WO2009017180A1 - Composition hybride organique-inorganique et article et composant optique obtenus à partir de cette composition - Google Patents

Composition hybride organique-inorganique et article et composant optique obtenus à partir de cette composition 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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group
substituted
unsubstituted
organic
hybrid composition
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PCT/JP2008/063713
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English (en)
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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/fr

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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

L'invention concerne une composition hybride organique-inorganique comprenant un composé représenté par la formule suivante (1) et une particule fine inorganique : dans cette formule R1 et R2 représentent un substituant, L représente un groupe oxy ou un groupe méthylène, a représente 0 ou 1, et m1 et m2 représentent 0 à 5.
PCT/JP2008/063713 2007-07-27 2008-07-24 Composition hybride organique-inorganique et article et composant optique obtenus à partir de cette composition WO2009017180A1 (fr)

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WO1991008241A1 (fr) * 1989-11-27 1991-06-13 Virginia Tech Intellectual Properties, Inc. Materiau hybride en ceramique/polymere a indice de refraction eleve
US5413988A (en) * 1993-04-16 1995-05-09 International Superconductivity Technology Center Method for manufacturing an oxide superconductor thin film and a target for use in the method
US20040044127A1 (en) * 2002-08-22 2004-03-04 Konica Corporation Organic-inorganic hybrid film, its manufacturing method, optical film, and polarizing film
WO2006028200A1 (fr) * 2004-09-09 2006-03-16 Mitsubishi Rayon Co., Ltd. Composition contenant une nanosubstance, procede de fabrication de ladite composition et composite realise avec ladite composition

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US6599631B2 (en) * 2001-01-26 2003-07-29 Nanogram Corporation Polymer-inorganic particle composites
JP2005146116A (ja) * 2003-11-14 2005-06-09 Nippon Zeon Co Ltd 樹脂組成物、光学材料および光学フィルム
JP2009520077A (ja) * 2005-12-15 2009-05-21 キャボット コーポレイション 透明ポリマー複合材料

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Publication number Priority date Publication date Assignee Title
WO1991008241A1 (fr) * 1989-11-27 1991-06-13 Virginia Tech Intellectual Properties, Inc. Materiau hybride en ceramique/polymere a indice de refraction eleve
US5413988A (en) * 1993-04-16 1995-05-09 International Superconductivity Technology Center Method for manufacturing an oxide superconductor thin film and a target for use in the method
US20040044127A1 (en) * 2002-08-22 2004-03-04 Konica Corporation Organic-inorganic hybrid film, its manufacturing method, optical film, and polarizing film
WO2006028200A1 (fr) * 2004-09-09 2006-03-16 Mitsubishi Rayon Co., Ltd. Composition contenant une nanosubstance, procede de fabrication de ladite composition et composite realise avec ladite composition
US20080281014A1 (en) * 2004-09-09 2008-11-13 Mitsubishi Rayon Co., Ltd. Nanosubstance-Containing Composition, Process for Producing the Same, and Composite Made With the Same

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