WO2009017180A1 - Organic-inorganic hybrid composition and its article and optical component - Google Patents

Organic-inorganic hybrid composition and its article and optical component Download PDF

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Publication number
WO2009017180A1
WO2009017180A1 PCT/JP2008/063713 JP2008063713W WO2009017180A1 WO 2009017180 A1 WO2009017180 A1 WO 2009017180A1 JP 2008063713 W JP2008063713 W JP 2008063713W WO 2009017180 A1 WO2009017180 A1 WO 2009017180A1
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Prior art keywords
group
substituted
unsubstituted
organic
hybrid composition
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PCT/JP2008/063713
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French (fr)
Inventor
Ryo Suzuki
Hiroaki Mochizuki
Tatsuhiko Obayashi
Osamu Sawanobori
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Fujifilm Corporation
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Publication of WO2009017180A1 publication Critical patent/WO2009017180A1/en

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/04—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of organic materials, e.g. plastics

Definitions

  • the present invention relates to an organic-inorganic hybrid composition which is excellent in high refraction properties, transparency, lightweight properties and processability and to an optical component configured to contain the same, inclusive of lens base materials (for example, spectacle lenses, optical instrument lenses, optoelectronic lenses, laser lenses, pickup lenses, vehicle-mounted camera lenses, mobile phone camera lenses, digital camera lenses, OHP lens, lenses for configuring a micro lens array) .
  • lens base materials for example, spectacle lenses, optical instrument lenses, optoelectronic lenses, laser lenses, pickup lenses, vehicle-mounted camera lenses, mobile phone camera lenses, digital camera lenses, OHP lens, lenses for configuring a micro lens array
  • resins In comparison with glasses, resins have such advantages that they are excellent in lightweight properties, impact resistance and moldability and that they are economical, and in recent optical components such as lenses, the substitution of optical glass with a resin is advancing.
  • a molding method of a resin methods such as an injection molding method for casting a molten resin into a die to achieve molding, an extrusion molding method and a compression molding method are widely employed.
  • the fluidity of the resin is often of a problem.
  • the development, etc. of a material in which an inorganic nano particle is finely dispersed in a resin for the purpose of realizing a high function such as high refractive index and high heat resistance is performed (see, for example, JP-A- ⁇ l-291650 and JP-A-2003-73564) .
  • the fluidity is deteriorated, resulting in a serious problem from the viewpoint of imparting moldability.
  • a method for using a plasticizer As a measure for enhancing the fluidity of a resin, a method for using a plasticizer has hitherto been known, and phthalic ester based plasticizers, phosphoric ester based plasticizers, esters of a polyhydric carboxylic acid (for example, adipic acid, citric acid) and so on are widely used as the plasticizer.
  • DOP di-2-ethylhexyl phthalate
  • its refractive index to D-line is low as 1.486. Therefore, its application to a high-refractive index material having a refractive index of 1. ⁇ or more was difficult because it lowers the refractive index of the material.
  • An object of the invention is to provide an organic-inorganic hybrid composition having a fine particle uniformly dispersed in a resin matrix, having excellent transparency and high refractive index and having excellent stability with time and an optical component using the same, for example, lens base materials .
  • an organic-inorganic hybrid composition containing, as raw materials, an inorganic fine particle having a specified refractive index and a specified resin has high refraction properties and excellent transparency due to a uniform dispersion effect of the fine particle, leading to accomplishment of the invention as described below.
  • An organic-inorganic hybrid composition comprising a compound represented by the following formula (1) and an inorganic fine particle.
  • R 1 and R 2 each independently represents a substituent; L represents an oxy group or a methylene group; a represents 0 or 1; and ml and m2 each independently represents an integer of from 0 to 5.
  • R 3 , R 4 , R 5 , R 6 and R 7 each independently represents a substituent;
  • Z 1 , Z 2 , Z 3 and Z 4 each independently represents a hydrogen atom or a substituent;
  • m3, m4 and m6 each independently represents an integer of from 0 to 4;
  • Ra, Rb and Rc each independently represents a substituent, A represents an oxy group or a methylene group; A 2 represents an oxy group, a substituted or unsubstituted alkylene group, a carbonyl group, a substituted or an unsubstituted imino group or a group composed of two or more members of these groups; nl and n2 each independently 5 represents an integer of from 0 to 5; n3 represents an integer of from 0 to 4; and p, q and r_ each independently represents 0 or 1, provided that when q is 0, then r is 0.
  • thermoplastic resin is a thermoplastic resin having a functional group selected among the following groups:
  • R 11 , R 12 , R 13 and R 14 each independently 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 aryl group) , -SO 3 H, -OSO 3 H, -CO 2 H and -Si (OR 15 ) m iR 16 3 -mi (wherein
  • R 15 and R 16 each independently 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 aryl group; and ml represents an integer of from 1 to 3) in a side chain thereof.
  • thermoplastic resin is a copolymer containing, as a polymerization unit, a monomer represented by the following formula (6) .
  • R represents a hydrogen atom, a halogen atom or a methyl group
  • X represents a divalent connecting group selected among -CO 2 -, -OCO-, -CONH-, -OCONH-, -0C00-, -0-, -S-, -NH- and a substituted or unsubstituted arylene group
  • Y represents a divalent connecting group having from 1 to 30 carbon atoms
  • q represents an integer of from 0 to 18
  • Z represents a functional group selected among the following groups:
  • R 11 , R 12 , R 13 and R 14 each independently 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 aryl group) , -SO 3 H, -OSO 3 H, -CO 2 H and -Si (OR 15 ) ml R 16 3 _mi (wherein R 15 and R 16 each independently 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 aryl group; and ml represents an integer of from 1 to 3) .
  • R 21 , R 22 , R 23 and R 24 each independently 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 aryl group) , -SO 3 H, -OSO 3 H, -CO 2 H and -Si (OR 25 ) m2 R 26 3-m2 (wherein R 25 and R 26 each independently 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 aryl group; and m2 represents an integer of from 1 to 3) in at least one polymer end thereof.
  • thermoplastic resin is a block copolymer constituted of a hydrophobic segment and a hydrophilic segment.
  • an organic-inorganic hybrid composition having excellent transparency and high refractive index and having excellent stability with time and an optical component using the same. Also, according to the invention, it is possible to arbitrarily control the refractive index.
  • the organic-inorganic hybrid composition of the invention is characterized by containing a compound represented by the following formula (1) together with an inorganic fine particle.
  • R 1 and R 2 each independently represents a substituent.
  • the substituent which can be taken by R 1 and R 2 is not particularly limited, examples thereof include a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom) , an alkyl group (for example, a methyl group, an ethyl group) , an aryl group (for example, a phenyl group, a naphthyl group) , an alkenyl group, an alkynyl group, a cyano group, a carboxyl group, an alkoxycarbonyl group
  • a halogen atom for example, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom
  • an alkyl group for example, a methyl group, an ethyl group
  • an aryl group for example, a phenyl group, a nap
  • a methoxycarbonyl group for example, a methoxycarbonyl group
  • an aryloxycarbonyl group for example, a phenoxycarbonyl group
  • a substituted or unsubstituted carbamoyl group for example, a carbamoyl group, an N-phenylcarbamoyl group, an N,N-dimethylcarbamoyl group
  • an alkylcarbonyl group for example, an acetyl group
  • an arylcarbonyl group for example, a benzoyl group
  • a nitro group for example, an acylamino group (for example, an acetoamide group, an ethoxycarbonylamino group) , a sulfonamide group (for example, a methanesulfonamide group)
  • an imide group for example, a succinimide group, a phthalimide group
  • an imino group for example, a benzylidenea
  • substituents may further be substituted.
  • the respective substituents may be the same or different.
  • the substituent may form a fused ring structure together with a benzene ring.
  • a halogen atom, an alkyl group, an aryl group, a cyano group, an alkoxycarbonyl group, an aryloxycarbonyl group, a substituted or unsubstituted carbamoyl group, an alkylcarbonyl group, an arylcarbonyl group, a sulfonamide group, an alkoxy group, an aryloxy group, an acyloxy group, a substituted or unsubstituted sulfamoyl group, an alkylsulfonyl group and an arylsulfonyl group are preferable; a halogen atom, an alkyl group, an aryl group, an alkoxy group, an aryloxy group and an arylsulfonyl group are more preferable; and a halogen atom, an alkyl group, an aryl group and aryloxy group are especially preferable, m
  • ml and m2 are each preferably from 0 to 3, more preferably from 0 to 2, and further preferably from 0 to 1.
  • the substituents on the same benzene ring may be the same or different.
  • a. represents 0 or 1.
  • a is 0, it is meant that the benzene rings are connected to each other by a single bond.
  • L represents an oxy group or a methylene group.
  • the benzene rings of the compound represented by the formula (1) are connected to each other by a single bond or via an oxy group or a methylene group, and preferably by a single bond or via an oxy group.
  • R 3 , R 4 , R 5 , R 6 and R 7 each independently represents a substituent; and Z 1 , Z 2 , Z 3 and Z 4 each independently represents a hydrogen atom or a substituent .
  • R 3 , R 4 , R 5 , R 6 , R 7 , Z 1 , Z 2 , Z 3 and Z 4 are the same as the details and preferred range of the substituent which can be taken by R 1 and R 2 of the foregoing formula (1) , a hydrogen atom is added in the preferred range, more preferred range and especially preferred range, respectively.
  • m3, m4 and m ⁇ each independently represents an integer of from 0 to 4, preferably from 0 to 2, more preferably from 0 to 1, and further preferably 0; andm5 andm7 each independently represents an integer of from 0 to 5, preferably from 0 to 3, more preferably from 0 to 2, and further preferably from 0 to 1.
  • m3, m4, m.5, m6 and m7 are each an integer of 2 or more, the substituents on the same benzene ring may be the same or different.
  • bl, b2 and b3 each independently represents an integer of 2 or more, preferably from 2 to 8, more preferably from 2 to 6, and further preferably from 2 to 4.
  • each bonding on the benzene ring may be any of ortho, meta or para, and it is preferably meta or para, and more preferably meta.
  • the positional relationship between Z 3 and 0 each bonding on the benzene ring in the formula (3) and the positional relationship between Z 4 and CH 2 each bonding on the benzene ring in the formula (4) are also the same.
  • Ra, Rb and Rc each independently represents a substituent. Details and preferred range of the substituent which can be taken by Ra, Rb and Rc are the same as the details and preferred range of the substituent which can be taken by R 1 and R 2 of the foregoing formula (1) .
  • a 1 represents an oxy group or a methylene group.
  • a 2 represents an oxy group, a substituted or unsubstituted alkylene group, a carbonyl group, a substituted or unsubstituted imino group or a group composed of two or more members of these groups.
  • the substituted or unsubstituted imino group as referred to herein is preferably a substituted or unsubstituted iminocarbonyl group or a substituted or unsubstituted carbonylimino group.
  • a 2 is preferably an oxy group, an unsubstituted methylene group, a carbonyl group, an unsubstituted imino group or a group composed of two or more members of these groups; more preferably an oxy group, an unsubstituted methylene group or a carbonyl group; and further preferably an oxy group or an unsubstituted methylene group.
  • Details and preferred range of the substituent which can be taken by the methylene group and the imino group are the same as the details and preferred range of the substituent which can be taken by R 1 and R 2 of the foregoing formula (1) .
  • the "group composed of two or more members of these groups" which can be taken by A 2 is a group obtained by bonding two or more groups selected from the group consisting of an oxy group, a substituted or unsubstituted methylene group, a carbonyl group and a substituted or unsubstituted imino group, and a plurality of the connecting groups of the same kind may be combined.
  • the "group composed of two or more members of these groups” include a hydroxycarbonyl group, a carbonyloxy group, an alkyleneoxy group (for example, a methyleneoxy group, an ethyleneoxy group) , a hydroxyalkylene group (for example, a hydroxymethylene group, a hydroxyethylene group) , a carbonyloxyalkylene group (for example, a carbonyloxymethylene group, a carbonyloxyethylene group) , an alkyleneoxycarbonyl group (for example, a methyleneoxycarbonyl group, an ethyleneoxycarbonyl group) , an iminocarbonyl group and a carbonylimino group.
  • an alkyleneoxy group for example, a methyleneoxy group, an ethyleneoxy group
  • a hydroxyalkylene group for example, a hydroxymethylene group, a hydroxyethylene group
  • a carbonyloxyalkylene group for example, a carbonyloxymethylene group, a carbony
  • p, q and r_ each independently represents 0 or 1. In the case where p and q are each 0, it is meant that the benzene rings are connected to each other by a single bond.
  • £ is 0.
  • nl and n2 each independently represents an integer of from 0 to 5.
  • nl and n2 are each preferably from 0 to 3, more preferably from 0 to 2, and more preferably from 0 to 1.
  • n3 represents an integer of from 0 to 4.
  • n3 is preferably from 0 to 2, and more preferably from 0 to 1.
  • the substituents on the same benzene ring may be the same or different.
  • its molecular weight is preferably less than 2, 000, more preferably less than 1,000, and more preferably less than 700.
  • the compound represented by the formula (1) may be synthesized according to a well-known method to a person skilled in the art or may be commercially available.
  • S-3101, S-3103, S-3105 andS-3230, all of which are manufactured by Muramatsu Sekiyu Kenkyusho can be used.
  • the addition amount of the compound represented by the formula (1) to the organic-inorganic hybrid composition is preferably from 0.1 to 30% by mass, more preferably from 0.3 to 25% by mass, and further preferably from 0.5 to 20% by mass.
  • the “bleeding” as referred to herein refers to a phenomenon that the added compound bleeds out on the surface of a molding.
  • the organic-inorganic hybrid composition of the invention contains an inorganic fine particle together with the compound represented by the formula (1) .
  • the inorganic fine particle to be used in the invention is not particularly limited, and fine particles described in, for example, JP-A-2002-241612, JP-A-2005-298717 and JP-A-2006-70069 can be used.
  • oxide fine particles for example, aluminum oxide, titanium oxide, niobium oxide, zirconium oxide, zinc oxide, magnesium oxide, tellurium oxide, yttrium oxide, indium oxide, tin oxide
  • composite oxide fine particles for example, lithium niobate, potassium niobate, lithium tantalate
  • sulfide fine oxides for example, zinc sulfide, cadmium sulfide
  • other semi-conductor crystal fine particles for example, zinc selenide, cadmium selenide, zinc telluride, cadmium telluride
  • LiAlSiO 4 , PbTiO 3 , Sc 2 W 3 Oi 2 , ZrW 2 O 8 , AlPO 4 , Nb 2 Os, LiNO 3 and the like can be used.
  • metal oxide fine particles are preferable.
  • any one member selected from the group consisting of zirconium oxide, zinc oxide, tin oxide and titanium oxide is preferable; and any one member selected from the group consisting of zirconium oxide, zinc oxide and titanium oxide is more preferable.
  • the inorganic fine particle to be used in the invention may be a hybrid material composed of plural components from the viewpoints of refractive index, transparency, stability and the like.
  • the inorganic fine particle may be doped with a dissimilar element, or the surface layer of the inorganic fine particle may be coated with a dissimilar metal oxide (for example, silica, alumina) or may be subjected to surface modification with a silane coupling agent, a titanate coupling agent, an aluminate coupling agent, an organic acid (for example, carboxylic acids, sulfonic acids, phosphoric acids, sulfonic acids) or the like.
  • a combination of two or more types thereof can be employed depending upon the purpose.
  • the inorganic fine particle to be used in the invention its refractive index is not particularly limited.
  • the organic-inorganic hybrid composition of the invention is used for an optical member to be required to have a high refractive index
  • the refractive index of the inorganic fine particle to be used is preferably from 1.9 to 3.0, more preferably 2.0 to 2.7, and especially preferably from 2.1 to 2.5 at 22 0 C and at a wavelength of 589 nm.
  • the refractive index of the fine particle is not more than 3.0, since a difference in .
  • refractive index from the resin is relatively small, there is a tendency that the Rayleigh scattering is easily inhibited. Also, when the refractive index is 1.9 ' or more, there is a tendency that an effect for realizing a high refractive index is easily obtained.
  • the refractive index of the inorganic fine particle can be, for example, estimated by a method of forming a hybrid material hybridized with the thermoplastic resin to be used in the invention into a transparent film, measuring its refractive index by an Abbe's refractometer (for example, "DM-M4", manufactured by Atago Co. , Ltd.) and calculating the refractive index of the inorganic fine particle from a refractive index of only the resin component as measured separately, a method of measuring refractive indexes of fine particle dispersions having a different concentration, thereby calculating the refractive index of the inorganic fine particle, or other method.
  • an Abbe's refractometer for example, "DM-M4", manufactured by Atago Co. , Ltd.
  • a lower limit value of the number average particle size of the inorganic fine particle to be used in the invention is preferably 1 nm or more, more preferably 2 nm or more, and further preferably 3 nm or more; and an upper limit value thereof is preferably not more than 15 nm, more preferably not more than 10 nm, and further preferably not more than 7 nm. That is, the number average particle size of the inorganic fine particle in the invention is preferably from 1 nm to 15 nm, more preferably from
  • the inorganic fine particle to be used in the invention is satisfied with the foregoing average particle size and has narrow particle size distribution as far as possible.
  • the numerical value specified range described in JP-A-2006-160992 is also applicable to the preferred particle size distribution range of the fine particle to be used in the invention.
  • the foregoing number average particle size can be measured by an X-ray diffraction (XRD) analyzer or a transmission electron microscope (TEM) or the like.
  • XRD X-ray diffraction
  • TEM transmission electron microscope
  • the manufacturing method of the inorganic fine particle to be used in the invention is not particularly limited, and any known methods can be employed.
  • the desired oxide fine particle can be obtained by using a metal halide or a metal alkoxide as a raw material and hydrolyzing it in a reaction system containing water. Details of this method are described in, for example,
  • a method of preparing an inorganic fine particle in an organic solvent or in an organic solvent having the thermoplastic resin of the invention dissolved therein may be employed.
  • surface treating agents for example, silane coupling agents, aluminate coupling agents, titanate coupling agents, organic acids (for example, carboxylic acids, sulfonic acids, phosphonic acids) ) may be made coexistent.
  • solvent to be used in these methods examples include acetone, 2-butanone, dichloromethane, chloroform, toluene, ethyl acetate, cyclohexanone and anisole. These solvents may be used singly or in admixture of plural kinds thereof.
  • Examples of the synthesis method of the inorganic fine particle include, in addition to the foregoing methods, a variety of general synthesis methods of a fine particle described in, for example, JP-A-2006-70069, including methods for preparing an inorganic fine particle in a vacuum process such as a molecular beam epitaxy method and a CVD method.
  • the content of the inorganic fine particle in the organic-inorganic hybrid composition of the invention is preferably from 20 to 95% by mass, more preferably from 25 to 70% by mass, and especially preferably from 30 to
  • a mass ratio of the inorganic fine particle to the thermoplastic resin (dispersed polymer) in the invention is preferably from
  • 1/0.01 to 1/100 more preferably from 1/0.05 to 1/10, and especially preferably from 1/0.05 to 1/5.
  • the organic-inorganic hybrid composition of the invention contains a thermoplastic resin.
  • the organic-inorganic hybrid composition of the invention contains a thermoplastic resin having at least a functional group capable of forming an arbitrary chemical bond with the inorganic fine particle in a polymer end or side chain thereof.
  • the chemical bond as referred to herein is defined to include a covalent bond, an ionic bond, a hydrogen bond and a coordination bond.
  • Preferred examples of such a thermoplastic resin include the following three types of thermoplastic resins.
  • Thermoplastic resin having, in a side chain thereof, a functional group selected among the following groups:
  • R 11 , R 12 , R 13 and R 14 each independently 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 aryl group) , -SO 3 H, -OSO 3 H, -CO 2 H and -Si (OR 15 ) m iR 16 3 -mi (wherein R 15 and R 16 each independently 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 aryl group; and ml represents an integer of from 1 to 3) .
  • Thermoplastic resin having a functional group selected among the following groups:
  • R 21 , R 22 , R 23 and R 24 each independently 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 aryl group) , -SO 3 H, -OSO 3 H, -CO 2 H and -Si (OR 25 ) m2 R 26 3 -m2 (wherein R 25 and R 26 each independently 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 aryl group; and m2 represents an integer of from 1 to 3) in at least one polymer end thereof.
  • thermoplastic resins (1) to (3) are hereunder described in detail.
  • the thermoplastic resin (1) to be used in the invention has a functional group capable of forming an arbitrary chemical bond with the inorganic fine particle in a side chain thereof.
  • the chemical bond as referred to herein include a covalent bond, an ionic bond, a coordination bond and a hydrogen bond.
  • these functional groups may be each one capable of forming a different chemical bond with the inorganic fine particle.
  • Whether or not a chemical bond can be formed is judged by whether or not when the thermoplastic resin and the inorganic fine particle are mixed in an organic solvent, the functional group or groups of the thermoplastic resin can form a chemical bond with the inorganic fine particle. All of the functional groups of the thermoplastic resin may form a chemical bond with the inorganic fine particle, or a part of the functional groups of the thermoplastic resin may form a chemical bond with the inorganic fine particle.
  • the functional group capable of being bound with the inorganic fine particle has a function for stably dispersing the inorganic fine particle in the thermoplastic resin upon the formation of a chemical bond with the inorganic fine particle.
  • the functional group capable of forming a chemical bond with the inorganic fine particle is a functional group selected among the following groups:
  • R 11 , R 12 , R 13 and R 14 each independently 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 aryl group), -SO 3 H, -OSO 3 H, -CO 2 H and -Si (OR 15 ) m iR 16 3 -mi (wherein R 15 and R 16 each independently 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 aryl group; and ml represents an integer of from 1 to 3) .
  • Preferred ranges of R 11 , R 12 , R 13 and R 14 are as follows.
  • the alkyl group preferably has from 1 to 30 carbon atoms, and more preferably from 1 to 20 carbon atoms, and examples thereof include a methyl group, an ethyl group and an n-propyl group.
  • the substituted alkyl group includes, for example, an aralkyl group.
  • the aralkyl group preferably has from 7 to 30 carbon atoms, and more preferably from 7 to 20 carbon atoms, and examples thereof include a benzyl group and a p-methoxybenzyl group.
  • the alkenyl group preferably has from 2 to 30 carbon atoms, and more preferably from 2 to 20 carbon atoms, and examples thereof include a vinyl group and a 2-phenylethenyl group.
  • the alkynyl group preferably has from 2 to 20 carbon atoms, and preferably from 2 to 10 carbon atoms, and examples thereof include an ethynyl group and a 2-phenylethynyl group.
  • the aryl group preferably has from 6 to 30 carbon atoms, andmore preferably from 6 to 20 carbon atoms, and examples thereof include a phenyl group, a 2, 4, ⁇ -tribromophenyl group and a 1-naphthyl group.
  • the aryl group as referred to herein includes a heteroaryl group.
  • each of the alkyl group, the alkenyl group, the alkynyl group and the aryl group examples include, in addition to these alkyl group, alkenyl group, alkynyl group and aryl group, a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom) and an alkoxy group (for example, a methoxy group and an ethoxy group) .
  • R 11 , R 12 , R 13 and R 14 are each preferably a hydrogen atom or an alkyl group, and especially preferably a hydrogen atom.
  • R 15 and R 16 are the same as in R 11 , R 12 , R 13 and R 14 .
  • ml is preferably 3.
  • thermoplastic resin to be used in the invention is especially preferably a copolymer having a repeating unit represented by the following formula (7) .
  • a copolymer can be obtained by copolymerizing a vinyl monomer represented by the following formula (6) .
  • R represents a hydrogen atom, a halogen atom or a methyl group
  • X represents a divalent connecting group selected from the group consisting of -CO 2 -, -OCO-, -CONH-, -OCONH-, -0C00-, -0-, -S-, -NH- and a substituted or unsubstituted arylene group, and preferably -CO 2 - or a p-phenylene group.
  • Y represents a divalent connecting group having from 1 to 30 carbon atoms, preferably from 1 to 20 carbon atoms, more preferably from 2 to 10 carbon atoms, and further preferably from 2 to 5 carbon atoms. Specific examples thereof include an alkylene group, an alkyleneoxy group, an alkyleneoxycarbonyl group, an arylene group, an aryleneoxy group, an aryleneoxycarbonyl group and a combination thereof, with an alkylene group being preferable.
  • q represents an integer of from 0 to 18, preferably an integer of from 0 to 10, more preferably an integer of from 0 to 5, and especially preferably an integer of from 0 to 1.
  • Z represents a functional group selected among the following groups:
  • R 11 , R 12 , R 13 , R 14 , R 15 , R 16 and ml are independently synonymous with the foregoing definitions, preferred ranges and specific examples of R 11 , R 12 , R 13 , R 14 , R 15 , R 16 and ml.
  • Specific examples thereof include compounds having one addition polymerizable unsaturated bond selected among styrene derivatives, 1-vinylnaphthalene, 2-vinylnaphthalene, vinylcarbazole, acrylic acid, methacrylic acid, acrylic esters, methacrylic esters, acrylamides, methacrylamides, allyl compounds, vinyl ethers, vinyl esters, dialkyl itaconates and dialkyl esters or monoalkyl esters of fumaric acid.
  • styrene derivatives examples include styrene, 2, 4, 6-tribromostyrene and 2-phenylstyrene.
  • acrylic esters examples include methyl acrylate, ethyl acrylate, propyl acrylate, n-butyl acrylate, tert-butyl acrylate, chloroethyl acrylate, 2-hydroxyethyl acrylate, trimethylolpropane monoacrylate, benzyl acrylate, methoxybenzyl acrylate, furfuryl acrylate and tetrahydrofurfuryl acrylate.
  • methacrylic esters examples include methyl methacrylate, ethyl methacrylate, propyl methacrylate, n-butyl methacrylate, tert-butyl methacrylate, chloroethyl methacrylate, 2-hydroxyethyl methacrylate, trimethylolpropane monomethacrylate, benzyl methacrylate, methoxybenzyl methacrylate, furfuryl methacrylate and tetrahydrofurfuryl methacrylate.
  • acrylamides examples include acrylamide, N-alkyl acrylamides (the alkyl group is one having from 1 to 3 carbon atoms, for example, a methyl group, an ethyl group, a propyl group) , N,N-dialkyl acrylamides (the alkyl group is one having from 1 to 6 carbon atoms), N-hydroxyethyl-N-methyl acrylamide and N-2-acetoamidoethyl-N-acetyl acrylamide.
  • N-alkyl acrylamides the alkyl group is one having from 1 to 3 carbon atoms, for example, a methyl group, an ethyl group, a propyl group
  • N,N-dialkyl acrylamides the alkyl group is one having from 1 to 6 carbon atoms
  • N-hydroxyethyl-N-methyl acrylamide N-2-acetoamidoethyl-N-acetyl acrylamide.
  • methacrylamides examples include methacrylamide, N-alkyl methacrylamides (the alkyl group is one having from 1 to 3 carbon atoms, for example, a methyl group, an ethyl group, a propyl group), N,N-dialkyl methacrylamides (the alkyl group is one having from 1 to 6 carbon atoms) , N-hydroxyethyl-N-methyl methacrylamide and N-2-acetoamidoethyl-N-acetyl methacrylamide .
  • allyl compounds examples include allyl esters (for example, allyl acetate, allyl caproate, allyl caprate, allyl laurate, allyl palmitate, allyl stearate, allyl benzoate, allyl acetoacetate, allyl lactate) and allyloxyethanol.
  • allyl esters for example, allyl acetate, allyl caproate, allyl caprate, allyl laurate, allyl palmitate, allyl stearate, allyl benzoate, allyl acetoacetate, allyl lactate
  • the vinyl ethers include alkyl vinyl ethers (the alkyl group is one having from 1 to 10 carbon atoms; for example, hexyl vinyl ether, octyl vinyl ether, decyl vinyl ether, ethylhexyl vinyl ether, methoxyethyl vinyl ether, ethoxyethyl vinyl ether, chloroethyl vinyl ether, l-methyl-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.
  • alkyl vinyl ethers the alkyl group is one having from 1 to 10 carbon atoms; for example, hexyl vinyl ether,
  • vinyl esters examples include vinyl butyrate, vinyl isobutyrate, vinyl trimethyl acetate, vinyl diethyl acetate, vinyl valerate, vinyl caproate, vinyl chloroacetate, vinyl dichloroacetate, vinyl methoxyacetate, vinyl butoxyacetate, vinyl lactate, vinyl- ⁇ -phenyl butyrate and vinyl cyclohexyl carboxylate.
  • dialkyl itaconates examples include dimethyl itaconate, diethyl itaconate and dibutyl itaconate; and examples of the dialkyl esters or monoalkyl esters of fumaric acid include dibutyl fumarate.
  • thermoplastic resin (1) to be used in the invention its weight average molecular weight is preferably from 1,000 to 500,000, more preferably from 3,000 to 300,000, and especially preferably from 10,000 to 100,000.
  • weight average molecular weight of the thermoplastic resin (1) is not more than 500,000, there is a tendency that the molding processability is enhanced; and when the weight average molecular weight of the thermoplastic resin (1) is 1, 000 or more, there is a tendency that the mechanical strength is enhanced.
  • the foregoing weight average molecular weight is a molecular weight measured by differential refractometer detection in tetrahydrofuran as a solvent by a GPC analyzer using columns of "TSKgel GMHxL", “TSKgel G4000HxL” and “TSKgel G2000HxL” (all of which are manufactured by Tosoh Corporation) and reduced into polystyrene.
  • the number of the foregoing functional group to be bound with the inorganic fine particle is preferably from 0.1 to 20, more preferably from 0.5 to 10, and especially preferably from 1 to 5 in average per one polymer chain.
  • the number of the functional group is not more than 20 in average per one polymer chain, there is a tendency that it is easy to prevent the matter that the thermoplastic resin (1) is coordinated with a plurality of the inorganic fine particle to cause high viscosity or gelation in a solution state from occurring. Also, when the number of the functional group is 0.1 or more in average per one polymer chain, there is a tendency that it is easy to stably disperse the inorganic fine particle.
  • its glass transition temperature is preferably from 80 °C to 400 °C, and more preferably from 130 0 C to 380 °C.
  • 80 °C or higher When a resin having a glass transition temperature of 80 °C or higher is used, it is easy to obtain an optical component having sufficient heat resistance. Also, when a resin having a glass transition temperature of not higher than 400 °C is used, there is a tendency that it is easy to achieve molding processing.
  • the refractive index of the thermoplastic resin (1) is about 1.48, it is possible to provide a transparent article% having a refractive index on a level of 1.60.
  • the refractive index of the thermoplastic resin (1) to be used in the invention is preferably 1.55 or more, and more preferably 1.58 or more. These refractive indexes are a value at 22 0 C and at a wavelength of 589 nm.
  • its light transmittance as reduced in a thickness of 1 mm at a wavelength of 589 nm is preferably 80% or more, more preferably 85% or more, and especially preferably 88% or more.
  • thermoplastic resin which can be preferably used in the invention are given below, but it should not be construed that the thermoplastic resin which can be used in the invention is limited thereto.
  • thermoplastic resin (1) may be used singly or in admixture of two or more kinds thereof . Also, the thermoplastic resin (1) may be used in combination with the following thermoplastic resins (2) and/or (3).
  • the thermoplastic resin (2) to be used in the invention has a functional group capable of forming a chemical bond with the inorganic fine particle in at least one polymer end thereof.
  • the functional group may be present in only one end of a polymer chain or may be present in both ends of a polymer chain, it is preferable that the functional group is present only one end of a polymer chain. Also, a plurality of the functional group may be present in the end.
  • end refers to a portion excluding a structure to be interposed between the repeating unit and the repeating unit constituting a polymer chain.
  • the "chemical bond” as referred to herein can be considered in the same meanings as in the foregoing thermoplastic resin (1) .
  • the functional group capable of forming a chemical bond with the inorganic fine particle is a functional group selected among the following groups:
  • R 21 , R 22 , R 23 and R 24 each independently 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 aryl group) , -SO 3 H, -OSO 3 H, -CO 2 H and -Si (OR 25 ) m2 R 26 3-m2 (wherein R 25 and R 26 each independently 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 aryl group; and m2 represents an integer of from 1 to 3) .
  • R 21 , R 22 , R 23 , R 24 , R 25 and R 26 are each a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkynyl group or a substituted or unsubstituted aryl group, preferred ranges thereof are the same as the preferred ranges described above for R 11 , R 12 , R 13 and R 14 .
  • m2 is preferably 3.
  • thermoplastic resin (2) to be used in the invention its basic skeleton is not particularly limited.
  • resin skeletons such as poly (meth) acrylates, polystyrenes, polyvinylcarbazoles, polyallylates, polycarbonates, polyurethanes, polyimides, polyethers, polyethersulfones, polyetherketones, polythioethers, cycloolefin polymers and cycloolefin copolymers can be employed.
  • vinyl polymers, polyallylates and aromatic-containing polycarbonates are preferable; and vinyl polymers are more preferable. Specific examples thereof are the same as those described above for the thermoplastic resin (1) .
  • its refractive index is preferably greater than 1.50, more preferably greater than 1.55, further preferably greater than 1.60, and especially preferably greater than 1.65.
  • the refractive index in the invention is a value measured regarding light at a wavelength of 589 nm . by an Abbe's refractometer (for example, "DM-M4", manufactured by Atago Co., Ltd.).
  • its glass transition temperature is preferably from 50 °C to 400 0 C, and more preferably from 80 °C to 380 0 C. When the glass transition temperature is 50 °C or higher, there is a tendency that the heat resistance is enhanced. Also, when the glass transition temperature is not higher than 400 0 C, there is a tendency that it is easy to achieve molding processing.
  • thermoplastic resin (2) to be used in the invention its light transmittance as reduced in a thickness of 1 mm at a wavelength of 589 nm is preferably 80% or more, and more preferably 85% or more.
  • the number average molecular weight of the thermoplastic resin (2) is from 1,000 to 500,000.
  • the number average molecular weight of the thermoplastic resin (2) is preferably from 3,000 to 300,000, more preferably from 5,000 to 200,000, and especially preferably from 10,000 to 100,000.
  • the number average molecular weight of the thermoplastic resin (2) is 1,000 or more, there is a tendency that the mechanical strength is enhanced; and when the number average molecular weight of the thermoplastic resin (2) is not more than 500,000, there is a tendency that the molding processability is enhanced.
  • the method for introducing the foregoing functional group into the end of a polymer chain is not particularly limited.
  • the functional group may be introduced at the time of polymerization, or after the polymerization, conversion of the terminal functional group of the polymer once isolated or decomposition of the principal chain may be performed.
  • a polymeric reaction such as a method for performing polymerization using an initiator, a stopping agent or a chain transfer agent each having a functional group and/or a protected functional group, etc.
  • thermoplastic resin (2) which can be preferably used in the invention are given below (Illustrative Compounds P-I to P-22), but it should not be construed that the thermoplastic resin (2) which can be used in the invention is limited thereto.
  • the structures within the square brackets each represents a repeating unit; and x and y in the repeating unit represent a copolymerization ratio (molar ratio) .
  • thermoplastic resin (2) may be used singly or in admixture of two or more kinds thereof. Also, these thermoplastic resins may contain other copolymerization component .
  • thermoplastic resin (3) to be used in the invention is a block copolymer constituted of a hydrophobic segment (A) and a hydrophilic segment (B) .
  • the hydrophobic segment (A) as referred to herein refers to a segment having such properties that a polymer composed of only the segment (A) is insoluble in water or methanol; and the hydrophilic segment (B) as referred to herein refers to a segment having such properties that a polymer composed of only the segment (B) is soluble in water or methanol.
  • Examples of a type of the block copolymer include an AB type, a B 1 AB 2 type (the two hydrophilic segments B 1 and B 2 may be the same or different) and an A 1 BA 2 type (the two hydrophobic segments A 1 and A 2 may be the same or different) .
  • block copolymers of an AB type or an A 1 BA 2 type are preferable; and in view of the manufacturing aptitude, block copolymers of an AB type or an ABA type (the two hydrophobic segments of the A 1 BA 2 type are the same) are more preferable, with an AB type being especially preferable.
  • the hydrophobic segment and the hydrophilic segment can be each selected among polymers which have hitherto been known, for example, vinyl polymers obtained through polymerization of a vinyl monomer, polyethers, ring-opening metathesis polymerization polymers and condensation polymers (for example, polycarbonates, polyesters, polyamides, polyetherketones, polyethersulfones) .
  • vinyl polymers, ring-opening metathesis polymerization polymers, polycarbonates and polyesters are preferable; and vinyl polymers are more preferable in view of manufacturing aptitude.
  • the vinyl monomer (A) for forming the hydrophobic segment (A) for example, the following can be exemplified. That is, examples thereof include acrylic esters or methacrylic esters (in which the ester group thereof is a substituted or unsubstituted aliphatic ester group or a substituted or unsubstituted aromatic ester group, for example, a methyl group, a phenyl group, a naphthyl group) ; acrylamides and methacrylamides, specifically N-mono-substituted acrylamides, N-di-substituted acrylamides, N-mono-substituted methacrylamides and N-di-substituted methacrylamides (in which the substituent of the mono-substituted materials and the di-substituted materials is a substituted or unsubstituted aliphatic group or a substituted or unsubstituted aromatic group, for example
  • Acrylic esters and methacrylic esters in which the ester group thereof is a substituted or unsubstituted aromatic group; and styrenes are more preferable.
  • the vinyl monomer (B) for forming the hydrophilic segment (B) for example, the following can be exemplified.
  • examples thereof include acrylic acid, methacrylic acid and acrylic esters and methacrylic esters each having a hydrophilic substituent in an ester site thereof; styrenes having a hydrophilic substituent in an aromatic ring moiety thereof; and vinyl ethers, acrylamides, methacrylamides, N-mono-substituted acrylamides, N-di-substituted acrylamides, N-mono-substituted methacrylamides and N-di-substituted methacrylamides each having a hydrophilic substituent.
  • the hydrophilic substituent is preferably one having a functional group selected among the following groups:
  • R 31 , R 32 , R 33 and R 34 each independently 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 aryl group), -SO 3 H, -OSO 3 H, -CO 2 H, -OH and -Si (OR 35 ) m3 R 36 3 - m3 (wherein R 35 and R 36 each independently 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 aryl group; and m3 represents an integer of from 1 to 3) .
  • R 31 , R 32 , R 33 , R 34 , R 35 and R 36 are each a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkynyl group or a substituted or unsubstituted aryl group, preferred ranges thereof are the same as the preferred ranges described above for R 11 , R 12 , R 13 and R 14 .
  • m3 is preferably 3.
  • the foregoing block copolymer has a functional group selected among the following groups :
  • acrylic acid, methacrylic acid, acrylic esters and methacrylic esters each having a hydrophilic substituent in an ester site thereof and styrenes having a hydrophilic substituent in an aromatic ring moiety thereof are preferable as the hydrophilic segment (B) .
  • a molar ratio of the vinyl monomer (A) to the vinyl monomer (B) to be contained in the hydrophobic segment (A) is preferably from 100/0 to 60/40.
  • a molar ratio of the vinyl monomer (B) to the vinyl monomer (A) to be contained in the hydrophilic segment (B) is preferably from 100/0 to 60/40.
  • the vinyl monomer (A) and the vinyl monomer (B) may be each used singly or in admixture of two or more kinds thereof.
  • the vinyl monomer (A) and the vinyl monomer (B) are each selected depending upon a variety of purposes (for example, adjustment of the acid content, adjustment of the glass transition point (Tg) , adjustment of solubility in an organic solvent or water, adjustment of the stability of a dispersion) .
  • the content of the functional group is preferably from 0.05 to 5.0 mmoles/g, more preferably from 0.1 to 4.5 mmoles/g, and especially preferably from 0.15 to 3.5 mmoles/g relative to the whole of the block copolymer.
  • the foregoing functional group may form a salt with a cationic ion such as an alkali metal ion (for example, Na + , K + ) and an ammonium ion.
  • its molecular weight (Mn) is preferably from 1,000 to 100,000, more preferably from 2,000 to 80, 000, and especially preferably from 3, 000 to 50,000.
  • Mn molecular weight
  • the molecular weight of the block copolymer is 1,000 or more, there is a tendency that a stable dispersion is easily obtained; and when it is not more than 100,000, there is a tendency that the solubility in an organic solvent is enhanced, and therefore, such is preferable.
  • its refractive index is preferably greater than 1.50, more preferably greater than 1.55, further preferably greater than 1.60, and especially preferably greater than 1.65.
  • the refractive index as referred to herein is a value measured regarding light at a wavelength of 589 nm by an Abbe's refractometer (for example, "DR-M4", manufactured by Atago Co. , Ltd. ) .
  • its glass transition temperature is preferably from 80 °C to 400 °C, and more preferably from 130 °C to 380 0 C. When the glass transition temperature is 80 0 C or higher, there is a tendency that the heat resistance is enhanced; and when the glass transition temperature is not higher than 400 0 C, there is a tendency that the molding processability is enhanced.
  • its light transmittance as reduced in a thickness of 1 mm at a wavelength of 589 nm is preferably 80% or more, and more preferably 85% or more.
  • block copolymer examples include but it should not be construed that the block copolymer to be used in the invention is limited thereto.
  • the block copolymer can be synthesized utilizing living radical polymerization or living ionic polymerization using a method such as protection of a carboxyl group, etc. and introduction of a functional group into the polymer as the need arises.
  • the block copolymer can also be synthesized through radical polymerization from a terminal functional group polymer or connection between terminal functional polymers each other. Above all, in view of the molecular weight control and the percent yield of the block polymer, it is preferable to utilize living radical polymerization or living ionic polymerization.
  • the manufacturing method of the block copolymer is described in, for example, Kobunshi no Gosei to Hanno (Synthesis and Reaction of Polymer) (1) (edited by The Society of Polymer Science, Japan and published by Kyoritsu Shuppan Co., Ltd. (1992) ); Seimitsu Jugo (Accurate Polymerization) (editedbyThe
  • the organic-inorganic hybrid composition of the invention may be properly compounded with a variety of additives in addition to the foregoing compound represented by the formula (1), inorganic fine particle and thermoplastic resin.
  • additives include a surface treating agent, an antistatic agent, adispersant, a plasticizer and a releasing agent .
  • a resin not having the foregoing functional agent may be added. Though such a resin is not particularly limited with respect to its type, those having the same optical physical properties, thermal physical properties and molecular weight as in the foregoing thermoplastic resin are preferable.
  • a blending proportion of such an additive varies depending upon the purpose, it is preferably from 0 to 50% by mass, more preferably from 0 to 30% by mass, and especially preferably from 0 to 20% by mass relative to the total sum of the foregoing inorganic fine particle and thermoplastic resin.
  • a fine particle surface modifying agent other than the foregoing thermoplastic resin may be added for a variety of purposes such as a purpose of enhancing extraction properties or substitution properties into the organic solvent, a purpose of enhancing the uniform dispersibility into the thermoplastic resin, a purpose of lowering the water absorption properties of the fine particle, or a purpose of enhancing the weather resistance.
  • its weight average molecular weight is preferably from 50 to 50, 000, more preferably from 100 to 20, 000, and further preferably from 200 to 10,000.
  • the surface treating agent is preferably one having a structure represented by the following formula (8) : Formula (8)
  • A represents a functional group capable of forming a chemical bond with the surface of the inorganic fine particle to be used in the invention
  • B represents a monovalent group having from 1 to 30 carbon atoms and having compatibility or reactivity with a resin matrix containing, as a major component, the thermoplastic resin to be used in the invention or a polymer.
  • the "chemical bond” as referred to herein refers to a covalent bond, an ionic bond, a coordination bond, a hydrogen bond or 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 to be used in the invention.
  • the chemical structure of the group represented by B is preferably the same as or analogous to the chemical structure of the thermoplastic resin which is the major component of the resin matrix.
  • the chemical structure of B has an aromatic ring similar to the foregoing thermoplastic resin.
  • Examples of the surface treating agent which is preferably used in the invention include p-octylbenzoic acid, p-propylbenzoic acid, acetic acid, propionic acid, cyclopentanecarboxylic acid, dibenzyl phosphate, monobenzyl phosphate, diphenyl phosphate, di- ⁇ -naphthyl phosphate, phenylphosphonic acid, phenylphosphonic acid monophenyl ester, KAYAMER PM-21 (a trade name, manufactured by Nippon Kayaku Co. , Ltd.
  • KAYAMER PM-2 (a trade name, manufactured by Nippon Kayaku Co., Ltd.), benzenesulfonic acid, naphthalenesulfonic acid, p-octylbenzenesulfonic acid and silane coupling agents described in JP-A-5-221640, JP-A-9-100111 and JP-A-2002-187921. However, it should not be construed that the invention is limited thereto.
  • Such a surface treating agent may be used singly or in combination of plural kinds thereof.
  • the total amount of the addition amount of such a surface treating agent is preferably from 0.01 to 2 times, more preferably from 0.03 to 1 time, and especially preferably from 0.05 to 0.5 times the amount of the inorganic fine particle in terms of a mass.
  • an antistatic agent can be added.
  • the inorganic fine particle per se which is added for the purpose of improving the optical properties, contributes to an antistatic effect as a separate effect.
  • the antistatic agent examples thereof include an anionic antistatic agent, a cationic antistatic agent, a nonionic antistatic agent, an ampholytic antistatic agent, a polymer antistatic agent and an antistatic fine particle.
  • Such an antistatic agent may be used in combination of two or more kinds thereof. Examples thereof include compounds described in JP-A-2007-4131 and JP-A-2003-201396.
  • the addition amount of the antistatic agent is divergent, it is preferably from 0.001 to 50% by mass, more preferably from 0.01 to 30% by mass, and especially preferably from 0.1 to 10% by mass of the total solids content.
  • waxes for the purposes of enhancing a release effect and further enhancing the fluidity at the time of molding, not only natural waxes such as vegetable waxes (for example, carnauba wax, rice wax, cotton wax, Japan wax) , animal waxes (for example, beeswax, lanolin) , mineral waxes (for example, ozokerite, ceresin) and petroleum waxes
  • vegetable waxes for example, carnauba wax, rice wax, cotton wax, Japan wax
  • animal waxes for example, beeswax, lanolin
  • mineral waxes for example, ozokerite, ceresin
  • petroleum waxes for example, ozokerite, ceresin
  • paraffins for example, paraffins, microcrystalline waxes, petrolatum
  • synthetic hydrocarbon waxes for example, Fischer-Tropsch wax, polyethylene wax
  • long-chain aliphatic amides for example, stearic acid amide, chlorinated hydrocarbons
  • synthetic waxes for example, esters, ketones, ethers
  • silicone oils for example, dimethyl silicone oil, methylphenyl silicone oil
  • fluorotelomers for example, ZONYL FSN and ZONYL FSO, all of which are manufactured by DuPont
  • deterioration preventive agents such as hindered phenol based, amine based, phosphorus based or thioether based deterioration preventive agents may be properly added.
  • a deterioration preventive agent is compounded, it is preferably added in an amount of from about 0.1 to 5% by mass relative to the total solids content of the resin composition.
  • the organic-inorganic hybrid composition of the invention is preferably manufactured by chemically bonding the inorganic fine particle with the foregoing functional group-containing thermoplastic resin to disperse it in the resin. At that time, the compound represented by the formula (1) is made present.
  • the inorganic fine particle to be used in the invention is small in particle size and high in surface energy, when isolated as a solid, it is difficult to be re-dispersed. Therefore, it is preferable that the inorganic fine particle is mixed with the thermoplastic resin in a dispersed state in a solution to form a stable dispersion.
  • Preferred examples of the manufacturing method of the organic-inorganic hybrid composition include [1] a method in which an inorganic fine particle is surface treated in the presence of the foregoing surface treating agent, the surface-treated inorganic fine particle is extracted into an organic solvent, and the extracted inorganic fine particle is uniformly mixed with the foregoing thermoplastic resin and the foregoing compound represented by the formula (1) to manufacture a hybrid material of the inorganic fine particle and the thermoplastic resin; and [2] a method in which an inorganic fine particle, a thermoplastic resin, a compound represented by the formula (1) and other additives are uniformly mixed using a solvent capable of uniformly dispersing or dissolving all of the components therein to manufacture a hybrid material of the inorganic fine particle and the thermoplastic resin.
  • a water-insoluble solvent such as toluene, ethyl acetate, methyl isobutyl ketone, chloroform, dichloroethane, dichloromethane, chlorobenzene and methoxybenzene is used as the organic solvent.
  • the surface treating agent to be used for extracting the inorganic fine particle into the organic solvent and the thermoplastic resin may be the same kind or a different kind, as to the surface treating agent to be preferably used, those described above in the ⁇ Surface treating agent> section are exemplified.
  • the compound represented by the formula (1) is added, and additives such as a plasticizer, a releasing agent and a polymer of other type may further be added as the need arises.
  • a single or mixed solvent of hydrophilic polar solvents for example, dimethylacetamide, dimethylformamide, dimethyl sulfoxide, benzyl alcohol, cyclohexanol, ethylene glycol monomethyl ether, l-methoxy-2-propanol, tert-butanol, acetic acid, propionic acid
  • hydrophilic polar solvents for example, dimethylacetamide, dimethylformamide, dimethyl sulfoxide, benzyl alcohol, cyclohexanol, ethylene glycol monomethyl ether, l-methoxy-2-propanol, tert-butanol, acetic acid, propionic acid
  • a mixed solvent of a water-insoluble resin for example, chloroform, dichloroethane, dichloromethane, ethyl acetate, methyl ethyl ketone, methyl isobutyl ketone, toluene, chlorobenzene, methoxybenzene
  • a water-insoluble resin for example, chloroform, dichloroethane, dichloromethane, ethyl acetate, methyl ethyl ketone, methyl isobutyl ketone, toluene, chlorobenzene, methoxybenzene
  • a disersant, a plasticizer, a releasing agent or a polymer of other type may be added as the need arises.
  • the water/methanol is concentrated and distilled off, thereby substituting a dispersion of the fine particle into the polar organic solvent, followed by mixing with the resin.
  • the foregoing surface treating agent may be added.
  • the solution of the organic-inorganic hybrid composition obtained in the foregoing method [1] or [2] can be subjected to cast molding as it is, to obtain a transparent molding.
  • a powdered solid is molded by a known method such as injection molding and compression molding.
  • the powdered organic-inorganic hybrid composition of the invention can be directly processed into a molding such as lenses by heat melting or compression. It is also possible to prepare an optical component such as lenses by once preparing a preform (precursor) having fixed weight and shape by a method such as an extrusion method and deforming the preform by compression molding. In that case, in order to efficiently prepare a desired shape, it is also possible to bring the preform with an appropriate curvature.
  • its light transmittance as reduced in a thickness of 1 mm at a wavelength of 589 nm is preferably 70% or more, more preferably 75% or more, and especially preferably 80% or more.
  • the light transmittance at a wavelength of 405 nm is preferably 60% or more, more preferably 65% or more, and especially preferably 70% or more.
  • the light transmittance as reduced in a thickness of 1 mm is a value obtained by molding the organic-inorganic hybrid composition to prepare a substrate having a thickness of 1.0 mm and measuring it by a spectrophotometer for ultraviolet and visible region (UV-3100, manufactured by Shimadzu Corporation) .
  • its refractive index at a wavelength of 589 nm is preferably 1.60 or greater, more preferably 1.65 or greater, and especially preferably 1.67 or greater.
  • the organic-inorganic hybrid composition of the invention is hardly electrified. Its dielectric strength is preferably from -2 to 15 kV, more preferably from
  • its glass transition temperature is preferably from 100 0 C to 400 °C, and more preferably from 130 °C to 380 °C.
  • the glass transition temperature is 100 0 C or higher, sufficient heat resistance is easily obtained; and when the glass transition temperature is not higher than 400 0 C, there is a tendency that it is easy to achieve molding processing.
  • the organic-inorganic hybrid composition of the invention it is preferable that when kept at 200 0 C for 2 hours, its volatile component content is not more than 2% by mass; it is more preferable that when kept at 230 °C for 2 hours, its volatile component content is not more than 2% by mass; and it is especially preferable that when kept at 250 0 C for 2 hours, its volatile component content is not more than 2% by mass.
  • its percentage of saturated water absorption is preferably not more than 2% by mass, more preferably not more than 1% by mass, and especially preferably not more than 0.5% by mass.
  • the organic-inorganic hybrid composition of the invention By forming the organic-inorganic hybrid composition of the invention to a particular shape (for example by molding) , it is possible to manufacture the article of the invention. As to the article of the invention, one exhibiting the refractive index and optical properties described above for the organic-inorganic hybrid composition is useful.
  • the article of the invention is especially useful for high-refractive index optical components having a thickness of 0.1 mm or more at maximum. It is preferable to apply the article of the invention to optical components having a thickness of from 0.1 to 5 mm; and it is especially preferable to apply the article of the invention to optical components having a thickness of from 1 to 3 mm.
  • the solvent is hardly discharged so that article is usually not easy.
  • the organic-inorganic hybrid composition of the invention molding is easy, a complicated shape such as non-spheres can be easily imparted, and a material having good transparency can be formed while utilizing high refractive index properties of the fine particle.
  • the article of the invention is an article having high refraction properties, light transmission properties and lightweight properties and having excellent optical properties.
  • the optical component of the invention is configured of such an article.
  • the type of the optical component of the invention is not particularly limited.
  • the optical component of the invention can be favorably utilized as an optical component utilizing excellent optical properties of the organic-inorganic hybrid composition, especially as an optical component capable of transmitting light therethrough (so-called passive optical component) .
  • optical functional devices examples include a variety of display devices (for example, liquid crystal displays, plasma displays) , a variety of projector devices (for example, OHP, liquid crystal projectors) , optical fiber communication devices (for example, optical waveguides, optical amplifiers) and imaging devices (for example, cameras, video cameras) .
  • display devices for example, liquid crystal displays, plasma displays
  • projector devices for example, OHP, liquid crystal projectors
  • optical fiber communication devices for example, optical waveguides, optical amplifiers
  • imaging devices for example, cameras, video cameras
  • examples of the passive optical component to be used in an optical functional device include lenses, prisms, prism sheets, panels (plate-like articles), films, optical waveguides (for example, film forms, fiber forms) , optical discs and sealing materials of LED.
  • a passive optical component may be of a multilayered structure provided with an arbitrary coating layer such as arbitrary additional functional layers, for example, a protective layer for preventing mechanical damages on the coated surface due to friction or abrasion, a light absorbing layer for absorbing light beams of an undesired wavelength which become a cause for deteriorating the inorganic particle or base material or the like, a transmission-blocking layer for suppressing or preventing the transmission of a reactive low-molecular weight molecule such as water and an oxygen gas, an antiglare layer, an antireflection layer and a low-refractive index layer.
  • Such an arbitrary coating layer include a transparent conductive membrane or a gas barrier membrane composed of an inorganic oxide coating layer; and a gas barrier membrane or a hard coat composed of an organic material coating layer.
  • the coating method there can be employed known coating methods such as a vacuum vapor deposition method, a CVD method, a sputtering method, a dip coating method and a spin coating method.
  • the optical component using the organic-inorganic hybrid composition of the invention is especially favorable for a lens base material.
  • the lens base material manufactured using the organic-inorganic hybrid composition of the invention has high refraction properties, light transmission properties and lightweight properties and is excellent in optical properties. Also, by properly adjusting the type of the monomer constituting the organic-inorganic hybrid composition and the amount of the inorganic fine particle to be dispersed, it is possible to arbitrarily adjust the refractive index of the lens base material .
  • the "lens base material” as referred to in the invention refers to a single member capable of exhibiting a lens function.
  • a membrane or a member can be provided on the surface or surroundings of the lens base material depending upon the use circumference or utilization of the lens.
  • a protective membrane, an antireflection membrane, a hard coat membrane and the like can be formed on the surface of the lens base material .
  • the surroundings of the lens base material can be put in and fixed to a base material holding frame or the like.
  • a membrane or frame is a member to be added to the lens base material as referred to in the invention and should be distinguished from the lens base material per se as referred to in the invention.
  • the lens base material in the invention may be solely used as a lens, or as described previously, it may be added to a membrane or frame and then used as a lens.
  • the type and shape of the lens using the lens base material of the invention is not particularly limited.
  • the lens base material of the invention is used for, for example, spectacle lenses, optical instrument lenses, optoelectronic lenses, laser lenses, pickup lenses, vehicle-mounted camera lenses, mobile phone camera lenses, digital camera lenses, OHP lens, lenses for configuring a micro lens array.
  • a sample to be measured was molded to prepare a substrate having a thickness of 1.0 mm, which was then measured for light transmittance by light at a wavelength of 589 nm using a spectrophotometer for ultraviolet and visible region (UV-3100, manufactured by Shimadzu Corporation) .
  • a dispersion of a titanium oxide fine particle was prepared in conformity with a method described in Synthesis
  • Example 9 of JP-A-2003-73559 The formation of an anatase type titanium oxide fine particle (number average particle size: about 5 nm) was confirmed by XRD and TEM. The fine particle had a refractive index of 2.5.
  • a zirconium oxychloride solution having a concentration of 50 g/L was neutralized with a 48% sodium hydroxide aqueous solution to obtain a zirconium hydrate suspension.
  • This suspension was filtered and then washed with ion exchanged water to obtain a zirconium hydrate cake.
  • This cake was adjusted with ion exchanged water as a solvent so as to have a concentration of 15% by mass as reduced into zirconium oxide, charged in an autoclave and then subjected to a hydrothermal treatment under a pressure of 150 atmospheres at 150 0 C for 24 hours, thereby obtaining a zirconium oxide fine particle suspension.
  • the formation of the zirconium oxide fine particle having a number average particle size of 5 nm was confirmed by TEM.
  • the fine particle had a refractive index of 2.1.
  • zirconium oxide fine particle suspension as synthesized in the foregoing (2) and a toluene solution having KAYAMER PM-21 (manufactured by Nippon Kayaku Co., Ltd.) dissolved therein were mixed, the mixture was stirred at 50 °C for 8 hours, and the toluene solution was extracted to prepare a zirconium oxide fine particle toluene dispersion.
  • KAYAMER PM-21 manufactured by Nippon Kayaku Co., Ltd.
  • thermoplastic resin B-Il (2) Synthesis of thermoplastic resin B-Il:
  • thermoplastic resin B-Il As a result of the measurement by GPC, the resin was found to have a weight average molecular weight of 32,000. Also, as a result of the measurement by an Abbe's refractometer, the resin was found to have a refractive index of 1.59.
  • thermoplastic resin B-10 (2) Synthesis of thermoplastic resin B-10:
  • thermoplastic resin P-8 246.25 g of methyl methacrylate, 3.75 g of ⁇ -carboxyethyl acrylate and 2.5 g of a polymerization initiator, V-601 (a trade name, manufactured by Wako Pure Chemical Industries, Ltd. ) were dissolved in 107.1 g of ethyl acetate, and the solution was polymerized under nitrogen at 80 °C, thereby synthesizing a thermoplastic resin B-10.
  • GPC the resin was found to have a weight average molecular weight of 35,000.
  • an Abbe's refractometer the resin was found to have a refractive index of 1.49.
  • thermoplastic resin Q-I (number average molecular weight: 18,000, weight average molecular weight: 20,000). Also, as a result of the measurement by an Abbe's refractometer, the resin was found to have a refractive index of 1.59. (4) Synthesis of thermoplastic resin Q-I:
  • a mixed solution consisting of 2.1 g of tert-butyl acrylate, 0.72 g of tert-butyl 2-bromopropionate, 0.46 g of copper (I) bromide, 0.56 g of N, N, N' ,N' ,N", N"-pentamethyl diethylenetetramine and 9 mL of methyl ethyl ketone was prepared and purged with nitrogen.
  • the resulting mixed solution was stirred at an oil bath temperature of 80 0 C for one hour, and 136.2 g of styrene was added dropwise under a nitrogen gas stream.
  • a formed precipitate was collected by filtration, washed with methanol and then dried to obtain 55 g of a block copolymer Q-I.
  • the resin was found to have a number average molecular weight of 32', 000 and a weight average molecular weight of 35,000.
  • the resin was found to have a refractive index of 1.59.
  • the thermoplastic resin B-Il, Compound PL-I and a surface treating agent (4-propylbenzoic acid) were added in a mass ratio of ZrO 2 solid/B-ll/PL-l/4-propylbenzoic acid of 41.7/41.7/8.3/8.3, uniformly stirred and mixed, and the dimethylacetamide solvent was then concentrated in vacuo by heating.
  • the concentration residue was heat compression molded in a die having a SUS-made surface (temperature: 180 0 C, pressure: 13.7 MPa, time: 2 minutes), thereby obtaining a article (lens base material) having a thickness of 1 mm.
  • a article (lens base material) of Comparative Example 4 was obtained in the same manner as in Example 2, except that in Example 2, di-2-ethylhexyl phthalate (DOP) was added in place of the compound represented by the formula (1) .
  • DOP di-2-ethylhexyl phthalate
  • Example 7 and Comparative Example 3 The foregoing titanium oxide dispersion was added dropwise to a chloroform solution having the thermoplastic resin P-8 and a surface treating agent (4-propybenzoic acid) dissolved therein at ordinary temperature over 5 minutes with stirring.
  • Compound PL-I represented by the formula (1) was added and dissolved in the obtained mixed solution, and the solvent was then distilled off (TiC>2 solid/P-8/PL-l/4-propylbenzoic acid of 37/46.9/7.4/8.6) .
  • the concentration residue was molded in the same manner as in Example 1 to obtain a article (lens base material) of Example 7.
  • a article (lens base material) of Comparative Example 3 was obtained in the same manner as in Example 1, except that in Example 7, the Compound PL-I represented by the formula (1) was not added.
  • Example 8 A article (lens base material) of Example 8 was obtained in the same manner as in Example 5, except that the temperature of the heat compression molding was 120 °C.
  • a article of Comparative Example 5 was obtained in the same manner as in Comparative Example 2, except that the temperature of the heat compression molding was 120 0 C.
  • Comparative Example 4 though the generation of a crack after elapsing was suppressed by the addition of a known plasticizer, the results revealed that the light transmittance and refractive index were inferior. In Comparative Example 5, only a white solid powder was obtained, but a transparent article could not be obtained.
  • the organic-inorganic hybrid composition of the invention is suitable for manufacturing an optical component having good moldability and stability with time and having a high refractive index and good transparency even in a thick article of 1 mm.
  • all of the material compositions of Examples 1 to 8 had a dielectric strength falling within the range of from -1.0 to 7.0 kV and a glass transition temperature falling within the range of from 100 to 400 °C and when kept at 250 °C for 2 hours, had a volatile component content of not more than 2% by mass and a percentage of saturated water absorption of 0.5% by mass. Also, it was confirmed that by using the organic-inorganic hybrid composition of the invention, a lens shape can be accurately formed with good productivity in conformity with the shape of a die such as a concave lens and a convex lens .
  • the organic-inorganic hybrid composition of the invention has excellent transparency and high refractive index and has excellent stability with time. Also, according to the invention, it is possible to arbitrarily control the refractive index. Furthermore, by using the organic-inorganic hybrid composition of the invention, it is easy to provide an optical component having good mechanical strength, heat resistance, weather resistance and moldability. In consequence, the invention is high in industrial applicability.

Abstract

An organic-inorganic hybrid composition comprising a compound represented by the following formula (1) and an inorganic fine particle: wherein R1 and R2 represent a substituent; L represents an oxy group or a methylene group; a represents 0 or 1; and m1 and m2 represent 0 to 5.

Description

DESCRIPTION
ORGANIC-INORGANIC HYBRID COMPOSITION AND ITS ARTICLE AND
OPTICAL COMPONENT
TECHNICAL FIELD
The present invention relates to an organic-inorganic hybrid composition which is excellent in high refraction properties, transparency, lightweight properties and processability and to an optical component configured to contain the same, inclusive of lens base materials (for example, spectacle lenses, optical instrument lenses, optoelectronic lenses, laser lenses, pickup lenses, vehicle-mounted camera lenses, mobile phone camera lenses, digital camera lenses, OHP lens, lenses for configuring a micro lens array) .
BACKGROUND ART
In comparison with glasses, resins have such advantages that they are excellent in lightweight properties, impact resistance and moldability and that they are economical, and in recent optical components such as lenses, the substitution of optical glass with a resin is advancing.
As a molding method of a resin, methods such as an injection molding method for casting a molten resin into a die to achieve molding, an extrusion molding method and a compression molding method are widely employed. But, the fluidity of the resin is often of a problem. In particular, in recent years, the development, etc. of a material in which an inorganic nano particle is finely dispersed in a resin for the purpose of realizing a high function such as high refractive index and high heat resistance is performed (see, for example, JP-A-βl-291650 and JP-A-2003-73564) . However, by dispersing the inorganic nano particle in the resin, there may be the case where the fluidity is deteriorated, resulting in a serious problem from the viewpoint of imparting moldability.
As a measure for enhancing the fluidity of a resin, a method for using a plasticizer has hitherto been known, and phthalic ester based plasticizers, phosphoric ester based plasticizers, esters of a polyhydric carboxylic acid (for example, adipic acid, citric acid) and so on are widely used as the plasticizer. Though DOP (di-2-ethylhexyl phthalate) is exemplified as the most general plasticizer (see JP-A-61-73754 ) , its refractive index to D-line is low as 1.486. Therefore, its application to a high-refractive index material having a refractive index of 1. β or more was difficult because it lowers the refractive index of the material.
On the other hand, the development of a substrate for information recording . medium with excellent transfer properties such as optical discs (see JP-A-2000-195099) and a substrate for reaction chip such as a DNA chip (see JP-A-2004-354131) using a biphenyl compound or a terphenyl compound as an additive of an aromatic polycarbonate resin is carried out. But, there is no description at all regarding its addition to an organic-inorganic composite material or its use for a lens base material.
DISCLOSURE OF THE INVENTION
Material compositions having high refraction properties, transparency and processability and capable of arbitrarily controlling a refractive index and optical components configured to contain the same have not been found yet, and the development thereof has been desired.
Under these circumstances, the invention has been made. An object of the invention is to provide an organic-inorganic hybrid composition having a fine particle uniformly dispersed in a resin matrix, having excellent transparency and high refractive index and having excellent stability with time and an optical component using the same, for example, lens base materials .
In order to achieve the foregoing object, the present inventors made extensive and intensive investigations. As a result, it has been found that an organic-inorganic hybrid composition containing, as raw materials, an inorganic fine particle having a specified refractive index and a specified resin has high refraction properties and excellent transparency due to a uniform dispersion effect of the fine particle, leading to accomplishment of the invention as described below. [1] An organic-inorganic hybrid composition comprising a compound represented by the following formula (1) and an inorganic fine particle.
Formula ( 1 )
Figure imgf000004_0001
In the formula (1), R1 and R2 each independently represents a substituent; L represents an oxy group or a methylene group; a represents 0 or 1; and ml and m2 each independently represents an integer of from 0 to 5.
[2] The organic-inorganic hybrid composition as set forth in [1] , wherein the compound is represented by any one of the following formulae (2) to (4) .
Formula (2)
Figure imgf000004_0002
Formula ( 3 )
Figure imgf000005_0001
Formula (4)
Figure imgf000005_0002
In the formula (2) to (4), R3, R4, R5, R6 and R7 each independently represents a substituent; Z1, Z2, Z3 and Z4 each independently represents a hydrogen atom or a substituent; m3, m4 and m6 each independently represents an integer of from 0 to 4; m5 and m7 each independently represents an integer of from Oto 5; andbl, b2 and b3 each independently represents an integer of 2 or more. [3] The organic-inorganic hybrid composition as set forth in [1] , wherein the compound is represented by the following formula (5) .
Formula (5)
Figure imgf000005_0003
In the formula (5), Ra, Rb and Rc each independently represents a substituent, A represents an oxy group or a methylene group; A2 represents an oxy group, a substituted or unsubstituted alkylene group, a carbonyl group, a substituted or an unsubstituted imino group or a group composed of two or more members of these groups; nl and n2 each independently 5 represents an integer of from 0 to 5; n3 represents an integer of from 0 to 4; and p, q and r_ each independently represents 0 or 1, provided that when q is 0, then r is 0.
[4] The organic-inorganic hybrid composition as set forth in any one of [1] to [3] , wherein the inorganic fine particle is 10 a metal oxide fine particle having a refractive index of from 1.90 to 3.00.
[5] The organic-inorganic hybrid composition as set forth in any one of [1] to [4], wherein the inorganic fine particle is a fine particle containing zirconium oxide, zinc oxide or 15 titanium oxide.
[6] The organic-inorganic hybrid composition as set forth in any one of [1] to [5] , wherein the inorganic fine particle has a number average particle size of from 1 to 15 ran.
[7] The organic-inorganic hybrid composition as set forth in 20. any one of [1] to [6], wherein the inorganic fine particle is contained in an amount of 20% by mass or more.
[8] The organic-inorganic hybrid composition as set forth in any one of [1] to [7] , wherein the compound represented by the formula (1) has a molecular weight of less than 1,000. 25 [9] The organic-inorganic hybrid composition as set forth in any one of [1] to [8], wherein a thermoplastic resin having a functional group capable of forming an arbitrary chemical bond with the inorganic fine particle in a polymer end or side chain thereof is contained. 30 [10] The organic-inorganic hybrid composition as set forth in
[9] , wherein the thermoplastic resin is a thermoplastic resin having a functional group selected among the following groups:
Figure imgf000007_0002
(wherein R11, R12, R13 and R14 each independently 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 aryl group) , -SO3H, -OSO3H, -CO2H and -Si (OR15)miR16 3-mi (wherein
R15 and R16 each independently 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 aryl group; and ml represents an integer of from 1 to 3) in a side chain thereof.
[11] The organic-inorganic hybrid composition as set forth in any one of [1] to [8] , wherein the functional group is contained in the number ranging from 0.1 to 20 in average per one polymer chain.
[12] The organic-inorganic hybrid composition as set forth in [10] or [11] , wherein the thermoplastic resin is a copolymer containing, as a polymerization unit, a monomer represented by the following formula (6) . Formula (6)
Figure imgf000007_0001
In the formula (6), R represents a hydrogen atom, a halogen atom or a methyl group; X represents a divalent connecting group selected among -CO2-, -OCO-, -CONH-, -OCONH-, -0C00-, -0-, -S-, -NH- and a substituted or unsubstituted arylene group; Y represents a divalent connecting group having from 1 to 30 carbon atoms; q represents an integer of from 0 to 18; and Z represents a functional group selected among the following groups:
Figure imgf000008_0001
(wherein R11, R12, R13 and R14 each independently 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 aryl group) , -SO3H, -OSO3H, -CO2H and -Si (OR15)mlR16 3_mi (wherein R15 and R16 each independently 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 aryl group; and ml represents an integer of from 1 to 3) . [13] The organic-inorganic hybrid composition as set forth in [9], wherein the thermoplastic resin is a thermoplastic resin having a functional group selected among the following groups:
Figure imgf000008_0002
(wherein R21, R22, R23 and R24 each independently 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 aryl group) , -SO3H, -OSO3H, -CO2H and -Si (OR25) m2R263-m2 (wherein R25 and R26 each independently 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 aryl group; and m2 represents an integer of from 1 to 3) in at least one polymer end thereof.
[14] The organic-inorganic hybrid composition as set forth in [9], wherein the thermoplastic resin is a block copolymer constituted of a hydrophobic segment and a hydrophilic segment. [15] An article obtained by forming the organic-inorganic hybrid composition as set forth in any one of [1] to [14] . [16] The article% ' as set forth in [15], having a light transmittance as reduced in a thickness of 1 mm of 70% or more at a wavelength of 589 nm.
[17] The article% as set forth in [15] or [16], having a refractive index of 1.60 or more at a wavelength of 589 nm. [18] The article% as set forth in any one of [15] to [17] , having a maximum thickness of 0.1 mm or more. [19] An optical component comprising the article% as set forth in any one of [15] to [18] .
[20] The optical component as set forth in [19] , which is a lens base material.
According to the invention, it is possible to provide an organic-inorganic hybrid composition having excellent transparency and high refractive index and having excellent stability with time and an optical component using the same. Also, according to the invention, it is possible to arbitrarily control the refractive index.
MODES FOR CARRYING OUT THE INVENTION
The organic-inorganic hybrid composition of the invention and optical component configured to contain the same, for example, lens base materials, are hereunder described in detail. The following description of the constitutional requirements is made on the basis of representative embodiments of the invention, but it should not be construed that the invention is limited to those embodiments. In this specification, numerical value ranges expressed by the term "to" mean that the numerical values described before and after it are included as a lower limit and an upper limit, respectively.
[Compound represented by the formula (I)]
The organic-inorganic hybrid composition of the invention is characterized by containing a compound represented by the following formula (1) together with an inorganic fine particle. Formula (1)
Figure imgf000010_0001
In the formula (1), R1 and R2 each independently represents a substituent. Though the substituent which can be taken by R1 and R2 is not particularly limited, examples thereof include a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom) , an alkyl group (for example, a methyl group, an ethyl group) , an aryl group (for example, a phenyl group, a naphthyl group) , an alkenyl group, an alkynyl group, a cyano group, a carboxyl group, an alkoxycarbonyl group
(for example, a methoxycarbonyl group) , an aryloxycarbonyl group (for example, a phenoxycarbonyl group) , a substituted or unsubstituted carbamoyl group (for example, a carbamoyl group, an N-phenylcarbamoyl group, an N,N-dimethylcarbamoyl group), an alkylcarbonyl group (for example, an acetyl group) , an arylcarbonyl group (for example, a benzoyl group) , a nitro group, an acylamino group (for example, an acetoamide group, an ethoxycarbonylamino group) , a sulfonamide group (for example, a methanesulfonamide group) , an imide group (for example, a succinimide group, a phthalimide group) , an imino group (for example, a benzylideneamino group) , an alkoxy group (for example, a methoxy group) , an aryloxy group (for example, a phenoxy group) , an acyloxy group (for example, an acetoxy group, a benzoyloxy group) , an alkylsulfonyloxy group (for example, a methanesulfonyloxy group) , an arylsulfonyloxy group (for example, a benzenesulfonyloxy group) , a sulfo group, a substituted or unsubstituted sulfamoyl group (for example, a sulfamoyl group, an N-phenylsulfamoyl group) , an alkylthio group (for example, a methylthio group) , an arylthio group (for example, a phenylthio group) , an alkylsulfonyl group (for example, a methanesulfonyl group) , an arylsulfonyl group (for example, a benzenesulfonyl group) , a formyl group and a heterocyclic ring. These substituents may further be substituted. In the case where plural substituents are present in the molecule represented by the formula (1) , the respective substituents may be the same or different. Also, the substituent may form a fused ring structure together with a benzene ring. As the substituent represented by R1 and R2, a halogen atom, an alkyl group, an aryl group, a cyano group, an alkoxycarbonyl group, an aryloxycarbonyl group, a substituted or unsubstituted carbamoyl group, an alkylcarbonyl group, an arylcarbonyl group, a sulfonamide group, an alkoxy group, an aryloxy group, an acyloxy group, a substituted or unsubstituted sulfamoyl group, an alkylsulfonyl group and an arylsulfonyl group are preferable; a halogen atom, an alkyl group, an aryl group, an alkoxy group, an aryloxy group and an arylsulfonyl group are more preferable; and a halogen atom, an alkyl group, an aryl group and aryloxy group are especially preferable, ml andm2 each independently represents an integer of from 0 to 5. ml and m2 are each preferably from 0 to 3, more preferably from 0 to 2, and further preferably from 0 to 1. In the case where ml and m2 are each an integer of 2 or more, the substituents on the same benzene ring may be the same or different. a. represents 0 or 1. In the case where ais 0, it is meant that the benzene rings are connected to each other by a single bond. When a is 1, the benzene rings are connected to each other via L. L represents an oxy group or a methylene group. In this way, the benzene rings of the compound represented by the formula (1) are connected to each other by a single bond or via an oxy group or a methylene group, and preferably by a single bond or via an oxy group.
In one aspect of the invention, compounds represented by the following formulae (2) to (4) are preferable as the compound represented by the formula (1) .
Formula (2)
Figure imgf000012_0001
Formula ( 3 )
Figure imgf000012_0002
Formula (4)
Figure imgf000012_0003
In the formulae (2) to (4), R3, R4, R5, R6 and R7 each independently represents a substituent; and Z1, Z2, Z3 and Z4 each independently represents a hydrogen atom or a substituent . Though details and preferred range of the substituent which can be taken by R3, R4, R5, R6, R7, Z1, Z2, Z3 and Z4 are the same as the details and preferred range of the substituent which can be taken by R1 and R2 of the foregoing formula (1) , a hydrogen atom is added in the preferred range, more preferred range and especially preferred range, respectively. m3, m4 and mβ each independently represents an integer of from 0 to 4, preferably from 0 to 2, more preferably from 0 to 1, and further preferably 0; andm5 andm7 each independently represents an integer of from 0 to 5, preferably from 0 to 3, more preferably from 0 to 2, and further preferably from 0 to 1. In the case where m3, m4, m.5, m6 and m7 are each an integer of 2 or more, the substituents on the same benzene ring may be the same or different. bl, b2 and b3 each independently represents an integer of 2 or more, preferably from 2 to 8, more preferably from 2 to 6, and further preferably from 2 to 4.
In the formula (2) , though the positional relationship between Z1 and Z2 each bonding on the benzene ring may be any of ortho, meta or para, and it is preferably meta or para, and more preferably meta. The positional relationship between Z3 and 0 each bonding on the benzene ring in the formula (3) and the positional relationship between Z4 and CH2 each bonding on the benzene ring in the formula (4) are also the same.
In another aspect of the invention, a compound represented by the following formula (5) is preferable as the compound represented by the formula (1) . Formula ( 5 )
Figure imgf000014_0001
In the formula (5) , Ra, Rb and Rc each independently represents a substituent. Details and preferred range of the substituent which can be taken by Ra, Rb and Rc are the same as the details and preferred range of the substituent which can be taken by R1 and R2 of the foregoing formula (1) .
In the formula (5), A1 represents an oxy group or a methylene group. A2 represents an oxy group, a substituted or unsubstituted alkylene group, a carbonyl group, a substituted or unsubstituted imino group or a group composed of two or more members of these groups. The substituted or unsubstituted imino group as referred to herein is preferably a substituted or unsubstituted iminocarbonyl group or a substituted or unsubstituted carbonylimino group. A2 is preferably an oxy group, an unsubstituted methylene group, a carbonyl group, an unsubstituted imino group or a group composed of two or more members of these groups; more preferably an oxy group, an unsubstituted methylene group or a carbonyl group; and further preferably an oxy group or an unsubstituted methylene group. Details and preferred range of the substituent which can be taken by the methylene group and the imino group are the same as the details and preferred range of the substituent which can be taken by R1 and R2 of the foregoing formula (1) . Also, the "group composed of two or more members of these groups" which can be taken by A2 is a group obtained by bonding two or more groups selected from the group consisting of an oxy group, a substituted or unsubstituted methylene group, a carbonyl group and a substituted or unsubstituted imino group, and a plurality of the connecting groups of the same kind may be combined. Specific examples of the "group composed of two or more members of these groups" include a hydroxycarbonyl group, a carbonyloxy group, an alkyleneoxy group (for example, a methyleneoxy group, an ethyleneoxy group) , a hydroxyalkylene group (for example, a hydroxymethylene group, a hydroxyethylene group) , a carbonyloxyalkylene group (for example, a carbonyloxymethylene group, a carbonyloxyethylene group) , an alkyleneoxycarbonyl group (for example, a methyleneoxycarbonyl group, an ethyleneoxycarbonyl group) , an iminocarbonyl group and a carbonylimino group.
Though A1 and A2 may be the same or different, when both A1 and A2 are present (p = r = 1) , it is preferable that A1 and A2 are the same. p, q and r_ each independently represents 0 or 1. In the case where p and q are each 0, it is meant that the benzene rings are connected to each other by a single bond. When q is 0, then £ is 0. nl and n2 each independently represents an integer of from 0 to 5. nl and n2 are each preferably from 0 to 3, more preferably from 0 to 2, and more preferably from 0 to 1. n3 represents an integer of from 0 to 4. n3 is preferably from 0 to 2, and more preferably from 0 to 1. In the case where nl, n2 and n3 are each an integer of 2 or more, the substituents on the same benzene ring may be the same or different.
In a compound having three or more benzene rings in the molecule thereof, in the case where though when q is 1, the formula (5) is not met, when q is 0, the formula (5) is met, the formula (5) is applied as q = 0.
In the compound represented by the formula (1) , its molecular weight is preferably less than 2, 000, more preferably less than 1,000, and more preferably less than 700.
Specific examples of the compound represented by the formula (1) are given below, but it should not be construed that the compound of the formula (1 ) which can be used in the invention is limited thereto.
Figure imgf000016_0001
Figure imgf000017_0001
The compound represented by the formula (1) may be synthesized according to a well-known method to a person skilled in the art or may be commercially available. For example, S-3101, S-3103, S-3105 andS-3230, all of which are manufactured by Muramatsu Sekiyu Kenkyusho, can be used. The addition amount of the compound represented by the formula (1) to the organic-inorganic hybrid composition is preferably from 0.1 to 30% by mass, more preferably from 0.3 to 25% by mass, and further preferably from 0.5 to 20% by mass. When the addition amount of the compound represented by the formula (1) is not more than 30% by mass, there is a tendency that bleeding during molding or storage is easily prevented; and when the addition amount of the compound represented by the formula (1) is 0.1% by mass or more, there is a tendency that effects to be brought by the addition are easily obtained. The "bleeding" as referred to herein refers to a phenomenon that the added compound bleeds out on the surface of a molding.
[Inorganic fine particle] The organic-inorganic hybrid composition of the invention contains an inorganic fine particle together with the compound represented by the formula (1) . The inorganic fine particle to be used in the invention is not particularly limited, and fine particles described in, for example, JP-A-2002-241612, JP-A-2005-298717 and JP-A-2006-70069 can be used.
Specifically, oxide fine particles (for example, aluminum oxide, titanium oxide, niobium oxide, zirconium oxide, zinc oxide, magnesium oxide, tellurium oxide, yttrium oxide, indium oxide, tin oxide) , composite oxide fine particles (for example, lithium niobate, potassium niobate, lithium tantalate) , sulfide fine oxides (for example, zinc sulfide, cadmium sulfide) , other semi-conductor crystal fine particles (for example, zinc selenide, cadmium selenide, zinc telluride, cadmium telluride) , LiAlSiO4, PbTiO3, Sc2W3Oi2, ZrW2O8, AlPO4, Nb2Os, LiNO3 and the like can be used.
In particular, of these, metal oxide fine particles are preferable. Above all, any one member selected from the group consisting of zirconium oxide, zinc oxide, tin oxide and titanium oxide is preferable; and any one member selected from the group consisting of zirconium oxide, zinc oxide and titanium oxide is more preferable. Furthermore, it is especially preferable to use a zirconium oxide fine particle having good transparency in a visible region and low photocatalytic activity.
The inorganic fine particle to be used in the invention may be a hybrid material composed of plural components from the viewpoints of refractive index, transparency, stability and the like. Also, for a variety of purposes of reducing photocatalytic activity, reducing a percentage of water absorption and the like, the inorganic fine particle may be doped with a dissimilar element, or the surface layer of the inorganic fine particle may be coated with a dissimilar metal oxide (for example, silica, alumina) or may be subjected to surface modification with a silane coupling agent, a titanate coupling agent, an aluminate coupling agent, an organic acid (for example, carboxylic acids, sulfonic acids, phosphoric acids, sulfonic acids) or the like. Furthermore, a combination of two or more types thereof can be employed depending upon the purpose.
In the inorganic fine particle to be used in the invention, its refractive index is not particularly limited. In the case where the organic-inorganic hybrid composition of the invention is used for an optical member to be required to have a high refractive index, it is preferable that the inorganic fine particle also has high refractive index properties in addition to the foregoing heat temperature dependency. In that case, the refractive index of the inorganic fine particle to be used is preferably from 1.9 to 3.0, more preferably 2.0 to 2.7, and especially preferably from 2.1 to 2.5 at 220C and at a wavelength of 589 nm. When the refractive index of the fine particle is not more than 3.0, since a difference in .refractive index from the resin is relatively small, there is a tendency that the Rayleigh scattering is easily inhibited. Also, when the refractive index is 1.9 'or more, there is a tendency that an effect for realizing a high refractive index is easily obtained.
The refractive index of the inorganic fine particle can be, for example, estimated by a method of forming a hybrid material hybridized with the thermoplastic resin to be used in the invention into a transparent film, measuring its refractive index by an Abbe's refractometer (for example, "DM-M4", manufactured by Atago Co. , Ltd.) and calculating the refractive index of the inorganic fine particle from a refractive index of only the resin component as measured separately, a method of measuring refractive indexes of fine particle dispersions having a different concentration, thereby calculating the refractive index of the inorganic fine particle, or other method. When the number average particle size of the inorganic fine particle to be used in the invention is too small, there may be the case where the properties inherent to a substance constituting the fine particle vary, whereas when the number average particle size is too large, there may be the case where influences of the Rayleigh scattering become noticeable, thereby extremely lowering the transparency of the organic-inorganic hybrid composition. In consequence, a lower limit value of the number average particle size of the inorganic fine particle to be used in the invention is preferably 1 nm or more, more preferably 2 nm or more, and further preferably 3 nm or more; and an upper limit value thereof is preferably not more than 15 nm, more preferably not more than 10 nm, and further preferably not more than 7 nm. That is, the number average particle size of the inorganic fine particle in the invention is preferably from 1 nm to 15 nm, more preferably from
2 nm to 10 nm, and especially preferably from 3 nm to 7 nm.
Also, it is desirable that the inorganic fine particle to be used in the invention is satisfied with the foregoing average particle size and has narrow particle size distribution as far as possible. There are a variety of manners for defining such a monodispersed particle. For example, the numerical value specified range described in JP-A-2006-160992 is also applicable to the preferred particle size distribution range of the fine particle to be used in the invention.
Here, the foregoing number average particle size can be measured by an X-ray diffraction (XRD) analyzer or a transmission electron microscope (TEM) or the like.
The manufacturing method of the inorganic fine particle to be used in the invention is not particularly limited, and any known methods can be employed.
For example, the desired oxide fine particle can be obtained by using a metal halide or a metal alkoxide as a raw material and hydrolyzing it in a reaction system containing water. Details of this method are described in, for example,
Japanese Journal of Applied Physics, Vol. 37, pages 4603 to 4608
(1998) or Langmuir, Vol. 16, No. 1, pages 241 to 246 (2000).
Also, as other methods than the method of hydrolysis in water, a method of preparing an inorganic fine particle in an organic solvent or in an organic solvent having the thermoplastic resin of the invention dissolved therein may be employed. On that occasion, a variety of surface treating agents (for example, silane coupling agents, aluminate coupling agents, titanate coupling agents, organic acids (for example, carboxylic acids, sulfonic acids, phosphonic acids) ) may be made coexistent.
Examples of the solvent to be used in these methods include acetone, 2-butanone, dichloromethane, chloroform, toluene, ethyl acetate, cyclohexanone and anisole. These solvents may be used singly or in admixture of plural kinds thereof.
Examples of the synthesis method of the inorganic fine particle include, in addition to the foregoing methods, a variety of general synthesis methods of a fine particle described in, for example, JP-A-2006-70069, including methods for preparing an inorganic fine particle in a vacuum process such as a molecular beam epitaxy method and a CVD method.
From the viewpoints of transparency and realization of a high refractive index, the content of the inorganic fine particle in the organic-inorganic hybrid composition of the invention is preferably from 20 to 95% by mass, more preferably from 25 to 70% by mass, and especially preferably from 30 to
60% by mass. Also, from the standpoint of dispersibility, a mass ratio of the inorganic fine particle to the thermoplastic resin (dispersed polymer) in the invention is preferably from
1/0.01 to 1/100, more preferably from 1/0.05 to 1/10, and especially preferably from 1/0.05 to 1/5.
[Thermoplastic resin]
It is preferable that the organic-inorganic hybrid composition of the invention contains a thermoplastic resin. In particular, it is preferable that the organic-inorganic hybrid composition of the invention contains a thermoplastic resin having at least a functional group capable of forming an arbitrary chemical bond with the inorganic fine particle in a polymer end or side chain thereof. The chemical bond as referred to herein is defined to include a covalent bond, an ionic bond, a hydrogen bond and a coordination bond. Preferred examples of such a thermoplastic resin include the following three types of thermoplastic resins.
(1) Thermoplastic resin having, in a side chain thereof, a functional group selected among the following groups:
Figure imgf000022_0001
(wherein R11, R12, R13 and R14 each independently 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 aryl group) , -SO3H, -OSO3H, -CO2H and -Si (OR15)miR16 3-mi (wherein R15 and R16 each independently 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 aryl group; and ml represents an integer of from 1 to 3) . (2) Thermoplastic resin having a functional group selected among the following groups:
Figure imgf000023_0001
(wherein R21, R22, R23 and R24 each independently 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 aryl group) , -SO3H, -OSO3H, -CO2H and -Si (OR25) m2R26 3-m2 (wherein R25 and R26 each independently 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 aryl group; and m2 represents an integer of from 1 to 3) in at least one polymer end thereof. (3) Block copolymer constituted of a hydrophobic segment and a hydrophilic segment
These thermoplastic resins (1) to (3) are hereunder described in detail.
<Thermoplastic resin (1)>
The thermoplastic resin (1) to be used in the invention has a functional group capable of forming an arbitrary chemical bond with the inorganic fine particle in a side chain thereof. Examples of the chemical bond as referred to herein include a covalent bond, an ionic bond, a coordination bond and a hydrogen bond. In the case where plural functional groups are present, these functional groups may be each one capable of forming a different chemical bond with the inorganic fine particle. Whether or not a chemical bond can be formed is judged by whether or not when the thermoplastic resin and the inorganic fine particle are mixed in an organic solvent, the functional group or groups of the thermoplastic resin can form a chemical bond with the inorganic fine particle. All of the functional groups of the thermoplastic resin may form a chemical bond with the inorganic fine particle, or a part of the functional groups of the thermoplastic resin may form a chemical bond with the inorganic fine particle.
The functional group capable of being bound with the inorganic fine particle has a function for stably dispersing the inorganic fine particle in the thermoplastic resin upon the formation of a chemical bond with the inorganic fine particle. The functional group capable of forming a chemical bond with the inorganic fine particle is a functional group selected among the following groups:
Figure imgf000024_0001
(wherein R11, R12, R13 and R14 each independently 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 aryl group), -SO3H, -OSO3H, -CO2H and -Si (OR15) miR16 3-mi (wherein R15 and R16 each independently 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 aryl group; and ml represents an integer of from 1 to 3) . Preferred ranges of R11, R12, R13 and R14 are as follows.
The alkyl group preferably has from 1 to 30 carbon atoms, and more preferably from 1 to 20 carbon atoms, and examples thereof include a methyl group, an ethyl group and an n-propyl group. The substituted alkyl group includes, for example, an aralkyl group. The aralkyl group preferably has from 7 to 30 carbon atoms, and more preferably from 7 to 20 carbon atoms, and examples thereof include a benzyl group and a p-methoxybenzyl group. The alkenyl group preferably has from 2 to 30 carbon atoms, and more preferably from 2 to 20 carbon atoms, and examples thereof include a vinyl group and a 2-phenylethenyl group. The alkynyl group preferably has from 2 to 20 carbon atoms, and preferably from 2 to 10 carbon atoms, and examples thereof include an ethynyl group and a 2-phenylethynyl group. The aryl group preferably has from 6 to 30 carbon atoms, andmore preferably from 6 to 20 carbon atoms, and examples thereof include a phenyl group, a 2, 4, β-tribromophenyl group and a 1-naphthyl group. The aryl group as referred to herein includes a heteroaryl group. Examples of the substituent of each of the alkyl group, the alkenyl group, the alkynyl group and the aryl group include, in addition to these alkyl group, alkenyl group, alkynyl group and aryl group, a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom) and an alkoxy group (for example, a methoxy group and an ethoxy group) . R11, R12, R13 and R14 are each preferably a hydrogen atom or an alkyl group, and especially preferably a hydrogen atom.
Preferred ranges of R15 and R16 are the same as in R11, R12, R13 and R14. ml is preferably 3.
Of these functional groups, the following groups:
Figure imgf000026_0003
-SO3H, -CO2H and -Si (OR15)mlR16 3-mi are preferable; the following groups:
Figure imgf000026_0004
and -CO2H are more preferable; and the following groups :
Figure imgf000026_0005
are especially preferable.
The thermoplastic resin to be used in the invention is especially preferably a copolymer having a repeating unit represented by the following formula (7) . Such a copolymer can be obtained by copolymerizing a vinyl monomer represented by the following formula (6) . Formula (6)
Figure imgf000026_0001
Formula (7)
Figure imgf000026_0002
In the formulae (6) and (7) , R represents a hydrogen atom, a halogen atom or a methyl group; and X represents a divalent connecting group selected from the group consisting of -CO2-, -OCO-, -CONH-, -OCONH-, -0C00-, -0-, -S-, -NH- and a substituted or unsubstituted arylene group, and preferably -CO2- or a p-phenylene group.
Y represents a divalent connecting group having from 1 to 30 carbon atoms, preferably from 1 to 20 carbon atoms, more preferably from 2 to 10 carbon atoms, and further preferably from 2 to 5 carbon atoms. Specific examples thereof include an alkylene group, an alkyleneoxy group, an alkyleneoxycarbonyl group, an arylene group, an aryleneoxy group, an aryleneoxycarbonyl group and a combination thereof, with an alkylene group being preferable. q represents an integer of from 0 to 18, preferably an integer of from 0 to 10, more preferably an integer of from 0 to 5, and especially preferably an integer of from 0 to 1.
Z represents a functional group selected among the following groups:
Figure imgf000027_0001
-SO3H, -OSO3H, -CO2H and -Si (OR15) miR163-mi- Of these functional groups, the following groups are preferable:
Figure imgf000027_0002
and the following group is more preferable.
Figure imgf000028_0002
Here, definitions, preferred ranges and specific examples of R11, R12, R13, R14, R15, R16 and ml are independently synonymous with the foregoing definitions, preferred ranges and specific examples of R11, R12, R13, R14, R15, R16 and ml.
Specific examples of the monomer represented by the formula (6) are given below, but it should not be construed that the monomer which can be used in the invention is limited thereto.
Figure imgf000028_0001
Figure imgf000029_0001
Figure imgf000029_0002
Figure imgf000029_0003
Figure imgf000029_0004
In the invention, as a monomer of other kind which is copolymerizable with the monomer represented by the formula (6) , those described in Polymer Handbook 2nd Ed. , J. Brandrup, Wiley Interscience (1975) , Chapter 2, pages 1 to 483 can be used. Specific examples thereof include compounds having one addition polymerizable unsaturated bond selected among styrene derivatives, 1-vinylnaphthalene, 2-vinylnaphthalene, vinylcarbazole, acrylic acid, methacrylic acid, acrylic esters, methacrylic esters, acrylamides, methacrylamides, allyl compounds, vinyl ethers, vinyl esters, dialkyl itaconates and dialkyl esters or monoalkyl esters of fumaric acid.
Examples of the styrene derivatives include styrene, 2, 4, 6-tribromostyrene and 2-phenylstyrene.
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, benzyl acrylate, methoxybenzyl acrylate, furfuryl acrylate and tetrahydrofurfuryl acrylate.
Examples of the methacrylic esters include methyl methacrylate, ethyl methacrylate, propyl methacrylate, n-butyl methacrylate, tert-butyl methacrylate, chloroethyl methacrylate, 2-hydroxyethyl methacrylate, trimethylolpropane monomethacrylate, benzyl methacrylate, methoxybenzyl methacrylate, furfuryl methacrylate and tetrahydrofurfuryl methacrylate. Examples of the acrylamides include acrylamide, N-alkyl acrylamides (the alkyl group is one having from 1 to 3 carbon atoms, for example, a methyl group, an ethyl group, a propyl group) , N,N-dialkyl acrylamides (the alkyl group is one having from 1 to 6 carbon atoms), N-hydroxyethyl-N-methyl acrylamide and N-2-acetoamidoethyl-N-acetyl acrylamide.
Examples of the methacrylamides include methacrylamide, N-alkyl methacrylamides (the alkyl group is one having from 1 to 3 carbon atoms, for example, a methyl group, an ethyl group, a propyl group), N,N-dialkyl methacrylamides (the alkyl group is one having from 1 to 6 carbon atoms) , N-hydroxyethyl-N-methyl methacrylamide and N-2-acetoamidoethyl-N-acetyl methacrylamide .
Examples of the allyl compounds include allyl esters (for example, allyl acetate, allyl caproate, allyl caprate, allyl laurate, allyl palmitate, allyl stearate, allyl benzoate, allyl acetoacetate, allyl lactate) and allyloxyethanol.
Examples of the vinyl ethers include alkyl vinyl ethers (the alkyl group is one having from 1 to 10 carbon atoms; for example, hexyl vinyl ether, octyl vinyl ether, decyl vinyl ether, ethylhexyl vinyl ether, methoxyethyl vinyl ether, ethoxyethyl vinyl ether, chloroethyl vinyl ether, l-methyl-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 valerate, vinyl caproate, vinyl chloroacetate, vinyl dichloroacetate, vinyl methoxyacetate, vinyl butoxyacetate, vinyl lactate, vinyl-β-phenyl butyrate and vinyl cyclohexyl carboxylate.
Examples of the dialkyl itaconates include dimethyl itaconate, diethyl itaconate and dibutyl itaconate; and examples of the dialkyl esters or monoalkyl esters of fumaric acid include dibutyl fumarate.
Besides, crotonic acid, itaconic acid, acrylonitrile, methacrylonitrile and malelonitrile can be exemplified. In the thermoplastic resin (1) to be used in the invention, its weight average molecular weight is preferably from 1,000 to 500,000, more preferably from 3,000 to 300,000, and especially preferably from 10,000 to 100,000. When the weight average molecular weight of the thermoplastic resin (1) is not more than 500,000, there is a tendency that the molding processability is enhanced; and when the weight average molecular weight of the thermoplastic resin (1) is 1, 000 or more, there is a tendency that the mechanical strength is enhanced.
Here, the foregoing weight average molecular weight is a molecular weight measured by differential refractometer detection in tetrahydrofuran as a solvent by a GPC analyzer using columns of "TSKgel GMHxL", "TSKgel G4000HxL" and "TSKgel G2000HxL" (all of which are manufactured by Tosoh Corporation) and reduced into polystyrene. In the thermoplastic resin (1) to be used in the invention, the number of the foregoing functional group to be bound with the inorganic fine particle is preferably from 0.1 to 20, more preferably from 0.5 to 10, and especially preferably from 1 to 5 in average per one polymer chain. When the number of the functional group is not more than 20 in average per one polymer chain, there is a tendency that it is easy to prevent the matter that the thermoplastic resin (1) is coordinated with a plurality of the inorganic fine particle to cause high viscosity or gelation in a solution state from occurring. Also, when the number of the functional group is 0.1 or more in average per one polymer chain, there is a tendency that it is easy to stably disperse the inorganic fine particle.
In the thermoplastic resin (1) to be used in the invention, its glass transition temperature is preferably from 80 °C to 400 °C, and more preferably from 1300C to 380 °C. When a resin having a glass transition temperature of 80 °C or higher is used, it is easy to obtain an optical component having sufficient heat resistance. Also, when a resin having a glass transition temperature of not higher than 400 °C is used, there is a tendency that it is easy to achieve molding processing.
In the case where a difference between a refractive index of the thermoplastic resin (1) and a refractive index of the inorganic fine particle is large, since the Rayleigh scattering is easy to occur, the amount of the fine particle capable of being hybridized while keeping the transparency becomes small. When the refractive index of the thermoplastic resin (1) is about 1.48, it is possible to provide a transparent article% having a refractive index on a level of 1.60. However, in order to realize a refractive index of 1.65 or more, the refractive index of the thermoplastic resin (1) to be used in the invention is preferably 1.55 or more, and more preferably 1.58 or more. These refractive indexes are a value at 220C and at a wavelength of 589 nm. In the thermoplastic resin (1) to be used in the invention, its light transmittance as reduced in a thickness of 1 mm at a wavelength of 589 nm is preferably 80% or more, more preferably 85% or more, and especially preferably 88% or more.
Specific examples of the thermoplastic resin which can be preferably used in the invention are given below, but it should not be construed that the thermoplastic resin which can be used in the invention is limited thereto.
Figure imgf000033_0001
Figure imgf000034_0001
Figure imgf000035_0001
Figure imgf000035_0002
Figure imgf000036_0001
Figure imgf000036_0002
Figure imgf000036_0003
Figure imgf000037_0001
Figure imgf000037_0002
Figure imgf000037_0003
Figure imgf000038_0001
Figure imgf000038_0002
Figure imgf000038_0003
Figure imgf000039_0001
Figure imgf000040_0001
Figure imgf000041_0001
Figure imgf000041_0002
Figure imgf000041_0003
The thermoplastic resin (1) may be used singly or in admixture of two or more kinds thereof . Also, the thermoplastic resin (1) may be used in combination with the following thermoplastic resins (2) and/or (3).
<Thermoplastic resin (2)>
The thermoplastic resin (2) to be used in the invention has a functional group capable of forming a chemical bond with the inorganic fine particle in at least one polymer end thereof. Though the functional group may be present in only one end of a polymer chain or may be present in both ends of a polymer chain, it is preferable that the functional group is present only one end of a polymer chain. Also, a plurality of the functional group may be present in the end. The term "end" as referred to herein refers to a portion excluding a structure to be interposed between the repeating unit and the repeating unit constituting a polymer chain. The "chemical bond" as referred to herein can be considered in the same meanings as in the foregoing thermoplastic resin (1) .
The functional group capable of forming a chemical bond with the inorganic fine particle is a functional group selected among the following groups:
Figure imgf000042_0001
(wherein R21, R22, R23 and R24 each independently 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 aryl group) , -SO3H, -OSO3H, -CO2H and -Si (OR25)m2R263-m2 (wherein R25 and R26 each independently 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 aryl group; and m2 represents an integer of from 1 to 3) .
In the case where R21, R22, R23, R24, R25 and R26 are each a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkynyl group or a substituted or unsubstituted aryl group, preferred ranges thereof are the same as the preferred ranges described above for R11, R12, R13 and R14. Also, m2 is preferably 3.
Of these functional groups, the following groups:
Figure imgf000042_0002
-SO3H, -CO2H and -Si (OR25) m2R26 3-m2 are preferable; the following groups :
Figure imgf000043_0001
-SO3H and -CO2H are more preferable; and the following groups:
Figure imgf000043_0002
and -SO3H are especially preferable.
In the thermoplastic resin (2) to be used in the invention, its basic skeleton is not particularly limited. Known resin skeletons such as poly (meth) acrylates, polystyrenes, polyvinylcarbazoles, polyallylates, polycarbonates, polyurethanes, polyimides, polyethers, polyethersulfones, polyetherketones, polythioethers, cycloolefin polymers and cycloolefin copolymers can be employed. Of these, vinyl polymers, polyallylates and aromatic-containing polycarbonates are preferable; and vinyl polymers are more preferable. Specific examples thereof are the same as those described above for the thermoplastic resin (1) .
In the thermoplastic resin (2) to be used in the invention, its refractive index is preferably greater than 1.50, more preferably greater than 1.55, further preferably greater than 1.60, and especially preferably greater than 1.65. The refractive index in the invention is a value measured regarding light at a wavelength of 589 nm.by an Abbe's refractometer (for example, "DM-M4", manufactured by Atago Co., Ltd.). In the thermoplastic resin (2) to be used in the invention, its glass transition temperature is preferably from 50 °C to 4000C, and more preferably from 80 °C to 3800C. When the glass transition temperature is 50 °C or higher, there is a tendency that the heat resistance is enhanced. Also, when the glass transition temperature is not higher than 400 0C, there is a tendency that it is easy to achieve molding processing.
In the thermoplastic resin (2) to be used in the invention, its light transmittance as reduced in a thickness of 1 mm at a wavelength of 589 nm is preferably 80% or more, and more preferably 85% or more.
In the thermoplastic resin (2) to be used in the invention, its number average molecular weight is from 1,000 to 500,000. The number average molecular weight of the thermoplastic resin (2) is preferably from 3,000 to 300,000, more preferably from 5,000 to 200,000, and especially preferably from 10,000 to 100,000. When the number average molecular weight of the thermoplastic resin (2) is 1,000 or more, there is a tendency that the mechanical strength is enhanced; and when the number average molecular weight of the thermoplastic resin (2) is not more than 500,000, there is a tendency that the molding processability is enhanced.
The method for introducing the foregoing functional group into the end of a polymer chain is not particularly limited. For example, as described in Shin Kobunshi Jikken-gaku (New Polymer Experimentology) 4, Synthesis and Reaction (3) of Polymer, Reaction and Decomposition of Polymer, Chapter 3: Terminal Reactive Polymer (edited by The Society of Polymer Science, Japan) , the functional group may be introduced at the time of polymerization, or after the polymerization, conversion of the terminal functional group of the polymer once isolated or decomposition of the principal chain may be performed. A polymeric reaction such as a method for performing polymerization using an initiator, a stopping agent or a chain transfer agent each having a functional group and/or a protected functional group, etc. to obtain a polymer or a method for modifying a phenol terminal moiety of polycarbonate obtained from, for example, bisphenol A with a functional group-containing reacting agent can be employed. For example, radical polymerization of a vinyl based monomer by a chain transfer method using a sulfur-containing chain transfer agent described in Shin Kobunshϊ Jikken-gaku (New Polymer Experimentology) 2, Synthesis and Reaction (1) of Polymer, Synthesis of Addition Polymer (edited by The Society of Polymer Science, Japan), pages 110 to 112; living cationic polymerization using a functional group-containing initiator and/or a functional group-containing stopping agent described in Shin Kobunshi Jikken-gaku (New Polymer Experimentology) 2, Synthesis and Reaction (1) of Polymer, Synthesis of Addition Polymer (edited by The Society of Polymer Science, Japan) , pages 255 to 256; and ring-opening metathesis polymerization using a sulfur-containing chain transfer agent described in Macromolecules, Vol. 36, pages 7020 to 7026 (2003) can be exemplified.
Specific examples of the thermoplastic resin (2) which can be preferably used in the invention are given below (Illustrative Compounds P-I to P-22), but it should not be construed that the thermoplastic resin (2) which can be used in the invention is limited thereto. The structures within the square brackets each represents a repeating unit; and x and y in the repeating unit represent a copolymerization ratio (molar ratio) .
Figure imgf000046_0001
Figure imgf000047_0001
Figure imgf000048_0001
The thermoplastic resin (2) may be used singly or in admixture of two or more kinds thereof. Also, these thermoplastic resins may contain other copolymerization component .
<Thermoplastic resin (3)>
The thermoplastic resin (3) to be used in the invention is a block copolymer constituted of a hydrophobic segment (A) and a hydrophilic segment (B) .
The hydrophobic segment (A) as referred to herein refers to a segment having such properties that a polymer composed of only the segment (A) is insoluble in water or methanol; and the hydrophilic segment (B) as referred to herein refers to a segment having such properties that a polymer composed of only the segment (B) is soluble in water or methanol. Examples of a type of the block copolymer include an AB type, a B1AB2 type (the two hydrophilic segments B1 and B2 may be the same or different) and an A1BA2 type (the two hydrophobic segments A1 and A2 may be the same or different) . Of these, in view of good dispersion properties, block copolymers of an AB type or an A1BA2 type are preferable; and in view of the manufacturing aptitude, block copolymers of an AB type or an ABA type (the two hydrophobic segments of the A1BA2 type are the same) are more preferable, with an AB type being especially preferable.
The hydrophobic segment and the hydrophilic segment can be each selected among polymers which have hitherto been known, for example, vinyl polymers obtained through polymerization of a vinyl monomer, polyethers, ring-opening metathesis polymerization polymers and condensation polymers (for example, polycarbonates, polyesters, polyamides, polyetherketones, polyethersulfones) . Of these, vinyl polymers, ring-opening metathesis polymerization polymers, polycarbonates and polyesters are preferable; and vinyl polymers are more preferable in view of manufacturing aptitude.
As the vinyl monomer (A) for forming the hydrophobic segment (A) , for example, the following can be exemplified. That is, examples thereof include acrylic esters or methacrylic esters (in which the ester group thereof is a substituted or unsubstituted aliphatic ester group or a substituted or unsubstituted aromatic ester group, for example, a methyl group, a phenyl group, a naphthyl group) ; acrylamides and methacrylamides, specifically N-mono-substituted acrylamides, N-di-substituted acrylamides, N-mono-substituted methacrylamides and N-di-substituted methacrylamides (in which the substituent of the mono-substituted materials and the di-substituted materials is a substituted or unsubstituted aliphatic group or a substituted or unsubstituted aromatic group, for example, a methyl group, a phenyl group, a naphthyl group) ; olefins, specifically dicyclopentadiene, norbornene derivatives, ethylene, propylene, 1-butene, 1-pentene, vinyl chloride, vinylidene chloride, isoprene, chloroprene, butadiene, 2, 3-dimethylbutadiene, vinylcarbazole, etc.; styrenes, specifically styrene, methylstyrene, diemthylstyrene, trimethylstyrene, ethylstyrene, isopropylstyrene, chloromethylstyrene, methoxystyrene, acetoxystyrene, chlorostyrene, dichlorostyrene, bromostyrene, tribromostyrene, methyl vinylbenzoate, etc.; vinyl ethers, specifically methyl vinyl ether, butyl vinyl ether, phenyl vinyl ether, methoxyethyl vinyl ether, etc. ; and other monomers, for example, butyl crotonate, hexyl crotonate, dimethyl itaconate, dibutyl itaconate, diethyl maleate, dimethyl maleate, dibutyl maleate, diethyl fumarate, dimethyl fumarate, dibutyl fumarate, methyl vinyl ketone, phenyl vinyl ketone, methoxyethyl vinyl ketone, N-vinyloxazolidone, N-vinylpyrrolidone, vinylidene chloride, -methylene malonitrile, vinylidene, diphenyl-2-acryloyloxyethyl phosphate, diphenyl-2-methacryloyloxyethyl phosphate, dibutyl-2-acryloyloxyethyl phosphate, dioctyl-2-methcryloyloxyethyl phosphate . Of these, acrylic esters and methacrylic esters in which the ester group thereof is an unsubstituted aliphatic group or a substituted or unsubstituted aromatic group; N-mono-substituted acrylamides, N-di-substituted acrylamides, N-mono-substituted methacrylamides and N-di-substituted methacrylamides in which the substituent thereof is an unsubstituted aliphatic group or a substituted or unsubstituted aromatic group; and styrenes are preferable. Acrylic esters and methacrylic esters in which the ester group thereof is a substituted or unsubstituted aromatic group; and styrenes are more preferable.
As the vinyl monomer (B) for forming the hydrophilic segment (B) , for example, the following can be exemplified.
That is, examples thereof include acrylic acid, methacrylic acid and acrylic esters and methacrylic esters each having a hydrophilic substituent in an ester site thereof; styrenes having a hydrophilic substituent in an aromatic ring moiety thereof; and vinyl ethers, acrylamides, methacrylamides, N-mono-substituted acrylamides, N-di-substituted acrylamides, N-mono-substituted methacrylamides and N-di-substituted methacrylamides each having a hydrophilic substituent.
The hydrophilic substituent is preferably one having a functional group selected among the following groups:
Figure imgf000051_0001
(wherein R31, R32, R33 and R34 each independently 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 aryl group), -SO3H, -OSO3H, -CO2H, -OH and -Si (OR35) m3R36 3-m3 (wherein R35 and R36 each independently 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 aryl group; and m3 represents an integer of from 1 to 3) . In the case where R31, R32, R33, R34, R35 and R36 are each a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkynyl group or a substituted or unsubstituted aryl group, preferred ranges thereof are the same as the preferred ranges described above for R11, R12, R13 and R14. Also, m3 is preferably 3.
Of these functional groups, the following groups:
Figure imgf000052_0001
-CO2H and -Si (OR35)m3R36 3-m3 are preferable; the following groups:
Figure imgf000052_0002
and -CO2H are more preferable; and the following groups:
Figure imgf000052_0003
are especially preferable.
In the invention, it is especially preferable that the foregoing block copolymer has a functional group selected among the following groups :
Figure imgf000052_0004
-SO3H, -OSO3H, -CO2H, -OH and -Si (OR35)m3R36 3_m3 that the content of the functional group is 0.05 mmoles/g or more and not more than 5.0 mmoles/g.
Above all, acrylic acid, methacrylic acid, acrylic esters and methacrylic esters each having a hydrophilic substituent in an ester site thereof and styrenes having a hydrophilic substituent in an aromatic ring moiety thereof are preferable as the hydrophilic segment (B) .
The vinyl monomer (A) for forming the hydrophobic segment
(A) may contain the vinyl monomer (B) within the range where the hydrophobic properties are not hindered. A molar ratio of the vinyl monomer (A) to the vinyl monomer (B) to be contained in the hydrophobic segment (A) is preferably from 100/0 to 60/40.
The vinyl monomer (B) for forming the hydrophilic segment
(B) may contain the vinyl monomer (A) within the range where the hydrophilic properties are not hindered. A molar ratio of the vinyl monomer (B) to the vinyl monomer (A) to be contained in the hydrophilic segment (B) is preferably from 100/0 to 60/40.
The vinyl monomer (A) and the vinyl monomer (B) may be each used singly or in admixture of two or more kinds thereof. The vinyl monomer (A) and the vinyl monomer (B) are each selected depending upon a variety of purposes (for example, adjustment of the acid content, adjustment of the glass transition point (Tg) , adjustment of solubility in an organic solvent or water, adjustment of the stability of a dispersion) .
The content of the functional group is preferably from 0.05 to 5.0 mmoles/g, more preferably from 0.1 to 4.5 mmoles/g, and especially preferably from 0.15 to 3.5 mmoles/g relative to the whole of the block copolymer. When the content of the functional group is too small, there may be the case where the dispersion aptitude is low; and when the content of the functional group is too large, there may be the case where the water solubility becomes too high, or the organic-inorganic hybrid composition is gelated. In the block copolymer, the foregoing functional group may form a salt with a cationic ion such as an alkali metal ion (for example, Na+, K+) and an ammonium ion.
In the block copolymer, its molecular weight (Mn) is preferably from 1,000 to 100,000, more preferably from 2,000 to 80, 000, and especially preferably from 3, 000 to 50,000. When the molecular weight of the block copolymer is 1,000 or more, there is a tendency that a stable dispersion is easily obtained; and when it is not more than 100,000, there is a tendency that the solubility in an organic solvent is enhanced, and therefore, such is preferable.
In the block copolymer to be used in the invention, its refractive index is preferably greater than 1.50, more preferably greater than 1.55, further preferably greater than 1.60, and especially preferably greater than 1.65. The refractive index as referred to herein is a value measured regarding light at a wavelength of 589 nm by an Abbe's refractometer (for example, "DR-M4", manufactured by Atago Co. , Ltd. ) . In the block copolymer to be used in the invention, its glass transition temperature is preferably from 80 °C to 400 °C, and more preferably from 130 °C to 380 0C. When the glass transition temperature is 800C or higher, there is a tendency that the heat resistance is enhanced; and when the glass transition temperature is not higher than 400 0C, there is a tendency that the molding processability is enhanced.
In the block copolymer to be used in the invention, its light transmittance as reduced in a thickness of 1 mm at a wavelength of 589 nm is preferably 80% or more, and more preferably 85% or more.
Specific examples of the block copolymer are given below (Illustrative Compounds Q-I to Q-20) , but it should not be construed that the block copolymer to be used in the invention is limited thereto.
Figure imgf000055_0001
Figure imgf000056_0001
The block copolymer can be synthesized utilizing living radical polymerization or living ionic polymerization using a method such as protection of a carboxyl group, etc. and introduction of a functional group into the polymer as the need arises. The block copolymer can also be synthesized through radical polymerization from a terminal functional group polymer or connection between terminal functional polymers each other. Above all, in view of the molecular weight control and the percent yield of the block polymer, it is preferable to utilize living radical polymerization or living ionic polymerization. The manufacturing method of the block copolymer is described in, for example, Kobunshi no Gosei to Hanno (Synthesis and Reaction of Polymer) (1) (edited by The Society of Polymer Science, Japan and published by Kyoritsu Shuppan Co., Ltd. (1992) ); Seimitsu Jugo (Accurate Polymerization) (editedbyThe
Society of Polymer Science, Japan and published by Japan
Scientific Societies Press (1993) ) ; Kobunshi no Gosei to Hanno
(Synthesis and Reaction of Polymer) (1) (edited by The Society of Polymer Science, Japan and published by Kyoritsu Shuppan Co . , Ltd. (1995) ) ; "Telechelic Polymer: Synthesis and Properties, Application" (R. Jerome, et al., Prog. Polym. Sci., Vol. 16, pages 837 to 906 (1991) ) ; "Synthesis of Block or Graft Copolymer by Light" (Y. Yagch, et al . , Prog. Polym. Sci., Vol. 15, pages 551 to 601 (1990)); and U.S. Patent No. 5,085,698. These resins may be used singly or in admixture of two or more kinds thereof.
[Other additives]
From the viewpoints of uniform dispersibility, release properties, weather resistance and the like, the organic-inorganic hybrid composition of the invention may be properly compounded with a variety of additives in addition to the foregoing compound represented by the formula (1), inorganic fine particle and thermoplastic resin. Examples of such additives include a surface treating agent, an antistatic agent, adispersant, a plasticizer and a releasing agent . Also, in addition to the foregoing resin, a resin not having the foregoing functional agent may be added. Though such a resin is not particularly limited with respect to its type, those having the same optical physical properties, thermal physical properties and molecular weight as in the foregoing thermoplastic resin are preferable.
Though a blending proportion of such an additive varies depending upon the purpose, it is preferably from 0 to 50% by mass, more preferably from 0 to 30% by mass, and especially preferably from 0 to 20% by mass relative to the total sum of the foregoing inorganic fine particle and thermoplastic resin.
<Surface treating agent>
In the invention, in mixing the inorganic fine particle dispersed in water or an alcohol solvent as described later with the thermoplastic resin, a fine particle surface modifying agent other than the foregoing thermoplastic resin may be added for a variety of purposes such as a purpose of enhancing extraction properties or substitution properties into the organic solvent, a purpose of enhancing the uniform dispersibility into the thermoplastic resin, a purpose of lowering the water absorption properties of the fine particle, or a purpose of enhancing the weather resistance. In the surface treating agent, its weight average molecular weight is preferably from 50 to 50, 000, more preferably from 100 to 20, 000, and further preferably from 200 to 10,000.
The surface treating agent is preferably one having a structure represented by the following formula (8) : Formula (8)
A-B
In the formula (8), A represents a functional group capable of forming a chemical bond with the surface of the inorganic fine particle to be used in the invention; and B represents a monovalent group having from 1 to 30 carbon atoms and having compatibility or reactivity with a resin matrix containing, as a major component, the thermoplastic resin to be used in the invention or a polymer. The "chemical bond" as referred to herein refers to a covalent bond, an ionic bond, a coordination bond, a hydrogen bond or 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 to be used in the invention.
On the other hand, from the viewpoint of compatibility, the chemical structure of the group represented by B is preferably the same as or analogous to the chemical structure of the thermoplastic resin which is the major component of the resin matrix. In particular, in the invention, from the viewpoint of realizing a high refractive index, it is preferable that the chemical structure of B has an aromatic ring similar to the foregoing thermoplastic resin.
Examples of the surface treating agent which is preferably used in the invention include p-octylbenzoic acid, p-propylbenzoic acid, acetic acid, propionic acid, cyclopentanecarboxylic acid, dibenzyl phosphate, monobenzyl phosphate, diphenyl phosphate, di-α-naphthyl phosphate, phenylphosphonic acid, phenylphosphonic acid monophenyl ester, KAYAMER PM-21 (a trade name, manufactured by Nippon Kayaku Co. , Ltd. ) , KAYAMER PM-2 (a trade name, manufactured by Nippon Kayaku Co., Ltd.), benzenesulfonic acid, naphthalenesulfonic acid, p-octylbenzenesulfonic acid and silane coupling agents described in JP-A-5-221640, JP-A-9-100111 and JP-A-2002-187921. However, it should not be construed that the invention is limited thereto.
Such a surface treating agent may be used singly or in combination of plural kinds thereof.
The total amount of the addition amount of such a surface treating agent is preferably from 0.01 to 2 times, more preferably from 0.03 to 1 time, and especially preferably from 0.05 to 0.5 times the amount of the inorganic fine particle in terms of a mass. <Antistatic agent>
In order to adjust the dielectric strength of the organic-inorganic hybrid composition- of the invention, an antistatic agent can be added. In the organic-inorganic hybrid composition of the invention, there may be the case where the inorganic fine particle per se, which is added for the purpose of improving the optical properties, contributes to an antistatic effect as a separate effect. In the case where the antistatic agent is added, examples thereof include an anionic antistatic agent, a cationic antistatic agent, a nonionic antistatic agent, an ampholytic antistatic agent, a polymer antistatic agent and an antistatic fine particle. Such an antistatic agent may be used in combination of two or more kinds thereof. Examples thereof include compounds described in JP-A-2007-4131 and JP-A-2003-201396.
Though the addition amount of the antistatic agent is divergent, it is preferably from 0.001 to 50% by mass, more preferably from 0.01 to 30% by mass, and especially preferably from 0.1 to 10% by mass of the total solids content.
<Others>
In addition to the foregoing compounds, for the purposes of enhancing a release effect and further enhancing the fluidity at the time of molding, not only natural waxes such as vegetable waxes (for example, carnauba wax, rice wax, cotton wax, Japan wax) , animal waxes (for example, beeswax, lanolin) , mineral waxes (for example, ozokerite, ceresin) and petroleum waxes
(for example, paraffins, microcrystalline waxes, petrolatum) , but synthetic hydrocarbon waxes (for example, Fischer-Tropsch wax, polyethylene wax) , long-chain aliphatic amides (for example, stearic acid amide, chlorinated hydrocarbons), synthetic waxes (for example, esters, ketones, ethers) , silicone oils (for example, dimethyl silicone oil, methylphenyl silicone oil) and fluorotelomers (for example, ZONYL FSN and ZONYL FSO, all of which are manufactured by DuPont) can also be added. Also, for the purpose of improving the light fastness or heat deterioration, known deterioration preventive agents such as hindered phenol based, amine based, phosphorus based or thioether based deterioration preventive agents may be properly added. In the case where such a deterioration preventive agent is compounded, it is preferably added in an amount of from about 0.1 to 5% by mass relative to the total solids content of the resin composition.
[Manufacturing method of organic-inorganic hybrid composition]
The organic-inorganic hybrid composition of the invention is preferably manufactured by chemically bonding the inorganic fine particle with the foregoing functional group-containing thermoplastic resin to disperse it in the resin. At that time, the compound represented by the formula (1) is made present.
Since the inorganic fine particle to be used in the invention is small in particle size and high in surface energy, when isolated as a solid, it is difficult to be re-dispersed. Therefore, it is preferable that the inorganic fine particle is mixed with the thermoplastic resin in a dispersed state in a solution to form a stable dispersion. Preferred examples of the manufacturing method of the organic-inorganic hybrid composition include [1] a method in which an inorganic fine particle is surface treated in the presence of the foregoing surface treating agent, the surface-treated inorganic fine particle is extracted into an organic solvent, and the extracted inorganic fine particle is uniformly mixed with the foregoing thermoplastic resin and the foregoing compound represented by the formula (1) to manufacture a hybrid material of the inorganic fine particle and the thermoplastic resin; and [2] a method in which an inorganic fine particle, a thermoplastic resin, a compound represented by the formula (1) and other additives are uniformly mixed using a solvent capable of uniformly dispersing or dissolving all of the components therein to manufacture a hybrid material of the inorganic fine particle and the thermoplastic resin.
In the case where a hybrid material of the inorganic fine particle and the thermoplastic resin is manufactured by the foregoing method [1] , a water-insoluble solvent such as toluene, ethyl acetate, methyl isobutyl ketone, chloroform, dichloroethane, dichloromethane, chlorobenzene and methoxybenzene is used as the organic solvent. Though the surface treating agent to be used for extracting the inorganic fine particle into the organic solvent and the thermoplastic resin may be the same kind or a different kind, as to the surface treating agent to be preferably used, those described above in the <Surface treating agent> section are exemplified.
In mixing the inorganic fine particle extracted into the organic solvent and the thermoplastic resin, the compound represented by the formula (1) is added, and additives such as a plasticizer, a releasing agent and a polymer of other type may further be added as the need arises.
In the case where the foregoing method [2] is employed, a single or mixed solvent of hydrophilic polar solvents (for example, dimethylacetamide, dimethylformamide, dimethyl sulfoxide, benzyl alcohol, cyclohexanol, ethylene glycol monomethyl ether, l-methoxy-2-propanol, tert-butanol, acetic acid, propionic acid) is preferably used as the solvent. Alternatively, a mixed solvent of a water-insoluble resin (for example, chloroform, dichloroethane, dichloromethane, ethyl acetate, methyl ethyl ketone, methyl isobutyl ketone, toluene, chlorobenzene, methoxybenzene) and the foregoing polar solvent is preferably used as the solvent. On that occasion, apart from the foregoing thermoplastic resin, adispersant, a plasticizer, a releasing agent or a polymer of other type may be added as the need arises. In using a fine particle dispersed in water/methanol, it is preferable that after adding a hydrophilic solvent capable of dissolving the thermoplastic resin therein at a higher boiling point than that of water/methanol, the water/methanol is concentrated and distilled off, thereby substituting a dispersion of the fine particle into the polar organic solvent, followed by mixing with the resin. At that time, the foregoing surface treating agent may be added. The solution of the organic-inorganic hybrid composition obtained in the foregoing method [1] or [2] can be subjected to cast molding as it is, to obtain a transparent molding. However, in the invention, it is especially preferable that after removing the solvent from the solution by a method such as concentration, freeze-drying and reprecipitation from an appropriate poor solvent, a powdered solid is molded by a known method such as injection molding and compression molding. Also, on that occasion, the powdered organic-inorganic hybrid composition of the invention can be directly processed into a molding such as lenses by heat melting or compression. It is also possible to prepare an optical component such as lenses by once preparing a preform (precursor) having fixed weight and shape by a method such as an extrusion method and deforming the preform by compression molding. In that case, in order to efficiently prepare a desired shape, it is also possible to bring the preform with an appropriate curvature.
[Organic-inorganic hybrid composition]
In the organic-inorganic hybrid composition, its light transmittance as reduced in a thickness of 1 mm at a wavelength of 589 nm is preferably 70% or more, more preferably 75% or more, and especially preferably 80% or more. Also, the light transmittance at a wavelength of 405 nm is preferably 60% or more, more preferably 65% or more, and especially preferably 70% or more. When the light transmittance as reduced in a thickness of 1 mm at a wavelength of 589 run is 70% or more, it is easy to obtain a lens base material having more preferable properties. In the invention, the light transmittance as reduced in a thickness of 1 mm is a value obtained by molding the organic-inorganic hybrid composition to prepare a substrate having a thickness of 1.0 mm and measuring it by a spectrophotometer for ultraviolet and visible region (UV-3100, manufactured by Shimadzu Corporation) . Also, in the organic-inorganic hybrid composition of the invention, its refractive index at a wavelength of 589 nm is preferably 1.60 or greater, more preferably 1.65 or greater, and especially preferably 1.67 or greater.
For the purpose of preventing the deposition of dusts, it is desirable that the organic-inorganic hybrid composition of the invention is hardly electrified. Its dielectric strength is preferably from -2 to 15 kV, more preferably from
-1.5 to 7.5 kV, and especially preferably from -1.0 to 7.0 kV.
In the organic-inorganic hybrid composition of the invention, its glass transition temperature is preferably from 1000C to 400 °C, and more preferably from 130 °C to 380 °C. When the glass transition temperature is 1000C or higher, sufficient heat resistance is easily obtained; and when the glass transition temperature is not higher than 400 0C, there is a tendency that it is easy to achieve molding processing.
In the organic-inorganic hybrid composition of the invention, it is preferable that when kept at 2000C for 2 hours, its volatile component content is not more than 2% by mass; it is more preferable that when kept at 230 °C for 2 hours, its volatile component content is not more than 2% by mass; and it is especially preferable that when kept at 2500C for 2 hours, its volatile component content is not more than 2% by mass.
In the organic-inorganic hybrid composition of the invention, its percentage of saturated water absorption is preferably not more than 2% by mass, more preferably not more than 1% by mass, and especially preferably not more than 0.5% by mass.
[Article]
By forming the organic-inorganic hybrid composition of the invention to a particular shape (for example by molding) , it is possible to manufacture the article of the invention. As to the article of the invention, one exhibiting the refractive index and optical properties described above for the organic-inorganic hybrid composition is useful.
Also, the article of the invention is especially useful for high-refractive index optical components having a thickness of 0.1 mm or more at maximum. It is preferable to apply the article of the invention to optical components having a thickness of from 0.1 to 5 mm; and it is especially preferable to apply the article of the invention to optical components having a thickness of from 1 to 3 mm.
In manufacturing such a thick article by a solution casting method, the solvent is hardly discharged so that article is usually not easy. However, by using the organic-inorganic hybrid composition of the invention, molding is easy, a complicated shape such as non-spheres can be easily imparted, and a material having good transparency can be formed while utilizing high refractive index properties of the fine particle.
[Optical components]
The article of the invention is an article having high refraction properties, light transmission properties and lightweight properties and having excellent optical properties. The optical component of the invention is configured of such an article. The type of the optical component of the invention is not particularly limited. In particular, the optical component of the invention can be favorably utilized as an optical component utilizing excellent optical properties of the organic-inorganic hybrid composition, especially as an optical component capable of transmitting light therethrough (so-called passive optical component) . Examples of optical functional devices provided with such an optical component include a variety of display devices (for example, liquid crystal displays, plasma displays) , a variety of projector devices (for example, OHP, liquid crystal projectors) , optical fiber communication devices (for example, optical waveguides, optical amplifiers) and imaging devices (for example, cameras, video cameras) .
Also, examples of the passive optical component to be used in an optical functional device include lenses, prisms, prism sheets, panels (plate-like articles), films, optical waveguides (for example, film forms, fiber forms) , optical discs and sealing materials of LED. If desired, such a passive optical component may be of a multilayered structure provided with an arbitrary coating layer such as arbitrary additional functional layers, for example, a protective layer for preventing mechanical damages on the coated surface due to friction or abrasion, a light absorbing layer for absorbing light beams of an undesired wavelength which become a cause for deteriorating the inorganic particle or base material or the like, a transmission-blocking layer for suppressing or preventing the transmission of a reactive low-molecular weight molecule such as water and an oxygen gas, an antiglare layer, an antireflection layer and a low-refractive index layer. Specific examples of such an arbitrary coating layer include a transparent conductive membrane or a gas barrier membrane composed of an inorganic oxide coating layer; and a gas barrier membrane or a hard coat composed of an organic material coating layer. As the coating method, there can be employed known coating methods such as a vacuum vapor deposition method, a CVD method, a sputtering method, a dip coating method and a spin coating method.
The optical component using the organic-inorganic hybrid composition of the invention is especially favorable for a lens base material. The lens base material manufactured using the organic-inorganic hybrid composition of the invention has high refraction properties, light transmission properties and lightweight properties and is excellent in optical properties. Also, by properly adjusting the type of the monomer constituting the organic-inorganic hybrid composition and the amount of the inorganic fine particle to be dispersed, it is possible to arbitrarily adjust the refractive index of the lens base material .
The "lens base material" as referred to in the invention refers to a single member capable of exhibiting a lens function. A membrane or a member can be provided on the surface or surroundings of the lens base material depending upon the use circumference or utilization of the lens. For example, a protective membrane, an antireflection membrane, a hard coat membrane and the like can be formed on the surface of the lens base material . Also, the surroundings of the lens base material can be put in and fixed to a base material holding frame or the like. However, such a membrane or frame is a member to be added to the lens base material as referred to in the invention and should be distinguished from the lens base material per se as referred to in the invention.
In utilizing the lens base material in the invention as a lens, the lens base material per se of the invention may be solely used as a lens, or as described previously, it may be added to a membrane or frame and then used as a lens. The type and shape of the lens using the lens base material of the invention is not particularly limited. The lens base material of the invention is used for, for example, spectacle lenses, optical instrument lenses, optoelectronic lenses, laser lenses, pickup lenses, vehicle-mounted camera lenses, mobile phone camera lenses, digital camera lenses, OHP lens, lenses for configuring a micro lens array.
EXAMPLES
The characteristics of the invention are hereunder described in more detail with reference to the following Examples. Materials, use amounts, proportions, treatment contents, treatment procedures and the like as shown in the following Examples can be properly changed. In consequence, it should not be construed that the scope of the invention is limitedly interpreted.
[Analysis and evaluation methods] (1) Observation by transmission electron microscope (TEM) :
The observation was carried out by "H-9000 UHR model transmission electron microscope", manufactured by Hitachi, Ltd. (accelerating voltage: 200 kV, degree of vacuum at the time of observation: about 7.6 x 10"9 Pa). (2) Measurement of light transmittance:
A sample to be measured was molded to prepare a substrate having a thickness of 1.0 mm, which was then measured for light transmittance by light at a wavelength of 589 nm using a spectrophotometer for ultraviolet and visible region (UV-3100, manufactured by Shimadzu Corporation) .
(3) Measurement of refractive index:
The measurement was carried out by light at a wavelength of 589 nm using an Abbe's refractometer (λΛDR-M4", manufactured by Atago Co., Ltd.). (4) Measurement of X-ray diffraction (XRD) spectrum:
The measurement was carried out at 230C using "RINT 1500", manufactured by Rigaku Corporation (X-ray source: copper Ka rays, wavelength: 1.5418 angstroms)
(5) Measurement of molecular weight: The measurement was carried out for number average molecular weight and weight average molecular weight using tetrahydrofuran as a solvent by a GPC analyzer using columns of "TSKgel GMHxL", "TSKgel G4000HxL" and "TSKgel G2000HxL" (all of which are manufactured by Tosoh Corporation) . The molecular weight was measured by differential refractometer detection and expressed as reduced into polystyrene.
[Preparation of fine particle dispersion] (1) Preparation of titanium oxide fine particle dispersion:
A dispersion of a titanium oxide fine particle was prepared in conformity with a method described in Synthesis
Example 9 of JP-A-2003-73559. The formation of an anatase type titanium oxide fine particle (number average particle size: about 5 nm) was confirmed by XRD and TEM. The fine particle had a refractive index of 2.5.
(2) Synthesis of zirconium oxide fine particle:
A zirconium oxychloride solution having a concentration of 50 g/L was neutralized with a 48% sodium hydroxide aqueous solution to obtain a zirconium hydrate suspension. This suspension was filtered and then washed with ion exchanged water to obtain a zirconium hydrate cake. This cake was adjusted with ion exchanged water as a solvent so as to have a concentration of 15% by mass as reduced into zirconium oxide, charged in an autoclave and then subjected to a hydrothermal treatment under a pressure of 150 atmospheres at 150 0C for 24 hours, thereby obtaining a zirconium oxide fine particle suspension. The formation of the zirconium oxide fine particle having a number average particle size of 5 nm was confirmed by TEM. The fine particle had a refractive index of 2.1.
(3) Preparation of zirconium oxide fine particle toluene dispersion:
The zirconium oxide fine particle suspension as synthesized in the foregoing (2) and a toluene solution having KAYAMER PM-21 (manufactured by Nippon Kayaku Co., Ltd.) dissolved therein were mixed, the mixture was stirred at 50 °C for 8 hours, and the toluene solution was extracted to prepare a zirconium oxide fine particle toluene dispersion. (4) Preparation of zirconium oxide dimethylacetamide dispersion:
500 g of N, N' -dimethylacetamide was added to 500 g of the zirconium oxide fine particle suspension (concentration: 15% by mass) as synthesized in the foregoing (2), the mixture was concentrated in vacuo to an extent of not more than about 500 g to achieve solvent substitution, and the concentration was then adjusted by the addition of N, N' -dimethylacetamide, thereby obtaining a 15% by mass zirconium oxide dimethylacetamide dispersion.
[Synthesis of thermoplastic resin]
(1) Synthesis of thermoplastic resin B-Il:
246.25 g of styrene, 3.75 g of β-carboxyethyl acrylate and 2.5 g of a polymerization initiator, V-601 (a trade name, manufactured by Wako Pure Chemical Industries, Ltd.) were dissolved in 107.1 g of ethyl acetate, and the solution was polymerized under nitrogen at 80 °C, thereby synthesizing a thermoplastic resin B-Il. As a result of the measurement by GPC, the resin was found to have a weight average molecular weight of 32,000. Also, as a result of the measurement by an Abbe's refractometer, the resin was found to have a refractive index of 1.59.
(2) Synthesis of thermoplastic resin B-10:
246.25 g of methyl methacrylate, 3.75 g of β-carboxyethyl acrylate and 2.5 g of a polymerization initiator, V-601 (a trade name, manufactured by Wako Pure Chemical Industries, Ltd. ) were dissolved in 107.1 g of ethyl acetate, and the solution was polymerized under nitrogen at 80 °C, thereby synthesizing a thermoplastic resin B-10. As a result of the measurement by GPC, the resin was found to have a weight average molecular weight of 35,000. Also, as a result of the measurement by an Abbe's refractometer, the resin was found to have a refractive index of 1.49. (3) Synthesis of thermoplastic resin P-8:
<Synthesis of living radical polymerization initiator A>
In a 200-mL three-necked flask equipped with a reflux condenser and a gas-introducing cock, 20 g (75.8 mmoles) of α,α' -dibromo-p-xylene and 70 mL of m-xylene were charged, and a solution of 16.8 g (80.7 mmoles) of triisopropyl phosphite dissolved in 20 mL of m-xylene was added dropwise under a nitrogen gas stream while heat refluxing. After completion of the dropwise addition, the reaction mixture was heat refluxed for 3 hours, and the solvent was distilled off. The residue was purified by silica gel column chromatography to obtain an initiator A in a percent yield of 53%.
Figure imgf000071_0001
<Synthesis of Illustrative Compound P-8> In a 200-mL three-necked flask equipped with a reflux condenser and a gas-introducing cock, 0.41 g (2.86 mmoles) of copper bromide, 42.7 g (0.407 moles) of styrene, 0.5 g (2.86 mmoles) of N, N, N' ,N' ,N"-pentamethyl diethylenetriamine and 1.0 g (2.86 mmoles) of the initiator A were charged, and after purging with nitrogen five times, the mixture was heated under a nitrogen gas stream at 80 0C for 5 hours. After returning to room temperature, 30 g of alumina and 50 mL of toluene were added, and the mixture was stirred for 10 minutes and subjected to celite filtration. The filtrate was thrown into a large amount of methanol to form a precipitate, and the precipitate was collected by filtration, washed with a large amount of methanol and then dried in vacuo at 600C for 3 hours. A percent yield was 38%.
In a 100-mL three-necked flask equipped with a gas-introducing cock, 10 g of the thus obtained polymer, 2.3 g (15 mmoles) of trimethylsilyl bromide and 40 mL of methylene chloride were charged, and the mixture was stirred under a nitrogen gas stream at room temperature for 24 hours. 10 mL of water was added, and after stirring for one hour, the resulting mixture was thrown into a large amount of methanol to form a precipitate. The precipitate was collected by filtration, washed with a large amount of methanol and then dried in vacuo at 60 0C for 3 hours. A percent yield was 97%
(number average molecular weight: 18,000, weight average molecular weight: 20,000). Also, as a result of the measurement by an Abbe's refractometer, the resin was found to have a refractive index of 1.59. (4) Synthesis of thermoplastic resin Q-I:
A mixed solution consisting of 2.1 g of tert-butyl acrylate, 0.72 g of tert-butyl 2-bromopropionate, 0.46 g of copper (I) bromide, 0.56 g of N, N, N' ,N' ,N", N"-pentamethyl diethylenetetramine and 9 mL of methyl ethyl ketone was prepared and purged with nitrogen. The resulting mixed solution was stirred at an oil bath temperature of 80 0C for one hour, and 136.2 g of styrene was added dropwise under a nitrogen gas stream. The mixture was stirred at an oil bath temperature of 900C for 16 hours, and after returning to room temperature, 100 mL of ethyl acetate and 30 g of alumina were added, followed by stirring for 30 minutes. This reaction solution was filtered, and the filtrate was added dropwise to an excess of methanol. A formed precipitate was collected by filtration, washed with methanol and then dried to obtain 61 g of a resin. This resin was dissolved in 300 mL of toluene, 6 g of p-toluenesulfonic acid monohydrate was added, and the mixture was heat refluxed for 3 hours. This reaction solution was added dropwise to an excess of methanol. A formed precipitate was collected by filtration, washed with methanol and then dried to obtain 55 g of a block copolymer Q-I. As a result of the measurement by GPC, the resin was found to have a number average molecular weight of 32', 000 and a weight average molecular weight of 35,000. Also, as a result of the measurement by an Abbe' s refractometer, the resin was found to have a refractive index of 1.59.
[Preparation of organic-inorganic hybrid composition and preparation of article (lens base material) ] [Example 1]
In the foregoing zirconium oxide dimethylacetamide dispersion, the thermoplastic resin B-Il, Compound PL-I and a surface treating agent (4-propylbenzoic acid) were added in a mass ratio of ZrO2 solid/B-ll/PL-l/4-propylbenzoic acid of 41.7/41.7/8.3/8.3, uniformly stirred and mixed, and the dimethylacetamide solvent was then concentrated in vacuo by heating. The concentration residue was heat compression molded in a die having a SUS-made surface (temperature: 1800C, pressure: 13.7 MPa, time: 2 minutes), thereby obtaining a article (lens base material) having a thickness of 1 mm.
[Examples 2 to 6 and Comparative Examples 1, 2 and 4]
Articles (lens base materials) of Examples 2 to 6 were obtained in the same manner as in Example 1, except that the thermoplastic resin in Example 1 and the compound represented by the formula (1) were replaced as shown in the following Table
3.
Articles (lens base materials) of Comparative Examples 1 and 2 were obtained in the same manner as in Example 1, except that in the methods of Examples 1 and 5, the compound represented by the formula (1) was not added.
A article (lens base material) of Comparative Example 4 was obtained in the same manner as in Example 2, except that in Example 2, di-2-ethylhexyl phthalate (DOP) was added in place of the compound represented by the formula (1) .
[Example 7 and Comparative Example 3] The foregoing titanium oxide dispersion was added dropwise to a chloroform solution having the thermoplastic resin P-8 and a surface treating agent (4-propybenzoic acid) dissolved therein at ordinary temperature over 5 minutes with stirring. Compound PL-I represented by the formula (1) was added and dissolved in the obtained mixed solution, and the solvent was then distilled off (TiC>2 solid/P-8/PL-l/4-propylbenzoic acid of 37/46.9/7.4/8.6) . The concentration residue was molded in the same manner as in Example 1 to obtain a article (lens base material) of Example 7.
A article (lens base material) of Comparative Example 3 was obtained in the same manner as in Example 1, except that in Example 7, the Compound PL-I represented by the formula (1) was not added.
[Example 8 and Comparative Example 5]
A article (lens base material) of Example 8 was obtained in the same manner as in Example 5, except that the temperature of the heat compression molding was 120 °C. A article of Comparative Example 5 was obtained in the same manner as in Comparative Example 2, except that the temperature of the heat compression molding was 120 0C.
[Test Example] With respect to the respective articles (lens base materials) as prepared in Examples 1 to 8 and Comparative Examples 1 to 5, an external appearance immediately after molding and an external appearance, a light transmittance and a refractive index after a lapse of 720 hours at room temperature n air at a humidity of 50% are shown in the following Table .
Figure imgf000075_0001
As is clear from Table 3, according to the invention, optical components having a refractive index of greater than 1.60 and having good transparency were obtained even after elapsing (Examples 1 to 8) . In Comparative Examples 1 to 3, a crack was generated in the article after elapsing so that the light transmittance and refractive index could not be measured. In Comparative Example 4, though the generation of a crack after elapsing was suppressed by the addition of a known plasticizer, the results revealed that the light transmittance and refractive index were inferior. In Comparative Example 5, only a white solid powder was obtained, but a transparent article could not be obtained.
It is noted from Table 3 that the organic-inorganic hybrid composition of the invention is suitable for manufacturing an optical component having good moldability and stability with time and having a high refractive index and good transparency even in a thick article of 1 mm.
Also, all of the material compositions of Examples 1 to 8 had a dielectric strength falling within the range of from -1.0 to 7.0 kV and a glass transition temperature falling within the range of from 100 to 400 °C and when kept at 250 °C for 2 hours, had a volatile component content of not more than 2% by mass and a percentage of saturated water absorption of 0.5% by mass. Also, it was confirmed that by using the organic-inorganic hybrid composition of the invention, a lens shape can be accurately formed with good productivity in conformity with the shape of a die such as a concave lens and a convex lens .
INDUSTRIAL APPLICABILITY
The organic-inorganic hybrid composition of the invention has excellent transparency and high refractive index and has excellent stability with time. Also, according to the invention, it is possible to arbitrarily control the refractive index. Furthermore, by using the organic-inorganic hybrid composition of the invention, it is easy to provide an optical component having good mechanical strength, heat resistance, weather resistance and moldability. In consequence, the invention is high in industrial applicability.
While the present invention has been described in detail and with reference to specific embodiments thereof, it will be apparent to one skilled in the art that various changes and modifications can be made therein without departing from the spirit and scope thereof.
The present disclosure relates to the subject matter contained in Japanese Patent Application No. 195490/2007 filed on July 27, 2007, which is expressly incorporated herein by reference in its entirety. All the publications referred to in the present specification are also expressly incorporated herein by reference in their entirety.
The foregoing description of preferred embodiments of the invention has been presented for purposes of illustration and description, and is not intended to be exhaustive or to limit the invention to the precise form disclosed. The description was selected to best explain the principles of the invention and their practical application to enable others skilled in the art to best utilize the invention in various embodiments and various modifications as are suited to the particular use contemplated. It is intended that the scope of the invention not be limited by the specification, but be defined claims set forth below.

Claims

1. An organic-inorganic hybrid composition comprising a compound represented by the following formula (1) and an inorganic fine particle:
Formula (1)
Figure imgf000078_0001
wherein R1 and R2 each independently represents a substituent; L represents an oxy group or a methylene group; a. represents 0 or 1; and ml and m.2 each independently represents an integer of from 0 to 5.
2. The organic-inorganic hybrid composition according to claim 1, wherein the compound is represented by any one of the following formulae (2) to (4) :
Formula (2)
Figure imgf000078_0002
Formula (3)
Figure imgf000078_0003
Formula (4)
Figure imgf000079_0001
wherein R3, R4, R5, R6 and R7 each independently represents a substituent; Z1, Z2, Z3 and Z4 each independently represents a hydrogen atom or a substituent; m3, m4 and mβ each independently represents an integer of from 0 to 4; m.5 andm7 each independently represents an integer of from 0 to 5; and bl, b2 and b3 each independently represents an integer of 2 or more.
3. The organic-inorganic hybrid composition according to claim 1, wherein the compound is represented by the following formula (5) :
Formula (5)
Figure imgf000079_0002
wherein Ra, Rb and Rc each independently represents a substituent; A1 represents an oxy group or a methylene group; A2 represents an oxy group, a substituted or unsubstituted alkylene group, a carbonyl group, a substituted or an unsubstituted imino group or a group composed of two or more members of these groups; nl and n2 each independently represents an integer of from 0 to 5; n3 represents an integer of from 0 to 4; and p, q and r_ each independently represents 0 or 1, provided that when q is 0, then £ is 0.
4. The organic-inorganic hybrid composition according to any one of claims 1 to 3, wherein the inorganic fine particle is a metal oxide fine particle having a refractive index of from
1 . 90 to 3 . 00 .
5. The organic-inorganic hybrid composition according to any one of claims 1 to 4, wherein the inorganic fine particle is a fine particle containing zirconium oxide, zinc oxide or titanium oxide.
6. The organic-inorganic hybrid composition according to any one of claims 1 to 5, wherein the inorganic fine particle has a number average particle size of from 1 to 15 nm.
7. The organic-inorganic hybrid composition according to any one of claims 1 to 6, wherein the inorganic fine particle is contained in an amount of 20% by mass or more.
8. The organic-inorganic hybrid composition according to any one of claims 1 to 7, wherein the compound represented by the formula (1) has a molecular weight of less than 1,000.
9. The organic-inorganic hybrid composition according to any one of claims 1 to 8, wherein a thermoplastic resin having a functional group capable of forming a chemical bond with the inorganic fine particle in a polymer end or side chain thereof is contained.
10. The organic-inorganic hybrid composition according to claim 9, wherein the thermoplastic resin is a thermoplastic resin having, in a side chain thereof, a functional group selected among the following groups:
Figure imgf000080_0001
, wherein R11, R12, R13 and R14 each independently 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 aryl group, -SO3H, -OSO3H, -CO2H and -Si (OR15)miR16 3-mi, wherein R15 and R16 each independently 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 aryl group; and ml represents an integer of from 1 to 3.
11. The organic-inorganic hybrid composition according to claim 10, wherein the functional group is contained in the number ranging from 0.1 to 20 in average per one polymer chain.
12. The organic-inorganic hybrid composition according to claims 10 or 11, wherein the thermoplastic resin is a copolymer containing a repeating unit formed from a monomer represented by the following formula (6):
Formula (6)
Figure imgf000081_0001
wherein R represents a hydrogen atom, a halogen atom or a methyl group; X represents a divalent connecting group selected among
-CO2-, -OCO-, -CONH-, -OCONH-, -OCOO-, -0-, -S-, -NH- and a substituted or unsubstituted arylene group; Y represents a divalent connecting group having from 1 to 30 carbon atoms; q represents an integer of from 0 to 18; and Z represents a 'functional group selected among the following groups:
Figure imgf000081_0002
wherein R11, R12, R13 and R14 each independently 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 aryl group,
-SO3H, -OSO3H, -CO2H and -Si (OR15)miR16 3_mi, wherein R15 and R16 each independently 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 aryl group; and ml represents an integer of from 1 to 3.
13. The organic-inorganic hybrid composition according to claim 9, wherein the thermoplastic resin is a thermoplastic resin having, in at least one polymer end thereof, a functional group selected among the following groups:
Figure imgf000082_0001
wherein R21, R22, R23 and R24 each independently 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 aryl group, -SO3H, -OSO3H, -CO2H and -Si (OR25)m2R263-m2, wherein R25 and R26 each independently 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 aryl group; and m2 represents an integer of from 1 to 3.
14. The organic-inorganic hybrid composition according to claim 9, wherein the thermoplastic resin is a block copolymer constituted of a hydrophobic segment and a hydrophilic segment.
15. An article obtained by forming the organic-inorganic hybrid composition of any one of claims 1 to
14.
16. The article according to claim 15, having a light transmittance as reduced in a thickness of 1 mm of 70% or more at a wavelength of 589 nin.
17. The article according to claim 15 or 16, having a refractive index of 1.60 or more at a wavelength of 589 ran.
18. The article according to any one of claims 15 to 17, having a maximum thickness of 0.1 mm or more.
19. An optical component comprising the article of any one of claims 15 to 18.
20. The optical component according to claim 19, which is a lens base material.
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