JP2007238930A - Organic-inorganic composite composition, its preparation process, molded item, and optical component - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an optical component having excellent transparency and a high refractive index. <P>SOLUTION: This optical component uses an organic-inorganic composite composition containing inorganic fine particles whose refractive index is 1.90-3.00 and a thermoplastic resin which has a functional group that can form a chemical bond with the inorganic fine particle at least on its one polymer chain terminal and whose number average molecular weight is 1,000-500,000. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

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

  In recent years, research on optical materials has been actively conducted, and particularly in the field of lens materials, materials that are excellent in high refraction, heat resistance, transparency, easy moldability, light weight, chemical resistance, solvent resistance, etc. Development of 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. .

  Accordingly, it is required to increase the refractive index of the material itself for the purpose of thinning the lens and miniaturizing the image sensor. For example, a technique for introducing a sulfur atom into a polymer (for example, see Patent Documents 1 and 2), a technique for introducing a halogen atom or an aromatic ring into a polymer (for example, see Patent Document 3), and the like have been actively studied. It was. However, a plastic material that has a large refractive index and good transparency and can be used as a substitute for glass has not yet been developed. In addition, in an optical fiber or an optical waveguide, materials having different refractive indexes are used in combination, or materials having a distribution in refractive index are used. In order to provide a material having a different refractive index depending on a part as described above, development of a technique capable of arbitrarily adjusting the refractive index is also desired.

  Since it is difficult to increase the refractive index with only an organic substance, a technique for increasing the refractive index of a resin by dispersing an inorganic substance having a high refractive index in a resin matrix has been reported (for example, 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, it has not been possible to disperse the fine particles in the resin matrix at a high concentration without reducing the transparency of the resin.

  Also, a molded product mainly comprising a thermoplastic resin composition in which ultrafine particles having a number average particle size of 0.5 to 50 nm are dispersed, wherein the average birefringence per 1 mm of light wavelength is 10 nm or less. A thermoplastic material composition comprising a molded body (for example, see Patent Document 5), a thermoplastic resin having a refractive index and an Abbe number indicated by a specific mathematical formula, and inorganic fine particles having a specific average particle diameter and refractive index. Articles and optical parts using the same have been reported (for example, see Patent Documents 6 and 7). These are also those in which inorganic fine particles are dispersed in the resin, but none of them exhibit sufficient performance from the viewpoint of dispersing the fine particles in the resin matrix at a high concentration without reducing the transparency of the resin. It was.

On the other hand, as the organic-inorganic composite composition, for example, a method of melt-kneading inorganic particles whose surface has been modified with an acidic group-containing resin has been reported, but the addition amount of the inorganic particles is about 1% by mass, which is sufficient It cannot be said (see Patent Document 8). In addition, an organic-inorganic composite composition in which the surface modification group of inorganic particles and a resin are bonded via a linker has been reported (see Patent Document 9), but the operation is complicated such as requiring high temperature for bond formation and gelation. From the viewpoint of molding processability, sufficient performance was not exhibited. In addition, none of these patent documents describes a thick transparent molded body that can be used for a lens having a high refractive index.
JP 2002-131502 A Japanese Patent Laid-Open No. 10-298287 JP 2004-244444 A JP 2003-73559 A JP 2003-147090 A JP 2003-73563 A JP 2003-73564 A JP 2004-217714 A Special table 2004-352975 gazette

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

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

[1] An inorganic fine particle having a refractive index of 1.90 to 3.00, a functional group capable of forming a chemical bond with the inorganic fine particle at at least one polymer chain end, and a number average molecular weight of 1,000. An organic-inorganic composite composition comprising a thermoplastic resin having a viscosity of ˜500,000.
[2] The functional group capable of forming a chemical bond with inorganic fine particles is

−ＳＯ₃Ｈ、−ＯＳＯ₃Ｈ、−ＣＯ₂Ｈ、および、−Ｓｉ（ＯＲ⁵）_mＲ⁶ _3-m〔Ｒ¹、Ｒ²、Ｒ³、Ｒ⁴、Ｒ⁵、Ｒ⁶はそれぞれ独立に水素原子、置換または無置換のアルキル基、置換または無置換のアルケニル基、置換または無置換のアルキニル基、あるいは置換または無置換のフェニル基を表す。ｍは１〜３の整数を表す。〕からなる群より選ばれる官能基またはその塩であることを特徴とする［１］に記載の有機無機複合組成物。
［３］ 前記熱可塑性樹脂の屈折率が１．５５より大きいことを特徴とする［１］または［２］に記載の有機無機複合組成物。
［４］ 前記無機微粒子の数平均粒子サイズが１ｎｍ〜１５ｎｍであることを特徴とする［１］〜［３］のいずれか一項に記載の有機無機複合組成物。
［５］ 前記無機微粒子としてチタン酸化物かジルコニウム酸化物の少なくとも一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組成物。
［７］ 熱可塑性であることを特徴とする［１］〜［６］のいずれか一項に記載の有機無機複合組成物。
［８］ 溶媒を含まない固体であることを特徴とする［１］〜［７］のいずれか一項に記載の有機無機複合組成物。

—SO ₃ H, —OSO ₃ H, —CO ₂ H, and —Si (OR ⁵ ) _m R ⁶ _3-m [R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ are each independent. Represents a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkynyl group, or a substituted or unsubstituted phenyl group. m represents an integer of 1 to 3. ] The organic-inorganic composite composition according to [1], which is a functional group selected from the group consisting of
[3] The organic-inorganic composite composition according to [1] or [2], wherein a refractive index of the thermoplastic resin is greater than 1.55.
[4] The organic-inorganic composite composition according to any one of [1] to [3], wherein the number average particle size of the inorganic fine particles is 1 nm to 15 nm.
[5] The organic-inorganic composite composition according to any one of [1] to [4], wherein the inorganic fine particles include at least one of titanium oxide and zirconium oxide.
[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 80% or more.
[7] The organic-inorganic composite composition according to any one of [1] to [6], which is thermoplastic.
[8] The organic-inorganic composite composition according to any one of [1] to [7], which is a solid containing no solvent.

[9] Inorganic fine particles having a refractive index of 1.90 to 3.00, a functional group capable of forming a chemical bond with the inorganic fine particles at at least one polymer chain end, and a number average molecular weight of 1,000. The manufacturing method of the organic inorganic composite composition characterized by including the process of mixing the thermoplastic resin which is -500,000 in an organic solvent.
[10] A step of surface-treating inorganic fine particles having a refractive index of 1.90 to 3.00 in water, alcohol, or a mixture of water and alcohol in the presence of a surface treatment agent, and surface-treated inorganic fine particles A step of extracting into an organic solvent, and the extracted inorganic fine particles have a functional group capable of forming a chemical bond with the inorganic fine particles at at least one polymer chain end and have a number average molecular weight of 1,000 to 500,000. The method for producing an organic-inorganic composite composition according to [9], further comprising a step of mixing with a thermoplastic resin.
[11] An organic solvent dispersion of inorganic fine particles having a refractive index of 1.90 to 3.00, a functional group capable of forming a chemical bond with the inorganic fine particles at at least one polymer chain end, and a number average The organic material according to [9] or [10], comprising a step of mixing a thermoplastic resin having a molecular weight of 1,000 to 500,000 and a step of distilling off the solvent from the mixed solution. A method for producing an inorganic composite composition.
[12] An organic solvent dispersion of inorganic fine particles having a refractive index of 1.90 to 3.00, a functional group capable of forming a chemical bond with the inorganic fine particles at at least one polymer chain end, and a number average The organic-inorganic composite as described in [9] or [10], comprising a step of mixing a thermoplastic resin having a molecular weight of 1,000 to 500,000 and a step of reprecipitation of the mixed solution A method for producing the composition.
[13] An organic-inorganic composite composition produced by the production method according to any one of [9] to [12].

[14] A molded article comprising the organic-inorganic composite composition according to any one of [1] to [8] or [13], wherein the maximum thickness is 0.1 mm or more.
[15] The molded article according to [14], wherein the light transmittance in terms of 1 mm thickness at a wavelength of 589 nm is 70% or more and the refractive index is 1.63 or more.

[16] An optical component comprising the molded article according to [14] or [15].
[17] The optical component according to [16], which is a lens base material.

  According to the present invention, an organic-inorganic composite composition having both excellent transparency and a high refractive index, and an optical component using the same can be provided. Moreover, 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 optical components such as a lens base material including the composition will be described in detail. The description of the constituent elements described below may be made based on typical embodiments of the present invention, but the present invention is not limited to such embodiments. In the present specification, a numerical range represented by using “to” means a range including numerical values described before and after “to” as a lower limit value and an upper limit value.

[Organic-inorganic composite composition]
The organic-inorganic composite composition of the present invention has an inorganic fine particle having a refractive index of 1.90 to 3.00, a functional group capable of forming a chemical bond with the inorganic fine particle at at least one polymer chain end, and And a thermoplastic resin having a number average molecular weight of 1,000 to 500,000. In the organic-inorganic composite composition of the present invention, inorganic fine particles are dispersed in the thermoplastic resin.

  The organic-inorganic composite composition of the present invention is preferably a solid. The solvent content is preferably 25% by mass or less, more preferably 20% by mass or less, further preferably 10% by mass or less, and most preferably no solvent.

  The refractive index of the organic-inorganic composite composition of the present invention is preferably 1.60 or more at a wavelength of 589 nm, more preferably 1.63 or more, further preferably 1.65 or more, and 1.67. The above is particularly preferable.

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

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

  Hereinafter, the thermoplastic resin and the inorganic fine particles, which are essential components of the organic-inorganic composite composition of the present invention, will be described in order. In addition to these essential components, the organic-inorganic composite composition of the present invention may contain additives such as a resin, a dispersant, a plasticizer, and a release agent that do not satisfy the conditions of the present invention.

[Thermoplastic resin]
The organic-inorganic composite composition of the present invention has a functional group capable of forming a chemical bond with inorganic fine particles at at least one polymer chain end, and has a number average molecular weight of 1,000 to 500,000. Contains resin.

  Even if the composition contains a large amount of inorganic fine particles whose particle size is sufficiently smaller than the wavelength of light, the aggregation of the inorganic fine particles cannot be prevented, and the transmitted light is attenuated by Rayleigh scattering. Since large attenuation of transmitted light must be avoided, the conventional method cannot increase the inorganic component in the organic-inorganic composite composition. However, in the present invention, not only inorganic fine particles having a small particle size but also a thermoplastic resin having a number average molecular weight of 1,000 to 500,000 having a specific functional group or a salt thereof at the end of the polymer chain is used as a matrix. An organic-inorganic composite composition that achieves uniform dispersion of inorganic fine particles in the matrix, suppresses scattering at the interface between the inorganic fine particles and the thermoplastic resin, and has a refractive index exceeding 1.70, and It is now possible to obtain an optical component including the above.

  The basic skeleton of the thermoplastic resin used in the present invention is not particularly limited, and poly (meth) acrylate, polystyrene, polyvinylcarbazole, polyarylate, polycarbonate, polyurethane, polyimide, polyether, polyethersulfone, polyetherketone , Known resin skeletons such as polythioether, cycloolefin polymer, and cycloolefin copolymer can be employed. Preferred are vinyl polymers, polyarylate, and aromatic-containing polycarbonates, and more preferred are vinyl polymers.

  Examples of monomers that can be used in the vinyl polymer include those described in Polymer Handbook 2nd ed., J. Brandrup, Wiley lnterscience (1975) Chapter 2 Page 1-483. Specifically, for example, styrene derivatives, 1-vinylnaphthalene, 2-vinylnaphthalene, vinylcarbazole, acrylic acid esters, methacrylic acid esters, acrylamides, methacrylamides, allyl compounds, vinyl ethers, vinyl esters, Examples thereof include compounds having one addition polymerizable unsaturated bond selected from dialkyl itaconates, dialkyl esters or monoalkyl esters of the fumaric acid.

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

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

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

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

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

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

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

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

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

  In addition, acrylonitrile, methacrylonitrile, maleilonitrile, maleimide (N-methylmaleimide, N-phenylmaleimide) and the like can also be exemplified.

  Monomers that can be used in the polyarylate and aromatic-containing polycarbonate include bisphenol derivatives (for example, bisphenol A, fluorene bisphenol, 9,9-bis [4- (2-hydroxyethoxy) phenyl] fluorene, etc.), phthalic acid derivatives (for example, Terephthalic acid, isophthalic acid), naphthalene dicarboxylic acid derivatives (for example, 2,6-naphthalene dicarboxylic acid, etc.), phosgene derivatives (for example, phosgene, phosgene dimer, etc.), carbonate ester derivatives (for example, diphenyl carbonate, etc.), etc. be able to.

  The thermoplastic resin used in the present invention preferably has a refractive index greater than 1.50, more preferably greater than 1.55, even more preferably greater than 1.60, and particularly preferably greater than 1.65. preferable. The refractive index in the present invention is a value measured with respect to light having a wavelength of 589 nm using an Abbe refractometer (manufactured by Atago Co., Ltd., “DR-M4”).

  The thermoplastic resin used in the present invention preferably has a glass transition temperature of 50 ° C to 400 ° C, and more preferably 80 ° C to 380 ° C. If a resin having a glass transition temperature of 50 ° 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.

  Further, the thermoplastic resin used in the present invention preferably has a light transmittance of 1% in thickness at a wavelength of 589 nm of 80% or more, more preferably 85% or more.

  The number average molecular weight of the thermoplastic resin used in the present invention is 1,000 to 500,000. The number average molecular weight of the thermoplastic resin is preferably 3,000 to 300,000, more preferably 5,000 to 200,000, and particularly preferably 10,000 to 100,000. When the number average molecular weight of the thermoplastic resin is less than 1,000, an organic-inorganic composite composition having sufficient mechanical strength cannot be obtained. On the other hand, when the number average molecular weight of the resin exceeds 500,000, molding processing becomes difficult.

  The thermoplastic resin used in the present invention has a functional group capable of forming a chemical bond with inorganic fine particles at at least one polymer chain end. Here, the “chemical bond” includes, for example, a covalent bond, an ionic bond, a coordination bond, a hydrogen bond, and the like, and when there are a plurality of functional groups, each can form a chemical bond different from the inorganic fine particles. It may be. Whether or not a chemical bond can be formed depends on whether the functional group of the thermoplastic resin is chemically bonded to the inorganic fine particles when the thermoplastic resin and the inorganic fine particles are mixed in an organic solvent as described in Examples described later. Judgment is made based on whether or not it can be formed. In the organic-inorganic composite composition of the present invention, all of the functional groups of the thermoplastic resin may form chemical bonds with the inorganic fine particles, or some of them may form chemical bonds with the inorganic fine particles. Good.

  The functional group capable of forming a chemical bond with inorganic fine particles is not particularly limited in its structure as long as it can form a chemical bond with inorganic fine particles.

−ＳＯ₃Ｈ、−ＯＳＯ₃Ｈ、−ＣＯ₂Ｈ、および、−Ｓｉ（ＯＲ⁵）_mＲ⁶ _3-mからなる群より選ばれる官能基またはその塩であることが好ましい。前記官能基またはその塩としては、

A functional group selected from the group consisting of —SO ₃ H, —OSO ₃ H, —CO ₂ H, and —Si (OR ⁵ ) _m R ⁶ _3-m or a salt thereof is preferable. As the functional group or a salt thereof,

−ＳＯ₃Ｈ、−ＣＯ₂Ｈ、および、−Ｓｉ（ＯＲ⁵）_mＲ⁶ _3-mからなる群より選ばれる官能基またはその塩が好ましく、

A functional group selected from the group consisting of —SO ₃ H, —CO ₂ H, and —Si (OR ⁵ ) _m R ⁶ _3-m or a salt thereof is preferable.

−ＳＯ₃Ｈ、−ＣＯ₂Ｈ、またはこれらの塩がより好ましく、

-SO ₃ H, -CO ₂ H or more preferably salts thereof,

−ＳＯ₃Ｈ、またはこれらの塩がさらに好ましい。

More preferred is —SO ₃ H or a salt thereof.

R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ are each independently a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkynyl group, or Represents a substituted or unsubstituted phenyl group, preferably a hydrogen atom or a substituted or unsubstituted alkyl group. m represents an integer of 1 to 3, and is preferably 3.

  The functional group capable of forming a chemical bond with the inorganic fine particles may be present only at one end of the polymer chain of the thermoplastic resin or at both ends, but only at one end of the polymer chain. It is preferable. Further, a plurality of functional groups may exist at the terminal. The term “terminal” as used herein means a portion excluding a structure sandwiched between repeating units constituting a polymer chain.

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

  Although the preferable specific example (Exemplary compound P-1 to P-14) of the thermoplastic resin which can be used by this invention is given to the following, the thermoplastic resin which can be used by this invention is not limited to these. Absent. The structure in [] represents a repeating unit, and x and y of the repeating unit represent a copolymerization ratio (mol ratio).

These thermoplastic resins may be used alone or in combination of two or more. Further, these thermoplastic resins may contain other copolymer components.
The organic-inorganic composite composition of the present invention may contain a resin that does not satisfy the conditions of the present invention together with the thermoplastic resin that satisfies the conditions of the present invention. For example, a resin that does not have a functional group at the end of the polymer chain and a thermoplastic resin that satisfies the conditions of the present invention may be mixed and used. Although there is no restriction | limiting in particular in the kind of resin which does not have a functional group at the polymer chain terminal, What satisfy | fills the optical physical property mentioned above, a thermophysical property, and molecular weight is preferable.

[Inorganic fine particles]
The organic-inorganic composite composition of the present invention includes inorganic fine particles having a refractive index of 1.90 to 3.00.
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, examples include titanium oxide fine particles, zinc oxide fine particles, zirconium oxide fine particles, tin oxide fine particles, zinc sulfide fine particles, barium titanate fine particles, and the like, preferably titanium oxide fine particles, zirconium oxide fine particles, sulfides. Zinc fine particles and barium titanate fine particles, more preferably fine particles containing titanium oxide and / or zirconium oxide. However, the inorganic fine particles that can be used in the present invention are not limited to the materials exemplified here.

  In the present invention, one type of inorganic fine particles may be used alone, or a plurality of types of inorganic fine particles may be used in combination. Moreover, you may use as a composite of these inorganic substances from a viewpoint of refractive index, transparency, or stability. These fine particles are doped with different elements for various purposes such as photocatalytic activity reduction and water absorption reduction, the surface layer is coated with different metal oxides such as silica and alumina, silane coupling agents, titanate coupling agents. Fine particles whose surface has been modified may be used.

The method for producing inorganic fine particles used in the present invention is not particularly limited, and any known method can be used. For example, desired oxide fine particles can be obtained by using a metal halide or an alkoxy metal as a raw material and hydrolyzing in a reaction system containing water.
Specifically, titanyl sulfate is exemplified as a synthetic raw material for titanium oxide nanoparticles, and zinc salts such as zinc acetate and zinc nitrate are exemplified as synthetic raw materials for zinc oxide nanoparticles. Metal alkoxides such as tetraethoxysilane and titanium tetraisopropoxide are also suitable as raw materials for inorganic fine particles. As a method for synthesizing such inorganic fine particles, for example, Japanese Journal of Applied Physics, Vol. 37, pages 4603-4608 (1998), or Langmuir, Vol. 16, No. 1, pages 241-246 (2000). ).

  In particular, when the oxide nanoparticles are synthesized by the sol generation method, for example, as in the synthesis of titanium oxide nanoparticles using titanyl sulfate as a raw material, this is passed through a precursor such as hydroxide, and then this is oxidized with acid or alkali. Procedures to form hydrosols by dehydration condensation or peptization 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 (trade name “Eleminol JS-2” manufactured by Sanyo Chemical Industries, Ltd.) is added to the resulting hydrosol. The sol particles may be isolated by making them water-insoluble. For example, a known method described in “Coloring Materials” Vol. 57, No. 6, pp. 305-308 (1984) can be used.

Further, as a method other than the method of hydrolyzing in water, a method of producing inorganic fine particles in an organic solvent can also be mentioned. At this time, the thermoplastic resin used in the present invention may be dissolved in the organic solvent.
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 influence of Rayleigh scattering becomes remarkable, and the organic-inorganic composite composition The transparency of the object may be extremely reduced. Therefore, the lower limit of the number average particle size of the inorganic fine particles used in the present invention is preferably 1 nm or more, more preferably 2 nm or more, further preferably 3 nm or more, and the upper limit is preferably 15 nm or less, more preferably 10 nm. Hereinafter, it is more preferably 5 nm or less. That is, the number average particle size of the inorganic fine particles in the present invention is preferably 1 nm to 15 nm, more preferably 2 nm to 10 nm, and particularly preferably 3 nm to 5 nm.
Here, the above-mentioned number average particle size can be measured, for example, by X-ray diffraction (XRD) or a transmission electron microscope (TEM).

  The range of the refractive index of the inorganic fine particles used in the present invention is 1.90 to 3.00 at a wavelength of 589 nm at 22 ° C., preferably 1.90 to 2.70, and preferably 2.00 to 2.70. More preferably, it is 70. If the refractive index of the inorganic fine particles in the present invention is 1.90 or more, it is easy to produce an organic-inorganic composite composition having a refractive index greater than 1.80. On the other hand, if the refractive index is 3.00 or less, it is easy to produce an organic-inorganic composite composition having a transmittance of 80% or more.

  The refractive index of the inorganic fine particles is determined by measuring the refractive index with an Abbe refractometer (for example, “DM-M4” manufactured by Atago Co., Ltd.) using a composite compounded with the thermoplastic resin used in the present invention as a transparent film. It can be estimated by a method of converting from the measured refractive index of only the resin component or a method of calculating the refractive index of the fine particles by measuring the refractive index of the fine particle dispersion having different concentrations.

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

[Additive]
In addition to the above thermoplastic resin and inorganic fine particles, the organic-inorganic composite composition of the present invention may contain various additives as appropriate from the viewpoint of uniform dispersibility, fluidity during molding, releasability, weather resistance, and the like. Good.
Although the blending ratio of these additives varies depending on the purpose, it is preferably 0 to 50% by mass and more preferably 0 to 30% by mass with respect to the total amount of the inorganic fine particles and the thermoplastic resin. 0 to 20% by mass is particularly preferable.

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

As said surface treating agent, what has a structure represented by following General formula (1) is preferable.
General formula (1)
AB

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

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

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

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

<Plasticizer>
When the glass transition temperature of the thermoplastic resin used in the present invention is high, molding of the composition may not always be easy. For this reason, a plasticizer may be used to lower the molding temperature of the composition of the present invention. When the plasticizer is added, the addition amount is preferably 1 to 50% by mass of the total amount of the organic-inorganic composite composition, more preferably 2 to 30% by mass, and 3 to 20% by mass. Is particularly preferred.
The plasticizer used in the present invention must be determined by comprehensively considering compatibility with the resin, weather resistance, plasticizing effect, etc. Although it cannot say, what has an aromatic ring from a viewpoint of refractive index is preferable, and what has a structure represented by following General formula (2) as a typical example can be mentioned.

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

(In the formula, B ¹ and B ² represent an alkyl group having 6 to 18 carbon atoms or an arylalkyl group having 6 to 18 carbon atoms, m represents 0 or 1, and X represents

のうちのいずれかであり、Ｒ¹¹ およびＲ¹² 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 ¹¹ and R ¹² each independently represents a hydrogen atom or an alkyl group having 4 or less carbon atoms. )

In the compound represented by the general formula (2), B ¹ and B ² may be any alkyl group or arylalkyl group within the range of 6 to 18 carbon atoms. If the number of carbon atoms is less than 6, the molecular weight may be too low to boil at the melting temperature of the polymer and generate bubbles. Moreover, when carbon number exceeds 18, compatibility with a polymer may worsen and an addition effect may become inadequate.

Specific examples of B ¹ and B ² include direct n-hexyl group, n-octyl group, n-decyl group, n-dodecyl group, n-tetradecyl group, n-hexadecyl group, n-octadecyl group and the like. Examples thereof include a chain alkyl group, a branched alkyl group such as a 2-hexyldecyl group and a methyl branched octadecyl group, and an arylalkyl group such as a benzyl group and a 2-phenylethyl group. Specific examples of the compound represented by the general formula (2) include the following compounds, among which W-1 (trade name “KP-L155” manufactured by Kao Corporation) is preferable.

<Other additives>
In addition to the above components, hindered phenols, amines and phosphoruss are added for the purpose of adding known release agents such as modified silicone oils for the purpose of improving moldability and improving light resistance and thermal degradation. Further, a known deterioration preventing agent such as thioether may be added as appropriate. When mix | blending these, it is preferable to set it as about 0.1-5 mass% with respect to the total solid of an organic inorganic composite composition.

[Method for producing organic-inorganic composite composition]
The inorganic fine particles used in the present invention are dispersed in the resin by chemically bonding with the thermoplastic resin having the functional group at at least one polymer chain end.
Since the inorganic fine particles used in the present invention have a small particle size and high surface energy, it is difficult to re-disperse when isolated as a solid. Therefore, the inorganic fine particles are preferably mixed with the thermoplastic resin in a state of being dispersed in the solution to form a stable dispersion. As a preferable method for producing a composite, (1) surface treatment of inorganic particles in the presence of the surface treatment agent, extraction of the surface-treated inorganic fine particles into an organic solvent, and extraction of the inorganic fine particles into the heat A method for producing a composite of inorganic fine particles and a thermoplastic resin by uniformly mixing with a plastic resin, and (2) using a solvent capable of uniformly dispersing or dissolving both the inorganic fine particles and the thermoplastic resin to uniformly mix both the inorganic fine particles and the thermoplastic resin. The method of manufacturing the composite of microparticles | fine-particles and a thermoplastic resin is mentioned.

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

  When the method (2) is employed, dimethylacetamide, dimethylformamide, dimethylsulfoxide, benzyl alcohol, cyclohexanol, ethylene glycol monomethyl ether, 1-methoxy-2-propanol, tert-butanol, acetic acid, propionic acid are used as the solvent. Hydrophilic polar solvents such as single or mixed solvents, or mixed solvents of non-water soluble solvents such as chloroform, dichloroethane, dichloromethane, ethyl acetate, methyl ethyl ketone, methyl isobutyl ketone, toluene, chlorobenzene, methoxybenzene and the above polar solvents Preferably used. In this case, a dispersant, a plasticizer, a mold release agent, or another type of polymer may be added as necessary in addition to the above-described thermoplastic resin. When using fine particles dispersed in water / methanol, after adding a hydrophilic solvent which has a higher boiling point than water / methanol and dissolves the thermoplastic resin, the water / methanol is concentrated and distilled to disperse the fine particles. After replacing the liquid with a polar organic solvent, it is preferable to mix with the resin. At this time, the surface treatment agent may be added.

  The solution of the organic-inorganic composite composition obtained by the methods (1) and (2) can be cast as it is to obtain a molded body. In the present invention, the solution is particularly concentrated, freeze-dried, Alternatively, after removing the solvent by a method such as reprecipitation from a suitable poor solvent, it is preferable to form the powdered solid content by a method such as injection molding or compression molding.

[Molded body]
The molded article of the present invention can be produced by molding the organic-inorganic composite composition of the present invention. As the molded article of the present invention, those showing the refractive index and optical properties described above in the description of the organic-inorganic composite composition are useful. Among them, a molded product having a light transmittance of 70% or more at a wavelength of 589 nm and a refractive index of 1.63 or more is useful.

  Moreover, it is preferable that the maximum thickness of the molded object of this invention is 0.1 mm or more. The maximum thickness is preferably 0.1 to 5 mm, and more preferably 1 to 3 mm. A molded body having these thicknesses is particularly useful as an optical component having a high refractive index. Such a thick molded body is generally not easy because it is difficult to remove the solvent even if it is manufactured by the solution casting method. However, if the organic-inorganic composite composition of the present invention is used, it is easy to mold and a complicated shape such as an aspherical surface can be easily realized. Thus, according to the present invention, it is possible to obtain a molded article having good transparency while utilizing the high refractive index characteristics of the fine particles.

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

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

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

  When the lens substrate in the present invention is used as a lens, the lens substrate itself of the present invention may be used alone as a lens, or may be used as a lens with a film or a frame added as described above. . The type and shape of the lens using the lens substrate of the present invention are not particularly limited. The lens substrate of the present invention includes, for example, a spectacle lens, an optical device lens, an optoelectronic lens, a laser lens, a pickup lens, an in-vehicle camera lens, a portable camera lens, a digital camera lens, an OHP lens, Used for microlens arrays and the like.

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

[Analysis and Evaluation Method]
(1) Observation with Transmission Electron Microscope (TEM) “H-9000UHR Transmission Electron Microscope” manufactured by Hitachi, Ltd. (acceleration voltage 200 kV, degree of vacuum at observation about 7.6 × 10 ⁻⁹ Pa) went.

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

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

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

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

[Synthesis of organic-inorganic composite composition]
(1) Synthesis of Titanium Oxide Fine Particles Titanium oxide fine particles were synthesized according to the method described in Synthesis Example 9 of JP-A-2003-73559. From XRD and TEM, it was confirmed that anatase-type titanium oxide fine particles (number average particle size was about 5 nm) were formed.

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

(3) Synthesis of zirconium oxide fine particle toluene dispersion (1) The zirconium oxide fine particle suspension synthesized in (2) above was mixed with a toluene solution in which “KAYAMER PM-21” manufactured by Nippon Kayaku was dissolved. After stirring at 0 ° C. for 8 hours, the toluene solution was extracted to prepare a zirconium oxide fine particle toluene dispersion.

(4) Preparation of Zirconium Oxide Dimethylacetamide Dispersion (2) 500 g of N, N′-dimethylacetamide was added to 500 g of the zirconium oxide dispersion (15% by mass aqueous dispersion) prepared in the above (1) to make it about 500 g or less. After concentration under reduced pressure until solvent substitution, the concentration was adjusted by addition of N, N′-dimethylacetamide to obtain a 15 mass% zirconium oxide dimethylacetamide dispersion (2).

(4) Synthesis of Exemplified Compound P-19 In a 300 ml three-necked flask equipped with a reflux condenser and a gas introduction cock, 96.9 g (0.55 mol) of benzyl methacrylate, 0.9 g of AIBN (azobisisobutyronitrile) ( 5.5 mmol), 0.39 g (5 mmol) of 2-mercaptoethanol, and 100 ml of THF are charged and heated at 65 ° C. for 3 hours under a nitrogen stream. A large amount of methanol was added to cause precipitation, and the precipitate was collected by filtration, washed with a large amount of methanol, and vacuum dried at 60 ° C. for 3 hours to obtain a polymer (yield 80%).
Next, a 100 ml three-necked flask equipped with a gas introduction cock was charged with 1.0 g (6.5 mmol) of phosphorus oxychloride, 1.2 g (12 mmol) of triethylamine, and 15 ml of THF, while keeping the internal temperature at 0 ° C. or lower in a nitrogen stream. A solution of 10 g of the polymer obtained above in 25 ml of THF was added dropwise. After completion of dropping, the mixture was stirred at room temperature for 8 hours. Furthermore, 10 ml of water was added and stirred at room temperature for 2 hours. Next, the mixture was poured into a large amount of methanol for precipitation, and the precipitate was collected by filtration, washed with a large amount of methanol, and dried in vacuo at 60 ° C. for 3 hours to obtain Exemplified Compound P-19. The yield of the obtained compound was 95%, the number average molecular weight was 21,100, and the weight average molecular weight was 38,300.

(5) 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. While heating under reflux, a solution of 16.8 g (80.7 mmol) of triisopropyl phosphite in 20 ml of m-xylene was added dropwise under a nitrogen stream. After completion of the dropwise addition, the mixture was heated to reflux for 3 hours, and the solvent was distilled off. Then, it refine | purified by silica gel column chromatography, and the living radical polymerization initiator A (initiator A) which has the following structure was obtained with 53% of the yield.

(6) Synthesis of Exemplified Compound P-8 In a 200 ml three-necked flask equipped with a reflux condenser and a gas introduction cock, 0.41 g (2.86 mmol) of copper bromide, 59.6 g (0.57 mol) of styrene, N, N, N ′, N ′, N ″ -pentamethyldiethylenetriamine (0.5 g, 2.86 mmol) and the initiator A (1.0 g, 2.86 mmol) were charged, and the atmosphere was purged with nitrogen five times. After the flask was returned to room temperature, 30 g of alumina and 50 ml of toluene were added, stirred for 10 minutes, filtered through celite, and then the filtrate was poured into a large amount of methanol for precipitation, and the precipitate was collected by filtration. This was washed with a large amount of methanol, and vacuum-dried at 60 ° C. for 3 hours to obtain a polymer (yield 38%).

  Next, 10 g of the polymer obtained above, 2.3 g (15 mmol) of trimethylsilyl bromide, and 40 ml of methylene chloride were charged into a 100 ml three-necked flask equipped with a gas introduction cock, and stirred at room temperature for 24 hours under a nitrogen stream. Further, 10 ml of water was added and stirred for 1 hour, and then poured into a large amount of methanol for precipitation. 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 Illustrative Compound P-8. The yield of the obtained compound was 96%, the number average molecular weight was 25,200, and the weight average molecular weight was 28,200.

(7) Synthesis of Exemplified Compound P-16 In a three-necked flask under nitrogen, 1.15 ml (1.61 mmol) of a 1.4 mol / L sec-butyllithium cyclohexane solution was added to 300 ml of dehydrated benzene, and the reaction temperature was 40 ° C. Styrene 50g (0.48mol) was dripped so that it might be kept at. After dripping, it cooled to 10 degreeC and added 0.1 ml of ethylene oxide. The mixture was heated to 40 ° C. and added to a benzene solution containing 0.5 ml of phosphorus oxychloride. After stirring at 40 ° C. for 3 hours, 10 ml of water is added, poured into a large amount of methanol and precipitated. The precipitate is collected by filtration, washed with a large amount of methanol, and vacuum dried at 60 ° C. for 3 hours to obtain a polymer. Obtained. The yield was 90%, the number average molecular weight was 30,400, and the weight average molecular weight was 31,900.

(7) Synthesis of PMMA (polymethyl methacrylate) Methyl methacrylate (5.00 g) and azobisisobutyronitryl (0.25 g) were added to 2-butanone, and polymerization was performed at 70 ° C. under nitrogen to synthesize PMMA. The weight average molecular weight was 100,000.

[Preparation of organic-inorganic composite composition and production of molded body]
(1) Examples 1-6, Comparative Examples 1-5
Each lens of Examples 1-6 and Comparative Examples 1-5 was manufactured in the following procedures. The type of thermoplastic resin and the type and amount of inorganic fine particles used in the following procedure are as shown in Table 1 below, and the refractive indexes of the thermoplastic resin and the inorganic fine particles are also shown. In Table 1, the amount of inorganic fine particles added is indicated on the basis of the mass of the molded article to be produced. In Comparative Examples 1 to 3, only the thermoplastic resin was molded without adding inorganic fine particles.
Titanium oxide fine particles or zirconium oxide fine particles dispersed in toluene were added dropwise to the anisole solution of the thermoplastic resin over 5 minutes, and the resulting mixture was stirred for 1 hour, and then the solvent was concentrated and distilled off. The obtained organic / inorganic composite composition was compression-molded by heating (temperature: 180 ° C., pressure: 13.7 MPa, time: 2 minutes) to produce a molded article for 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 thermoplastic resin. Further, light transmittance measurement and refractive index measurement were performed. These results are shown in Table 1 below. Thereafter, the lens molding was molded into a lens shape to obtain a lens as an optical component.

(2) Example 7
In the zirconium oxide dimethylacetamide dispersion, a thermoplastic resin P-19, n-octylbenzoic acid, and KP-L155 (trade name; manufactured by Kao Corporation) as a plasticizer have a mass ratio of ZrO ₂ solid content / P- After adding 19 / n-octylbenzoic acid / KP-L155 = 35.7 / 42.9 / 7 / 14.3, stirring and mixing uniformly, the dimethylacetamide solvent was heated under reduced pressure. Concentrated. The concentrated residue was heat compression molded under the same conditions as in Example 1 to prepare a transparent molded body (lens substrate). The molded body obtained in Example 7 was cut, and the cross section was observed with TEM. Further, light transmittance measurement and refractive index measurement were performed. The results are shown in Table 1 below.

(3) Examples 8 and 9
Transparent molded bodies (lens substrates) of Examples 8 and 9 were prepared in the same manner as in Example 7 except that the thermoplastic resin P-19 in Example 7 was changed to P-8 and P-16. The molded bodies obtained in Examples 8 and 9 were cut, and the cross section was observed with TEM. Further, light transmittance measurement and refractive index measurement were performed. The results are shown in Table 1 below.

(4) Example 10
The organic-inorganic composite composition of Example 10 was obtained by filtering and drying the precipitate obtained by adding the dimethylacetamide solution before concentration of the organic-inorganic composite composition described in Example 8 to a large excess of water. . A transparent molded body (lens substrate) of Example 10 was obtained in the same manner as Example 1 using the organic-inorganic composite composition. The transparent molded body obtained in Example 10 was cut and the cross section was observed with TEM. Further, light transmittance measurement and refractive index measurement were performed. The results are shown in Table 1 below.

From Table 1, it can be seen that the fine particle-containing transparent molded product of the present invention has a high refractive index, and even a 1 mm thick molded product shows good transparency, and can be suitably used for optical applications.
In addition, it was confirmed that the organic-inorganic composite composition of the present invention mainly composed of a thermoplastic resin can form a lens shape with high productivity and accurately in accordance with the shape of the mold.

  The optical component of the present invention includes an organic-inorganic composite composition having both high refractive properties, light transmittance and light weight. 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 (17)

  An inorganic fine particle having a refractive index of 1.90 to 3.00, a functional group capable of forming a chemical bond with the inorganic fine particle at at least one polymer chain end, and a number average molecular weight of 1,000 to 500, An organic-inorganic composite composition comprising a thermoplastic resin having a viscosity of 000. The functional group capable of forming a chemical bond with inorganic fine particles

—SO ₃ H, —OSO ₃ H, —CO ₂ H, and —Si (OR ⁵ ) _m R ⁶ _3-m [R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ are each independent. Represents a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkynyl group, or a substituted or unsubstituted phenyl group. m represents an integer of 1 to 3. The organic-inorganic composite composition according to claim 1, which is a functional group selected from the group consisting of   The organic-inorganic composite composition according to claim 1 or 2, wherein a refractive index of the thermoplastic resin is larger than 1.55.   4. The organic-inorganic composite composition according to claim 1, wherein the number average particle size of the inorganic fine particles is 1 nm to 15 nm.   The organic-inorganic composite composition according to any one of claims 1 to 4, wherein the inorganic fine particles include at least one of titanium oxide and zirconium oxide.   The organic-inorganic composite composition according to any one of claims 1 to 5, wherein the light transmittance in terms of 1 mm thickness at a wavelength of 589 nm is 80% or more.   It is thermoplasticity, The organic inorganic composite composition as described in any one of Claims 1-6 characterized by the above-mentioned.   The organic-inorganic composite composition according to any one of claims 1 to 7, which is a solid containing no solvent.   An inorganic fine particle having a refractive index of 1.90 to 3.00, a functional group capable of forming a chemical bond with the inorganic fine particle at at least one polymer chain end, and a number average molecular weight of 1,000 to 500, The manufacturing method of the organic inorganic composite composition characterized by including the process of mixing the thermoplastic resin which is 000 in an organic solvent.   A step of surface-treating inorganic fine particles having a refractive index of 1.90 to 3.00 in water, alcohol, or a mixture of water and alcohol in the presence of a surface treatment agent; and surface-treated inorganic fine particles in an organic solvent And a heat having a functional group capable of forming a chemical bond with the inorganic fine particles at at least one polymer chain end and having a number average molecular weight of 1,000 to 500,000. The method for producing an organic-inorganic composite composition according to claim 9, comprising a step of mixing with a plastic resin.   An organic solvent dispersion of inorganic fine particles having a refractive index of 1.90 to 3.00, a functional group capable of forming a chemical bond with the inorganic fine particles at at least one polymer chain end, and a number average molecular weight of 1 The organic-inorganic composite composition according to claim 9 or 10, comprising a step of mixing a thermoplastic resin having a viscosity of 1,000,000 to 500,000 and a step of distilling off the solvent from the mixed solution. Production method.   An organic solvent dispersion of inorganic fine particles having a refractive index of 1.90 to 3.00, a functional group capable of forming a chemical bond with the inorganic fine particles at at least one polymer chain end, and a number average molecular weight of 1 A method for producing an organic-inorganic composite composition according to claim 9 or 10, comprising a step of mixing a thermoplastic resin having a viscosity of 1,000,000 to 500,000 and a step of reprecipitation of the mixed solution. .   The organic inorganic composite composition manufactured by the manufacturing method as described in any one of Claims 9-12.   The maximum thickness is 0.1 mm or more, The molded object containing the organic inorganic composite composition as described in any one of Claims 1-8 or 13 characterized by the above-mentioned.   The molded article according to claim 14, wherein the light transmittance in terms of 1 mm thickness at a wavelength of 589 nm is 70% or more and the refractive index is 1.63 or more.   An optical component comprising the molded article according to claim 14 or 15.   The optical component according to claim 16, wherein the optical component is a lens substrate.