body was cut and the cross section was observed with a TEM to confirm whether the inorganic fine particles were uniformly dispersed in the thermoplastic resin. Further, light transmittance measurement and refractive index measurement were performed. These results are listed in Table 2 below. Thereafter, the lens molding was molded into a lens shape to obtain a lens as an optical component.

As is apparent from Table 2, an optical component having a refractive index greater than 1.65 and good transparency was obtained according to the present invention . In Comparative Examples 1 and 2, the lens surface is partially damaged due to poor releasability after molding. In Comparative Examples 3 and 4, there is no addition of inorganic fine particles, so that the optical component has a sufficiently high refractive index. In Comparative Example 5, the inorganic fine particles could not be uniformly dispersed, the fine particles were agglomerated, and the light transmittance was low, so that the refractive index could not be measured with an Abbe refractometer.

  The optical component of the present invention includes an organic-inorganic composite material having both high refraction, light transmittance, light weight, and releasability. ADVANTAGE OF THE INVENTION According to this invention, the optical component which adjusted the refractive index arbitrarily can be provided comparatively easily. Therefore, the present invention is useful for providing a wide range of optical components such as a high refractive lens, and has high industrial applicability.

Claims (20)

The thermoplastic resin having at least one unit structure represented by the following general formula (1) has a number average particle size of 1 to 15 nm and any one selected from the group consisting of zirconia, zinc oxide, tin oxide and titania. Inorganic fine particles are dispersed,
A unit structure represented by the general formula (1) is introduced into the thermoplastic resin by polymerization using a compound represented by the following general formula (2). material.

[In General Formula (1), R ¹ and R ² each independently represent a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group, A represents an oxygen atom, m Represents an integer of 1 or more, and n represents an integer of 2 or more. The m R ^{1 s} may be the same as or different from each other, and the m R ^{2 s} may be the same as or different from each other. ]

[In General Formula (2), R ¹⁰ represents a hydrogen atom or a methyl group, and R ^{11 to} R ¹⁴ each independently represents a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group. the stands, a ¹¹ and a ¹² represents an oxygen atom, represent an integer of 1 or more, respectively m11 and m12 independently represents an integer of two or more in each of n11 and n12 independently. When m11 is 2 or more, m11 R ¹¹ and R ¹² may be the same as or different from each other. When m12 is 2 or more, m12 R ¹³ and R ¹⁴ may be the same as each other. May be different. R ¹⁵ represents a hydrogen atom, an alkyl group, an aryl group or an alkylaryl group. ]   2. The organic-inorganic composite material according to claim 1, wherein the total content of the unit structure represented by the general formula (1) in the thermoplastic resin is 0.01 to 10% by mass. The organic-inorganic composite material according to claim 1 or 2, wherein the compound represented by the general formula (2) is a compound represented by the following general formula (2a).

[In the general formula (2a), R ²⁰ represents a hydrogen atom or a methyl group, R ²¹ and R ²² each independently represents a substituted or unsubstituted alkylene group, and n ²¹ and n ²² each independently represents an integer of 2 or more. R ²³ represents a hydrogen atom, an alkyl group, an aryl group or an alkylaryl group. ] The organic-inorganic composite material according to claim 1 or 2, wherein the compound represented by the general formula (2) is represented by the following S- 7 .

[In S-7, n represents 23. ]   The organic-inorganic composite material according to any one of claims 1 to 4, wherein the inorganic fine particles are zirconia.   The organic-inorganic composite material according to claim 1, wherein the thermoplastic resin has a number average molecular weight of 1,000 to 500,000.   The polymer which comprises the said thermoplastic resin has at least 1 type of the unit structure represented by the said General formula (1) through a chemical bond, It is any one of Claims 1-6 characterized by the above-mentioned. Organic inorganic composite material. The thermoplastic resin is

[R ^{11 to} R ¹⁶ each independently represents a hydrogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group. _{], - SO 3 H, -OSO} 3 H, -CO 2 H, -OH, and _{^{-Si (OR 17) x R 18}} 3-x [R 17 and R ¹⁸ each independently represent a hydrogen atom, a substituted or unsubstituted An alkyl group, or a substituted or unsubstituted aryl group, and x represents an integer of 1 to 3. The organic-inorganic composite material according to any one of claims 1 to 7, which has a functional group selected from the group consisting of:   The organic-inorganic composite material according to any one of claims 1 to 8, wherein the inorganic fine particles have a refractive index of 1.90 to 3.00 at a wavelength of 589 nm.   10. The organic / inorganic according to claim 1, wherein a refractive index at a wavelength of 589 nm is 1.63 or more, and a light transmittance in terms of 1 mm thickness at a wavelength of 589 nm is 80% or more. Composite material.   The optical component comprised including the organic inorganic composite material as described in any one of Claims 1-10.   The optical component according to claim 11, wherein the optical component is a lens substrate. The thermoplastic resin having at least one unit structure represented by the following general formula (1) has a number average particle size of 1 to 15 nm and any one selected from the group consisting of zirconia, zinc oxide, tin oxide and titania. A step of dispersing inorganic fine particles,
An organic inorganic material comprising a step of introducing a unit structure represented by the general formula (1) into the thermoplastic resin by polymerization using a compound represented by the following general formula (2) A method for producing a composite material.

[In General Formula (1), R ¹ and R ² each independently represent a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group, A represents an oxygen atom, m Represents an integer of 1 or more, and n represents an integer of 2 or more. The m R ^{1 s} may be the same as or different from each other, and the m R ^{2 s} may be the same as or different from each other. ]

[In General Formula (2), R ¹⁰ represents a hydrogen atom or a methyl group, and R ^{11 to} R ¹⁴ each independently represents a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group. the stands, a ¹¹ and a ¹² represents an oxygen atom, represent an integer of 1 or more, respectively m11 and m12 independently represents an integer of 2 or more in each of n11 and n12 independently. When m11 is 2 or more, m11 R ¹¹ and R ¹² may be the same as or different from each other. When m12 is 2 or more, m12 R ¹³ and R ¹⁴ may be the same as each other. May be different. R ¹⁵ represents a hydrogen atom, an alkyl group, an aryl group or an alkylaryl group. ]   14. The organic-inorganic composite material according to claim 13, wherein the total content of the unit structure represented by the general formula (1) in the thermoplastic resin is 0.01 to 10% by mass. Method. The method for producing an organic-inorganic composite material according to claim 13 or 14, wherein the compound represented by the general formula (2) is a compound represented by the following general formula (2a).

[In the general formula (2a), R ²⁰ represents a hydrogen atom or a methyl group, R ²¹ and R ²² each independently represents a substituted or unsubstituted alkylene group, and n ²¹ and n ²² each independently represents an integer of 2 or more. R ²³ represents a hydrogen atom, an alkyl group, an aryl group or an alkylaryl group. ] The method for producing an organic-inorganic composite material according to claim 13 or 14, wherein the compound represented by the general formula (2) is represented by the following S- 7 .

[In S-7, n represents 23. ]   The method for producing an organic-inorganic composite material according to any one of claims 13 to 16, wherein the inorganic fine particles are zirconia.   The number average molecular weight of the said thermoplastic resin is 1,000-500,000, The manufacturing method of the organic inorganic composite material as described in any one of Claims 13-17 characterized by the above-mentioned.   The method for producing an organic-inorganic composite material according to any one of claims 13 to 18, wherein the inorganic fine particles are dispersed in the thermoplastic resin in the presence of a dispersant.   13. The method for manufacturing an optical component according to claim 11, wherein the optical component is molded using a mold.