JP2008239921A - Organic/inorganic composite composition and optical component - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a material composition also having high refractility, transparency and light weight property. <P>SOLUTION: The organic/inorganic composite composition comprises a resin containing a repeating unit having a structure unit represented by the general formula (I) in a main chain of the repeating unit, and an inorganic particle. [Wherein, R represents an alkyl group, an aryl group, an alkoxy group, an aryloxy group or a hydroxyl group; and A represents an oxygen atom, a sulfur atom or a selenium atom]. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to an organic-inorganic composite composition excellent in high refraction, transparency, low birefringence, lightness, and processability, and an optical component comprising the composition (for example, for spectacle lenses, optical instruments) Lens, optoelectronic lens, laser lens, pickup lens, in-vehicle camera lens, portable camera lens, digital camera lens, OHP lens, and the like.

  In recent years, research on optical materials has been actively conducted, and particularly in the field of lens materials, high refraction, low dispersion (that is, high Abbe number), low birefringence, heat resistance, transparency, easy moldability, There is a strong demand for the development of materials with excellent lightness, chemical resistance and solvent resistance.

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 (Patent Document 3) has been actively researched, and a plastic material having a refractive index of more than 1.7 has been reported. It has no characteristics.

In addition, a method for producing a high refractive index material by dispersing an inorganic substance having a high refractive index in a resin matrix has been reported (see Patent Document 4). In order to reduce attenuation of transmitted light due to Rayleigh scattering, it is preferable to uniformly disperse inorganic fine particles having a particle size of 15 nm or less in the resin matrix. However, since primary particles having a particle size of 15 nm or less are very likely to aggregate, it is extremely difficult to uniformly disperse them in the resin matrix. In addition, when the attenuation of transmitted light in the optical path length corresponding to the thickness of the lens is taken into consideration, the amount of inorganic fine particles added must be limited. For this reason, by dispersing fine particles in a resin matrix, it has not been possible to produce a material that achieves both high refractive index (over 1.70) and high transparency.
JP 2002-131502 A Japanese Patent Laid-Open No. 10-298287 JP 2004-244444 A JP 2003-73564 A

Therefore, a plastic material having both high refraction, transparency and light weight, and an optical component such as a lens including the plastic material have not yet been found, and development thereof has been desired.
The present invention has been made in view of the above circumstances, and an object of the present invention is to provide an optical material comprising a material composition in which fine particles are uniformly dispersed in a resin matrix and has excellent transparency and a high refractive index. To provide parts.

  As a result of intensive studies to achieve the above-mentioned object, the present inventors have obtained a material composition in which inorganic fine particles having a high refractive index are dispersed in a specific resin excellent in transparency. As a result, it has been found that the film has high refractive properties and excellent transparency, and the present invention described in the following [1] to [9] has been completed.

［一般式（Ｉ）中、Ｒは、置換もしくは無置換のアルキル基、置換もしくは無置換のアリール基、置換もしくは無置換のアルコキシ基、置換もしくは無置換のアリールオキシ基、またはヒドロキシ基を表す。Ａは酸素原子、硫黄原子、もしくはセレン原子を表す。］
［２］ 前記繰返し単位が下記一般式（II）で表されることを特徴とする［１］に記載の有機無機複合組成物。
一般式（II）

［一般式（II）中、Ｒは、置換もしくは無置換のアルキル基、置換もしくは無置換のアリール基、置換もしくは無置換のアルコキシ基、置換もしくは無置換のアリールオキシ基、またはヒドロキシ基を表す。Ａ¹、Ａ²、およびＡ³はそれぞれ独立に、酸素原子、硫黄原子、もしくはセレン原子を表す。Ｌ¹、Ｌ²は置換もしくは無置換のアルキレン基、置換もしくは無置換のアリーレン基、またはこれらを組み合わせた連結基を表す。Ｘは炭素数２以上の連結基を表す。ｍ、ｎはそれぞれ独立に０もしくは１を表す。］
［３］ 前記無機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］または［２］に記載の有機無機複合組成物。
［４］ 前記無機粒子の屈折率が１．９以上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］ 前記無機粒子が、チタン酸化物、ジルコニウム酸化物、またはこれら両方を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］ 波長５８９ｎｍにおける厚さ１ｍｍ換算の光線透過率が７０％以上であることを特徴とする［１］〜［５］のいずれか一項に記載の有機無機複合組成物。 [1] An organic-inorganic composite composition comprising a resin containing a repeating unit having a structural unit represented by the following general formula (I) in the main chain of the repeating unit and inorganic particles.
Formula (I)

[In general formula (I), R represents a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted aryloxy group, or a hydroxy group. A represents an oxygen atom, a sulfur atom, or a selenium atom. ]
[2] The organic-inorganic composite composition according to [1], wherein the repeating unit is represented by the following general formula (II).
Formula (II)

[In general formula (II), R represents a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted aryloxy group, or a hydroxy group. A ¹ , A ² , and A ³ each independently represents an oxygen atom, a sulfur atom, or a selenium atom. L ¹ and L ^{2 each} represents a substituted or unsubstituted alkylene group, a substituted or unsubstituted arylene group, or a linking group obtained by combining these. X represents a linking group having 2 or more carbon atoms. m and n each independently represents 0 or 1. ]
[3] The organic-inorganic composite composition according to [1] or [2], wherein the inorganic particles have a number average particle size of 1 to 15 nm.
[4] The organic-inorganic composite composition according to any one of [1] to [3], wherein a refractive index of the inorganic particles is 1.9 or more.
[5] The organic-inorganic composite composition according to any one of [1] to [4], wherein the inorganic particles include titanium oxide, zirconium oxide, or both.
[6] The organic-inorganic composite composition according to any one of [1] to [5], wherein the light transmittance in terms of 1 mm thickness at a wavelength of 589 nm is 70% or more.

[7] An optical component comprising the organic-inorganic composite composition according to any one of [1] to [6].
[8] The optical component according to [7], wherein the optical component is a lens.
[9] The optical component according to [8], wherein the thickness is 500 μm or more.

  The organic-inorganic composite composition of the present invention and the optical component comprising the same have fine particles uniformly dispersed in the resin matrix, and have both excellent transparency and a high refractive index. Further, according to the present invention, it is easy to provide an optical component having good mechanical strength and heat resistance.

  Hereinafter, the organic-inorganic composite composition of the present invention and an 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.

[resin]
The resin used in the present invention contains a repeating unit having a structural unit represented by the following general formula (I) in the main chain of the repeating unit.
Formula (I)

  In general formula (I), R represents a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted aryloxy group, or a hydroxy group. R is preferably a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted alkoxy group, or a substituted or unsubstituted aryloxy group. Carbon number of the alkyl group which R can take is preferably 1-20, more preferably 1-18, and still more preferably 1-15. Specific examples include a methyl group, an ethyl group, a propyl group, an isopropyl group, and a cyclohexyl group. The number of carbon atoms of the aryl group that R can take is preferably 6 to 20, more preferably 6 to 18, and still more preferably 6 to 15. Specific examples include a phenyl group, a 1-naphthyl group, and a 2-naphthyl group. Carbon number of the alkoxy group which R can take is preferably 1-20, more preferably 1-18, and still more preferably 1-15. Specific examples of the alkyl moiety of the alkoxy group include those listed as specific examples of the alkyl group. Carbon number of the aryloxy group which R can take is preferably 6-20, more preferably 6-18, and still more preferably 6-15. Specific examples of the aryl moiety of the aryloxy group include those listed as specific examples of the aryl group.

  There are no particular restrictions on the substituents that can be substituted for the alkyl group, aryl group, alkoxy group, and aryloxy group. For example, a halogen atom (for example, fluorine atom, chlorine atom, bromine atom, iodine atom), alkyl group ( For example, methyl group, ethyl group), aryl group (for example, phenyl group, naphthyl group), alkenyl group, alkynyl group, cyano group, carboxyl group, alkoxycarbonyl group (for example, methoxycarbonyl group), aryloxycarbonyl group (for example, , Phenoxycarbonyl group), substituted or unsubstituted carbamoyl group (for example, carbamoyl group, N-phenylcarbamoyl, N, N-dimethylcarbamoyl group), alkylcarbonyl group (for example, acetyl group), arylcarbonyl group (for example, benzoyl) Group), nitro group, acyl Mino group (for example, acetamido group, ethoxycarbonylamino group), sulfonamide group (for example, methanesulfonamide group), imide group (for example, succinimide group, phthalimide group), imino group (for example, benzylideneamino group), alkoxy group (For example, methoxy group), aryloxy group (for example, phenoxy group), acyloxy group (for example, 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 group (for example, methylthio group), arylthio group (for example, phenylthio group), alkylsulfonyl group For example, methanesulfonyl group), an arylsulfonyl group (e.g., benzenesulfonyl group), and the like heterocyclic compounds.

  The substituent of R may be further substituted, and when there are a plurality of substituents, each substituent may be the same or different. The substituent may form a condensed ring with R. The substituent is preferably a halogen atom, alkyl group, aryl group, alkoxy group, aryloxy group, alkylthio group, arylthio group, carboxyl group, alkoxycarbonyl group, aryloxycarbonyl group, alkylcarbonyl group, arylcarbonyl group, An alkyl group, an aryl group, an alkoxy group, and an aryloxy group are more preferable, and an alkyl group and an aryl group are more preferable.

  A represents an oxygen atom, a sulfur atom, or a selenium atom, preferably an oxygen atom or a sulfur atom.

The repeating unit having the structural unit represented by the general formula (I) in the main chain of the repeating unit is preferably represented by the general formula (II).
Formula (II)

In general formula (II), R is synonymous with R of general formula (I), and its preferable range is also the same. A ¹ , A ² and A ³ each independently represents an oxygen atom, a sulfur atom or a selenium atom, preferably an oxygen atom or a sulfur atom. L ¹ and L ^{2 each} represents a substituted or unsubstituted alkylene group, a substituted or unsubstituted arylene group, or a linking group obtained by combining these. Carbon number of the alkylene group which L < ¹ >, L < ² > can take becomes like this. Preferably it is 2-20, More preferably, it is 2-15, More preferably, it is 2-12. Specific examples include a methylene group, an ethylene group, a propylene group, and a cyclohexene group. The number of carbon atoms of the arylene group that can be taken by L ¹ and L ² is preferably 6 to 20, more preferably 6 to 15, and still more preferably 6 to 12. Specific examples include a phenylene group, a biphenylene group, and a naphthylene group. Carbon number of the coupling group which combined the alkylene group and arylene group which L < ¹ >, L < ² > can take becomes like this. Preferably it is 7-20, More preferably, it is 7-15, More preferably, it is 7-12. As a specific example, one or more groups selected from the group consisting of a methylene group, an ethylene group, a propylene group and a cyclohexene group are combined with one or more groups selected from the group consisting of a phenylene group, a biphenylene group and a naphthylene group. Can be mentioned. There are no particular restrictions on the substituent for the alkylene group, the arylene group, or the linking group obtained by combining these groups, but those mentioned as the substituent for R in formula (I) can be applied, and the preferred ranges are also the same. X represents a linking group having 2 or more carbon atoms, preferably a divalent linking group having 2 to 40 carbon atoms, more preferably 2 to 30 carbon atoms, and more preferably a type selected from the group consisting of the following structural formulas. It is.

R ¹ and R ² represent a hydrogen atom, an alkyl group, or an aryl group, and R ¹ and R ² may form a ring structure. Examples of the ring structure formed by R ¹ and R ² include the following.

  The linking group that can be taken by X may have a substituent, and the substituent is not particularly limited, but those exemplified as the substituent for R in the general formula (I) can be applied, and the preferred range is also the same. . m and n each independently represents 0 or 1. Both m and n are preferably 0.

Among the structural units represented by the general formula (II), particularly structural units represented by the following general formula (III) and the following general formula (IV) are also included. These structural units can also be preferably employed in the present invention.

In general formula (III) and general formula (IV), R is synonymous with R of general formula (I), and its preferable range is also the same. A ¹ , A ² , A ³ , A ⁴ and A ⁵ each independently represents an oxygen atom, a sulfur atom or a selenium atom, preferably an oxygen atom or a sulfur atom. L ^1, L ² has the same meaning as L ^1, L ² of formula (II), and preferred ranges are also the same. X ¹ , X ² and X ³ each independently represent a linking group having 2 or more carbon atoms, and the preferred range is the same as X ¹ and X ^{2 in} formula (II). m and n each independently represents 0 or 1.

  The resin used in the present invention may have only one type of repeating unit having a structural unit represented by the general formula (I) in one molecule, or a structure represented by the general formula (I). You may have 1 or more types of another repeating unit which has a unit. In the case of a copolymer containing two or more kinds of repeating units in one molecule, it may be a block copolymer, a random copolymer, or a graft copolymer.

  Specific examples of preferred repeating units contained in the resin that can be used in the present invention are listed below, but the resins that can be used in the present invention are not limited to those having these repeating units. The repeating units a, b, c, d, x, and y represent the copolymerization ratio (mol ratio).

  The resin used in the present invention can be synthesized by a known method. For example, New Polymer Experimental Science 2, Polymer Synthesis / Reaction (2) Synthesis of Condensed Polymers (Edited by Polymer Society), 138-143, Journal of Polymer Science Part B, 38, 2409-2421 It can be synthesized by a polycondensation reaction of a phosphoric acid derivative described in the paragraph (2000) and a hydroxyl group-containing compound.

  In the organic-inorganic composite composition of the present invention, one type of resin having the structural unit represented by the general formula (I) may be used alone, or two or more types may be mixed and used. Moreover, you may mix and use resin which does not have a structural unit represented by general formula (I). For example, it can be used by mixing with a resin having no phosphorus atom in the repeating unit. Although there is no restriction | limiting in particular in the kind of resin which does not have a phosphorus atom in a repeating unit, It is preferable to select and use from the thing satisfy | filling the following optical physical property, thermophysical property, and molecular weight.

  The resin used in the present invention preferably has a refractive index greater than 1.50, more preferably greater than 1.60. In addition, the refractive index in this invention is the value measured about the light of wavelength 589nm with the Abbe refractometer (Atago Co., Ltd. DR-M4).

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

  The resin used in the present invention preferably has a light transmittance at a wavelength of 589 nm of 70% or more, and more preferably 80% or more. If the light transmittance is 80% or more, it is easy to obtain an optical component having more preferable properties.

  The resin used in the present invention is preferably a number average molecular weight of 1,000 to 500,000, more preferably a number average molecular weight of 3,000 to 300,000, still more preferably a number average molecular weight of 5,000 to 200,000, particularly preferably. Is a resin having a number average molecular weight of 10,000 to 100,000. If the number average molecular weight is 1,000 or more, an organic-inorganic composite composition having mechanical strength is easily obtained, and if it is 500,000 or less, molding tends to be easy.

[Inorganic fine particles]
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, for example, titanium oxide fine particles, zinc oxide fine particles, zirconium oxide, tin oxide, cerium oxide, zinc sulfide fine particles and the like, preferably titanium oxide fine particles, zirconium oxide zinc sulfide fine particles, and more Preferred are fine particles of titanium oxide and fine particles of zirconium oxide, but are not limited thereto. In the present invention, one kind of inorganic fine particles may be used alone, or a plurality of kinds of inorganic fine particles may be used in combination, or may be doped with any metal element such as barium, cobalt, yttrium and the like. The inorganic fine particles used in the present invention may be surface-coated with other metal oxides such as aluminum oxide.

The method for producing inorganic fine particles used in the present invention is not particularly limited, and any known method can be used. 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 for the synthesis of titanium oxide nanoparticles, and zinc salts such as zinc acetate and zinc nitrate are exemplified for the synthesis of zinc oxide nanoparticles. Metal alkoxides such as tetraethoxysilane and titanium tetraisopropoxide can also be suitably used as raw materials. For example, publicly known methods described in Japanese Journal of Applied Physics, 37, 4603-4608 (1998) and Langmuir, 16: 1 241-246 (2000) can be used. In particular, when oxide nanoparticles are synthesized by a sol formation method, for example, titanium oxide nanoparticles using titanyl sulfate as a raw material are synthesized and then dehydrated with an acid or alkali via a precursor such as hydroxide. Procedures that condense or peptize to form a hydrosol are 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. In addition, a basic solution is added to a metal salt solution to partially neutralize it by the method described in Japanese Patent Application Laid-Open No. 2006-16236, and then an inorganic salt is added to the solution to form a mixed solution, and this mixed solution is heated. Metal fine particles can also be obtained.

In addition to the method of hydrolyzing in water, the inorganic fine particles may be prepared in an organic solvent or an organic solvent in which the resin used in the present invention is dissolved.
Examples of the solvent used in these methods include acetone, 2-butanone, dichloromethane, chloroform, toluene, ethyl acetate, cyclohexanone, anisole and the like. These may be used alone or as a mixture of two or more.

  If the number average particle size of the inorganic fine particles used in the present invention is too small, the characteristics unique to the substance constituting the fine particles may change. Conversely, if the number average particle size is too large, the effect of Rayleigh scattering becomes significant. In addition, the transparency of the organic-inorganic composite composition containing inorganic fine particles may be extremely lowered. Therefore, the lower limit value of the number average particle size of the inorganic fine particles used in the present invention is preferably 1 nm, more preferably 2 nm, still more preferably 3 nm, and the upper limit value is preferably 15 nm, more preferably 10 nm, still more preferably 5 nm. It is.

  The range of the refractive index of the inorganic fine particles used in the present invention is preferably 1.90 or more, more preferably 1.90 to 3.00, and still more preferably 1.90 to 2.70. 2.00 to 2.70 is particularly preferable. If inorganic fine particles having a refractive index of 1.90 or more are used, it becomes easy to prepare an organic-inorganic composite composition having a refractive index of greater than 1.70. If inorganic fine particles having a refractive index of 3.00 or less are used, the transmittance is 80. % Or more of the organic-inorganic composite composition tends to be easily produced.

[Dispersant]
The fine particles used in the present invention may be dispersed in the resin using a dispersant. The molecular weight of the dispersant used in the present invention is usually 100 to 1000. When the molecular weight is too large, it tends to be difficult to increase the refractive index of the organic-inorganic composite composition.

  When the fine particles used in the present invention are coordinated or modified with an organic compound (referred to as “dispersant” in the present invention) having compatibility with the resin matrix mainly composed of the resin, the fine particles on the resin matrix Dispersibility is improved, and the transparency and mechanical strength of the organic-inorganic composite composition of the present invention may be improved. The effect of the dispersant is considered to be due to a combination of the effect of suppressing aggregation of fine particles and the effect of improving the compatibility with the resin matrix.

A preferred structure of such a dispersant is represented by the following general formula (V).
General formula (V)
A-R
However, A represents the functional group which can form arbitrary chemical bonds with the surface of microparticles | fine-particles, and R represents a C1-C30 monovalent group or polymer which has compatibility or reactivity with a resin matrix. The chemical bond is, for example, a covalent bond, an ionic bond, a coordination bond, a hydrogen bond, or the like.

  Although there is no limitation on the method of coordination of the dispersant to the inorganic fine particles and the modification method by covalent bonding and the molecular structure of the organic substance used therefor, specific examples of A coordinated on the fine particles include thiol and sulfonic acids. Effective sulfur-containing organic compounds, phosphorus-containing organic ligands with phosphine, phosphine oxide, phosphonic acid, phosphate esters, etc., nitrogen-containing ligands with alkylamines and aromatic amines, and ligands with carboxylic acids It is. Among these examples, phosphorus-containing organic ligands that are preferably used are, for example, KAYAMER PM-21 manufactured by Nippon Kayaku, dibenzyl phosphate, and diphenyl phosphate.

  Specific examples of the above-described A modified by covalent bond include silane coupling agents, titanate coupling agents, aluminum coupling agents and the like conventionally used for surface treatment of oxides such as silica, alumina, and titania. A metal alkoxide group which is an active functional group is effective. 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 is a group having compatibility or reactivity with the resin matrix, the chemical structure thereof is the same as or similar to part or all of the chemical structure of the resin that is the main component of the resin matrix. Is preferred.
These dispersants may be used alone or in combination of two or more.

一般式（VI）中、Ｂ¹およびＢ²は炭素数６〜１８のアルキル基またはアリールアルキル基、ｍは０または１、Ｘは

のうちのいずれかであり、Ｒ¹およびＲ²は水素原子または炭素数４以下のアルキル基を示す。 [Plasticizer]
If the glass transition temperature of the resin is high, molding may not always be easy. For this reason, a plasticizer may be used to lower the molding temperature. The plasticizer used in the present invention is not particularly limited, and dicarboxylic acid ester derivatives (dioctyl phthalate, diphenyl phthalate, dioctyl adipate, etc.), phosphoric acid ester derivatives (tricresyl phosphate, Reophos RDP (manufactured by Ajinomoto Fine Techno)) , Reofos BAPP (manufactured by Ajinomoto Fine Techno Co., Ltd.), acrylic polymer plasticizer (ARUFON UP-1010 (manufactured by Toagosei Co., Ltd.), etc.), and the like, known plasticizers can be used. As a plasticizer used by this invention, what has the structure represented by general formula (VI) is preferable.
General formula (VI)

In the general formula (VI), B ¹ and B ² are alkyl groups or arylalkyl groups having 6 to 18 carbon atoms, m is 0 or 1, and X is

R ¹ and R ^{2 each} represent a hydrogen atom or an alkyl group having 4 or less carbon atoms.

In the compound represented by the general formula (VI), 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, when the number of carbon atoms exceeds 18, the compatibility with the polymer is deteriorated, so that the effect of addition is insufficient.
Specific examples of the groups B ¹ and B ² include n-hexyl group, n-octyl group, n-decyl group, n-dodecyl group, n-tetradecyl group, n-hexadecyl group, n-octadecyl group and the like. Straight alkyl groups, branched alkyl groups such as 2-hexyldecyl group and methyl-branched octadecyl group, and arylalkyl groups such as benzyl group and 2-phenylethyl group. Specific examples of the compound represented by the general formula (VI) used in the present invention include the following, among which W-1 (trade name [KP-L155] manufactured by Kao Corporation) is preferable.

これらの可塑剤は、１種類を単独で用いてもよく、また複数種を併用してもよい。

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

[Organic-inorganic composite composition]
The method for producing the organic-inorganic composite composition of the present invention is not particularly limited. Specifically, a method of individually synthesizing a resin and inorganic fine particles and mixing them, a method of synthesizing a resin in the presence of pre-synthesized inorganic fine particles, and a method of synthesizing inorganic fine particles in the presence of a pre-synthesized resin Examples thereof include a method, a method of simultaneously synthesizing both a resin and inorganic fine particles, and any of these methods may be used.

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

  In the organic-inorganic composite composition of the present invention, the light transmittance at a wavelength of 589 nm is preferably 80% or more, and more preferably 90% or more. If the light transmittance at a wavelength of 589 nm is 80% or more, it is easy to obtain 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.

  The organic-inorganic composite composition of the present invention preferably has a glass transition temperature of 100 ° C to 400 ° C, 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.

  The organic-inorganic composite composition of the present invention is a material composition having high refractive properties, low dispersibility (high Abbe number), light transmittance, low birefringence, and light weight and excellent optical properties. Moreover, the refractive index of the organic-inorganic composite composition of the present invention can be arbitrarily adjusted.

[Optical parts]
The optical component of the present invention includes the organic-inorganic composite composition of the present invention. 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 composition of the present invention, 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 or wear, light with an undesired wavelength that causes deterioration of inorganic particles or 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 arbitrary 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.

[Synthesis of materials]
(1) Synthesis of methylene chloride dispersion of titanium oxide fine particles While stirring a 0.1 mol / L titanyl sulfate aqueous solution, a 1.5 mol / L sodium carbonate aqueous solution of 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 a methylene chloride solution of diphenyl phosphate was added and stirred for 8 hours. The methylene chloride solution was extracted and washed with water to obtain a titanium oxide fine particle methylene chloride solution. A part of this solution was concentrated, and the formation of anatase-type titanium oxide fine particles (number average particle size was about 5 nm) was confirmed from the residual XRD and TEM. Observation by TEM was performed with a transmission electron microscope (H-9000UHR, manufactured by Hitachi, Ltd.) at an acceleration voltage of 200 kV and a degree of vacuum of about 7.6 × 10 ⁻⁹ Pa during observation (the same applies hereinafter).

(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 weight in terms of zirconium oxide as a solvent with ion-exchanged water, placed in an autoclave, and hydrothermally treated for 24 hours at a pressure of 150 atm and 150 ° C. 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.

(3) Synthesis of zirconium oxide fine particle methylene chloride dispersion The zirconium oxide aqueous dispersion synthesized in (1) above and a methylene chloride solution in which dibenzyl phosphate (manufactured by Tokyo Chemical Industry) was dissolved were mixed and then stirred at room temperature for 8 hours. Thereafter, the methylene chloride solution was extracted and washed with water to prepare a zirconium oxide fine particle methylene chloride dispersion.

(4) Synthesis of Exemplary Compound P-5 Bisphenol A (11.42 g, 50 mmol) and benzyltriphenylphosphonium chloride (0.4 g, 1 mmol) were added to 100 ml of a 1 mol / L aqueous potassium hydroxide solution. The solution was cooled to 0 ° C., and a solution prepared by dissolving 9.74 g (50 mmol) of phenylphosphonic dichloride in 20 ml of methylene chloride was added dropwise over 20 minutes with vigorous stirring. The phenylphosphonic acid dichloride remaining in the dropping funnel was washed with 5 ml of methylene chloride and added. The polymerization temperature is kept at 0 ° C. ± 3 ° C. and stirred for 2 hours. The aqueous phase was removed by decanting and the organic phase was washed several times. The organic phase was diluted with 200 ml of methylene chloride and poured into methanol with stirring. The polymer was filtered off and dried under reduced pressure at 80 ° C. The polymer yield was 16.2 g (yield 92%), the number average molecular weight was 21,300, and the weight average molecular weight was 40,100.

(5) Synthesis of Exemplified Compound P-6 Exemplified Compound P-6 was obtained in the same manner as Exemplified Compound P-5 except that 17.52 g (50 mmol) of fluorene bisphenol was used instead of bisphenol A. The yield was 21.3 g (yield 90%), the number average molecular weight was 25,200, and the weight average molecular weight was 53,300.

(6) Synthesis of Exemplary Compound P-19 9,9-bis [4- (2-hydroxyethoxy) phenyl] fluorene 22.73 g (50 mmol), methylene chloride 150 ml, triethylamine 11.1 g (110 mmol) were mixed. After cooling the solution to 0 ° C., 12.5 g (50 mmol) of phenylphosphoric dichloride dissolved in 25 ml of methylene chloride was added dropwise over 1 hour with vigorous stirring. After completion of the dropping, the temperature was returned to room temperature, and the mixture was further refluxed for 4 hours. The polymer solution was washed with 1% dilute hydrochloric acid and then with water until the aqueous phase became neutral. The organic phase was poured into methanol, the polymer was filtered off, and dried under reduced pressure at 80 ° C. The polymer yield was 25.4 g (88% yield), the number average molecular weight was 28,600, and the weight average molecular weight was 62,900.

(7) Synthesis of Exemplified Compound P-22 7.0 g (20 mmol) of fluorene bisphenol, 16.1 g (60 mmol) of 1,1-bis (4-hydroxyphenyl) cyclohexane, 11.7 g (60 mmol) of phenyl phosphate dichloride, triphosgene 1.99 g (6.7 mmol) was used and synthesized according to the method described in Example 1 of JP-A No. 2004-269844. The polymer yield was 27.8 g (90% yield), the number average molecular weight was 70,200, and the weight average molecular weight was 127,000.

[Manufacture of optical components by thermoforming]
Each lens of Examples 1-7 and Comparative Examples 1-6 was manufactured in the following procedures. The type of resin used in the following procedure, the type of inorganic fine particles, and the amount used were as shown in Table 1. However, in Comparative Examples 1 to 4, only the resin was molded without adding inorganic fine particles.
Titanium oxide fine particles or zirconium oxide fine particles dispersed in methylene chloride were dropped into a methylene chloride solution of the resin over 5 minutes, and this was stirred for 1 hour, and then the solvent was removed. The obtained material composition was heat compression molded at 200 ° C. to prepare a molded article for a lens having a thickness of 1 mm.
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 resin. Moreover, the light transmittance of the molded article for lenses having a thickness of 1 mm was measured using an ultraviolet-visible absorption spectrum measuring apparatus (manufactured by Shimadzu Corporation, UV-3100). Further, the refractive index was measured for light having a wavelength of 589 nm using an Abbe refractometer (DR-M4 manufactured by Atago Co., Ltd.). These results are listed in Table 1 below.
Thereafter, the lens molding was molded into a lens shape to obtain a lens as an optical component.

  As is apparent from Table 1, optical components having a refractive index greater than 1.70 and good transparency were obtained according to the present invention (Examples 1 to 7). When only the resin was used without using the inorganic fine particles, the refractive index was low (Comparative Examples 1 to 4). In addition, when inorganic fine particles were added to the polycarbonate, the inorganic fine particles could not be uniformly dispersed and became cloudy, and a transparent lens could not be obtained (Comparative Examples 5 and 6).

  The organic-inorganic composite composition of the present invention has high refractive properties, transparency and lightness, and is extremely useful as a material composition for optical parts and the like. ADVANTAGE OF THE INVENTION According to this invention, the optical component which adjusted the refractive index arbitrarily can be provided comparatively easily. In addition, it is easy to provide optical components with good mechanical strength and heat resistance. 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 (9)

An organic-inorganic composite composition comprising a resin containing a repeating unit having a structural unit represented by the following general formula (I) in the main chain of the repeating unit, and inorganic particles.
Formula (I)

[In general formula (I), R represents a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted aryloxy group, or a hydroxy group. A represents an oxygen atom, a sulfur atom, or a selenium atom. ] The organic-inorganic composite composition according to claim 1, wherein the repeating unit is represented by the following general formula (II).
Formula (II)

[In general formula (II), R represents a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted aryloxy group, or a hydroxy group. A ¹ , A ² , and A ³ each independently represents an oxygen atom, a sulfur atom, or a selenium atom. L ¹ and L ^{2 each} represents a substituted or unsubstituted alkylene group, a substituted or unsubstituted arylene group, or a linking group obtained by combining these. X represents a linking group having 2 or more carbon atoms. m and n each independently represents 0 or 1. ]   The organic-inorganic composite composition according to claim 1 or 2, wherein the number average particle size of the inorganic particles is 1 to 15 nm.   The organic-inorganic composite composition according to any one of claims 1 to 3, wherein the refractive index of the inorganic particles is 1.9 or more.   The organic-inorganic composite composition according to any one of claims 1 to 4, wherein the inorganic particles contain titanium oxide, zirconium oxide, or both.   The organic-inorganic composite composition according to any one of claims 1 to 5, wherein a light transmittance in terms of a thickness of 1 mm at a wavelength of 589 nm is 70% or more.   The optical component comprised including the organic inorganic composite composition as described in any one of Claims 1-6.   The optical component according to claim 7, wherein the optical component is a lens.   The optical component according to claim 8, wherein the thickness is 500 μm or more.