TW200946584A - Organic-inorganic hybrid composition, transparent molding, optical component and lens - Google Patents

Abstract

An organic-inorganic hybrid composition comprising inorganic fine particles and a thermoplastic resin, wherein the thermoplastic resin has a structure in which a functional group capable of forming a chemical bond with the inorganic fine particles bonds to a main chain of the resin via a linking chain having a chain length of 4 or more atoms.

Description

200946584 30786pif.doc VI. Description of the invention: [Technical field to which the invention pertains] The present invention relates to an organic-inorganic hybrid composition having high refractive properties, high transparency, light grading properties and processability characteristics, And an optical element produced by the above-described organic-inorganic hybrid composition, wherein an optical element such as S is used for a mirror on a pair of glasses, a lens for an optical instrument, a lens for optoelectronics, a lens for a laser, and a head for a head. For lenses and car cameras, lenses, camcorders for portable cameras, lenses for digital cameras, over head projectors (OHP), and lenses for microlens arrays. [Prior Art] Compared with glass, resin has a large advantage because of its light weight, impact resistance, plasticity, and low cost. Recently, in the art of optical elements such as lenses, there has been a tendency to replace glass with a resin material to produce a lens, which is mainly achieved by means of improving the refractive index and light transmittance of the resin. 〇s know that there are quite a lot of methods for molding the resin, for example, injection molding (injection _d=g meth〇d) and extrusion molding (extnjsi〇n let 叩 (4) and the molding of the molten resin into the mold (CaSting) Compression molding method (compressi〇nm〇lding meth〇d), etc. However, in various methods of C, the fluidity of the resin (fl〇%) is usually asked by the above-mentioned 'in order to make the resin replace the glass, A material has been developed which has finely distributed inorganic nanoparticles in the crucible to increase the refractive index and heat resistance of the resin. For the case of cattle, refer to Japanese patents. Jp_A 2〇〇7_238929, 邛 and 3 200946584, 士.doc 2003-73564 iu m td a 地太半" and A 61_73754). However, the addition of helmet rice particles to the resin may make the resin material flow poor. In order to improve the fluidity of the resin material itself, the general practice is to reduce the molecular weight of the resin in the tree, or to reduce the molecular weight of the resin. However, these methods generally reduce the heat resistance of the resin. Sex and machinery The nature, because, can overcome the above problems, and develop a material with high glass transition temperature (g), high molecular weight and still have good fluidity, which is one of the problems to be overcome in the development of resin materials. A method for preparing a transparent mixed composition is also disclosed in which an organic-inorganic hybrid composition is melted and extruded under a high monthly b of not more than 100 MJ/m3 (refer to Japanese Patent Application (10) 6_13173 [Invention] y Under the condition of energy kneading, it is necessary to obtain high-quality optical components because the resin will degrade under the heat of shearing, so discoloration or miscellaneous problems may occur. As described above, how to overcome the above problems has developed high and good light transmission. The organic-inorganic hybrid group with excellent fluidity is one of the problems to be overcome in the development of resin materials. The present invention has been made in view of the above circumstances, and the object of the present invention is to provide an organic-inorganic hybrid domain. Has a high refractive index, good light transmittance ^ and excellent flowability' and the organic-inorganic hybrid composition is granulated at a small kneading energy The inventors of the invention have revealed that the organic-inorganic mixed composition, the high-folding ratio, the high-light (four) rate, and the distribution of the inorganic particles are all in 200946584 _?u / owjjif.doc (for example, See Patent 1), after which the inventors further studied the fluidity improvement technique of the above composition. The inventors have found that when the organic-inorganic hybrid composition uses a thermoplastic resin having a special structure, the fluidity of the composition is The invention can be significantly improved without being affected by other factors, and the present invention is completed as follows. An organic-inorganic hybrid composition comprising a plurality of inorganic fine particles and a thermoplastic resin having a structure in which a functional group capable of forming a chemical bond with the inorganic fine particles is bonded to the main chain of the thermoplastic tree Connected, and the chain length of the linker is greater than or equal to 4 atoms. [2] The functional group capable of forming a chemical bond with the inorganic fine particles in [1] is linked to the main chain of the resin structure by a linking chain, and the chain length of the linking chain is larger than 戍 to be equal to 5 atoms. [3] The functional group in [2] is selected from the group consisting of: 〇Rt1 OR1^—P-OR12—CHP-OR14 ο δ 〇 where RH, R12, R13 and R]4 may each represent a hydrogen atom, a substitution or Unsubstituted alkyl group, substituted or unsubstituted alkenyl group, substituted or unsubstituted alkynyl gr〇up, substituted or unsubstituted aryl group or capable of An atom or a group forming a salt; -S03H or a salt thereof, -〇S〇3H or a salt thereof, _c〇2H or a salt thereof or -Si(OR15)m]R]63-ml 'where r 〖5 and r]6 each independently represent a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted galenyl group, a substituted or unsubstituted alkynyl group, a substituted or unsubstituted aryl group or an atom capable of forming a salt. Or a group; and ml represents an integer from 1 to 3. Doc 200946584 [4] The thermoplastic resin in any of [1] to [3] has a structural unit represented by the formula (1): Formula (1)

R —*0 -W.

Z 〇 where R represents hydrogen, (iv) atom or methyl; w represents _〇_, -CO-, -NH-, -S~CS_, substituted or unsubstituted stilbene base her group group) The group of the silk-like wire (4) coffee gnmp) is selected from one or more groups of chains having a chain length greater than or equal to 4 atoms; and 2 is a function capable of linking with inorganic particles. The thermoplastic resin in any one of [1] to [3] has a structural unit 兀, which is represented by the formula: (7)

R

-C 〇J\. ❹

V 0 wherein R represents a hydrogen atom, a halogen atom or a fluorenyl group; and L represents a group consisting of -〇-, _CX>, _NH~'-S· ' _CS_, a substituted or unsubstituted alkylene group, and a substituted or unsubstituted aryl group. A group consisting of a group of more than one group of more than one atom is a linking group of two or more atoms. [6] Each polymerization of the thermoplastic resin in any of [1] to [5] 6 200946584 3U/8〇pif.d〇c The chain contains an average functional group content of 0.1 to 20. [7] The thermoplastic resin in any one of [1] to [6] has a Weight Average Molecular Weight (Mw) of 50,000 or more. [8] The inorganic fine particles in any one of [1] to [7] have an average particle diameter of from i to 20 nm. [9] The inorganic fine particles in any one of [1] to [8] include zirconmm 0Xlde, tin oxide, zinc oxide or titanium oxide. [10] The organic-inorganic hybrid composition in any one of [1] to [9] having a light transmittance of greater than or equal to 7 Å/0 at a thickness of 1 cm and a wavelength of 589 nm. [11] The refractive index of the organic-inorganic hybrid composition in any one of [1] to [10] is greater than or equal to 16 Å. [12] A transparent molded article having an organic-inorganic hybrid composition of any of [^ to ^^. The inter-optical optical element 'has any of the organic-inorganic hybrid compositions between _. [14] A lens having any of the inorganic mixed compositions of (1) to Π1]. The present invention (4)-inorganic hybrid group has a high refractive index and a good light transmittance, and can be kneaded under a small energy condition. The organic-inorganic hybrid composition of the present invention is easy to mold and is compatible with the manufacture of optical quality optical elements and lenses. TIAN, 丄 doc 200946584 [Embodiment] The organic-inorganic hybrid composition of the present invention is further described. The constituent elements described in the examples are in accordance with the invention: they are not intended to limit the invention. In the following description, the numerical range of the first two as the lower limit falls between [organic-inorganic age composition] and the post-value as the upper limit. The organic species includes a plurality of inorganic fine particles and a thermoplastic resin by a main chain linkage of a functional group capable of forming a chemical bond with the inorganic fine particles, and a chain length of the linked chain is suitable for the production of the present invention. The organic-inorganic hybrid composition has an equivalent content;;,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,, Refraction = 2 - The inorganic mixed composition is preferably at a wavelength of 589 nm, preferably at 1.70. Preferably, it is preferable to mix the composition at a thickness of 1 cm and a wavelength greater than or equal to 7 G% by more than or equal to 589 Si. It is more than or equal to 80 °/. For better. In addition to the 200946584 ju/oopif.doc, the mixed composition is preferably greater than or equal to _ at a thickness of i mm and a wavelength of 4 〇 5 ♦ m, and the towel is greater than the scale at 65% = 仏, and greater than or equal to 70% is better. When the composition is mixed = cm and the wavelength is 589 nm, the light transmittance is greater than or equal to qing. Thereafter, a lens substrate having better characteristics can be obtained. Further, in the present invention, the green transmittance at = ❹ ❹ = 11 cm was measured in the following manner. : The organic-inorganic hybrid composition was just formed to prepare a thick-thickness material, and then was measured by ultraviolet-visible mass spectrometry (UV-3100, “Mr. Co., Ltd.”) to obtain the county permeability value. The glass transition overflow (Tg) of the composition without it is better, wherein 9 (TC to 38 (rc is preferred). When the temperature is greater than or equal to 8 存在, it is easy to obtain sufficient heat resistance, and when the glass transition temperature is broken When it is less than or equal to 4 〇〇, there is a tendency to be easily produced. The main constituents of the organic-inorganic hybrid composition of the present invention are as follows: inorganic fine particles and thermoplastic resin. Further, the present invention has inorganic The mixed composition may further contain additives such as other resins, dispersants, addition or release agents which do not meet the limitations of the month of J. [Thermoplastic resin] 妩, the inventive thermoplastic resin has a structure, and this structure The functional group capable of forming a chemical bond with no i: ^ ^ is bonded to the thermoplastic resin by a linking chain, and the chain length of the linking bond is greater than or equal to 4 atoms. (Basic Structure of Thermoplastic Resin) The present invention is not particularly Defining a basic structure of the thermoplastic resin, the traditional 200946584,

-/v/ / w/|^ii«QOC

The resin structure is, for example, poly(meth)acrylic acid ester, polystyrene (polyester carbazole), polyvinyl carbazole, polylactic acid (P〇lyester), polyaryl vinegar. (polyary丨ate), polycarbonate, polyurethane, polyimide, polyether, p〇iyether sulfone, polyether ketone, and poly Sulfur-(p〇iythi〇ether) can be used in the present invention, wherein vinyl polymer, polyacrylate and aryl-containing polycarbonate are preferred, and ethyl ester is extended. A polymer is preferred. (Function group capable of chemically bonding with inorganic fine particles) The functional group capable of chemically bonding with inorganic fine particles means a functional group which is chemically bonded to the inorganic fine particles in the thermoplastic oxime of the present invention.所谓 The so-called chemical bonds here include covalent bonds, ionic bonds, coordination bonds, and hydrogen bonds. When there is more than one functional group present, there may be more than one chemical bond with inorganic fine particles. Whether the chemical bond can be formed depends on whether or not the functional group of the thermoplastic resin can form a chemical bond with the inorganic fine particles mixed in the organic solvent towel, as exemplified below. In the organic-inorganic hybrid composition of the present invention, all of the functional groups of the thermal recording resin can form a chemical _' (four) part of the functional group to form a chemical bond with the domain particles. The team stably disperses into the _ resin by forming chemical bonds with the inorganic particles. The base forms the chemical particles into the chemical particles, as long as it can react with the inorganic micro 10 Ο.

G 200946584 JU/oupif.doc 9n11

P-ORt2 CHP-ORW ° O wherein R11, R12, R13 are further substituted, == (d), substituted or substituted: ==: substituted alkynyl, substituted or unsubstituted aryl: undecided Atom or group: Na or its salt, gamma 4 salt RT/it^^^" 'Si(〇R15)miRi^^5 Ris ^ can each represent a gas atom, a substituted 3 unsubstituted thin base a substituted or unsubstituted filament or a substituted radical or an atom or a group capable of forming a salt; and as = an integer of Tables 1 to 3. ^下下| R1, Rl2, Rl3, R] 4, Rl5j^R〗 6___ The alkyl group is preferably 1 to 30 carbon atoms, preferably 丨 to 2 〇 carbon atoms: for example, methyl, Ethyl and n-propyl. The substituted filaments include the Fangyuan base. Fang. The base is preferably from 7 to 30 carbon atoms, more preferably from 7 to 20 carbon atoms, such as benzylgr〇up and p-methoxybenzyl group. The alkenyl group is preferably 2 to 30 carbon atoms, more preferably 2 to 20 carbon atoms, such as a vinyl group and a 2-phenylethynyl group. The alkynyl group is preferably 2 to 20 carbon atoms, more preferably 2 to 10 carbon atoms, such as an ethynyl group and a 2-phenylethynyl group. The aryl group is preferably 6 to 3 carbon atoms, and preferably 6 to 20 carbon atoms 'e.g., phenyl group, 2,4,6-tribromophenyl (2,4,6-tribrom〇) Phenyl group) and 1-naphthyl gr0Up 11 200946584, . Here, the group of oxime includes a heterocyclic aryl group (heter〇ajy) gr〇Up). In addition to the aforementioned alkyl, alkenyl, alkynyl and aryl groups, the substituent of these alkyl, alkenyl, alkynyl or aryl groups is, for example, a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom). Alkoxy (alk〇xy) (eg methoxy and ethoxy). Ru, R12, R13, rH, Rl5 and rI6 are preferably a hydrogen atom or a calcined group, and more preferably a hydrogen atom. m is preferably 3. Among the above functional groups, preferred are OR11 〇Ri3 P~ORt2 — ◎ Ο C〇2H or a salt thereof or SOsH or a salt thereof, -〇s〇3h or a salt thereof, & is -Si( OR15) mlR163_ml. More preferably, it is 9R11 OR13 ο f'OR〇^ORi4 and -C02H or its salts. 〇There is no specific method for introducing a functional group into a hotline. It is possible to copolymerize a monomer having a functional group or a single functional group. After the body filament, the precursor portion is converted into a functional group by a method such as hydrolysis. Alternatively, a resin having a precursor of a reaction zone such as a trans group, an amine group or an aromatic ring may be formed, and then the region 33 = region. Further, a monomer having a functional group is copolymerized by a month b (a structural unit of a thermoplastic resin) 12 200946584 3UV80pif.doc, the thermoplastic resin of the present invention has a granule opening > a chemically bonded functional singer T, this /, inorganic micro, and the bond of the chain of the long-chain fat in the main chain of the thermoplastic resin has a common atom. Preferably, the functional group bonded in the prior art is attached to the main chain of the resin by a linking chain in which a chemical chain can be formed with the inorganic particles, and the chain length of the linking bond is greater than or equal to 5 ± difficult It is preferred that the connection is equal to 100 atoms, and the chain length of the 1 (tetra) chain is less than ❹ ❹ , and the wavelength of less than or equal to 20 atoms is more preferably the atom, in the preparation of the Μ ... 为good. § Chain length greater than or equal to 4 Particles can be improved in small kneading energy:: homogenous: mixed composition, inorganic 'and thus the above organic two = 1 is uniformly (four) dispersed into the thermoplastic tree. ..., /tb σ composition light energy transmission properties to obtain structural units, the resin is preferably - structural unit, and the formula (1) η z \ in the formula (1), R represents a gas - which A hydrogen atom or a methyl group is preferred. a functional group bonded to an inorganic particle by a filament or a monomethyl group, wherein Z is in the group of the above-mentioned muco... muscle, |, _cs_, substituted or unsubstituted or unsubstituted aryl group Group selection a 13 .丄doc 200946584 _ _ 峨 峨 峨 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 To 5 is better. For example, the excipients include sub-, ex-ethylene, propyl, butyl, and pentyl. The number of carbon atoms in the aryl group is preferably from 6 to 20, more preferably from 6 to 6, and from 6 to 1 Å. In this case, work _ ^ Wang η horse and naphthylene. Nujia. For example, the green color includes the extension of the phenyl group. Both the base and the extended aryl group may have substituents. For example, a substituted beauty may be a (iv) atom (eg, a fluorine atom, a chlorine atom, a desert atom, and a hard atom), a base (=methyl, ethyl), an aryl (eg, phenyl, naphthyl), a banyl group. , a thiol group, an aerobic acid group (such as a methoxy group), an aryloxy county (such as the present oxygen), a substituted or unsubstituted amine carbenyl group (such as a urethane group, N-aniline formazan) a hydrazinyl group, a decyl group (for example, an ethoxy group), an aryl group (for example, a benzoyl group), a decyl group, a decylamino group (for example, an acetamino group, a Oxycarbonylamino), sulfonylamino (eg, methanesulfonyl), quinone (for example, amber imino, phthalimido), imine, such as benzylidene , alkoxy (e.g., methoxy), aryloxy (e.g., phenyl, yl), decyloxy (e.g., methoxy), alkyl sulfonyloxy (e.g., sulfonyloxy), aromatic A sulfonyloxy group (e.g., phenylsulfonyloxy), a sulfo group, a substituted or unsubstituted amine sulfonyl group (e.g., an amine sulfonyl group, an N-thinylsulfonyl group), an alkylthio group (e.g., a methylthio group) ), arylthio (eg phenylthio), Item acyl group (e.g., Yue% with group), an aryl group continued acyl (e.g. phenyl determined acyl), heterocycles and the like. The aforementioned substituent may be substituted with the above substituent. 14 200946584

And the substituted or unsubstituted Shenfang w can be #白合敌冲土土 &,,, and replace the aryl group, the child. W may be a group having a bond length greater than or equal to 4 > 2 or more groups selected from the group consisting of: -, -CS-, substituted or unsubstituted exudyl groups. The structure including two groups is, for example, seven c〇_, _nhco • CONH-, -SCS-, -CSS--〇-extension, -CO-alkylene, -NH-

Base, extension ^ ' base - extension yard base, which is better with _〇C〇^_c〇〇_. The structure including the three groups is, for example, 〇〇〇 伸 _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ Anthracenyl, -oco-exoaryl, -coo.aryl, _NHC0 aryl, •CONH-exoaryl, -SCS-exoaryl, _CSS-extended aryl, alkyl-hydrazine-stretch Base, extended alkyl-CO-alkylene, alkylene *_NH_alkylene, alkylene O _S_alkylene, alkyl-CS-alkylene, alkyl _ 〇 _ aryl , alkyl-CO_ extended aryl, alkyl _NH_ extended aryl, alkyl-S- extended aryl, extended alkyl-CS-extended aryl, alkyl-arylene-extension Alkyl, aryl-aryl-alkylene, aryl-CO-alkylene, aryl-NH alkyl, aryl-s-alkyl, aryl-CS-alkyl , aryl group _cm aryl, aryl 〇 伸 aryl, aryl _ ΝΗ · aryl, aryl _ s _ aryl, aryl _CS - aryl and stretching An aryl-alkylene-aryl group, wherein an -OCO-alkylene group and a -COO-alkylene group are preferred. • doc 200946584 The group bonded to z is preferably an extended or extended aryl group, wherein == is =. The group bonded to the main chain is preferably a - or aryl group, and 1 = is further - 〇) 0 or a phenyl group is preferred. The preferred range of chain length is such that the unit plastic resin preferably has a structural unit, and the structural formula (7) ^CH2-C-^― 0 ❹

L 0H

V In the formula (2), R represents a hydrogen atom, and all of the above are preferred. A self-priming atom or a fluorenyl group, L represents a chain consisting of -〇-, -CO-,., and a substituted or unsubstituted, substituted or unsubstituted or more than one group:: = group selection of the group - the group. For example, connect the atoms of the atom to the exposed person in the formula (1). The chain length of L is === sub' and is preferably greater than or equal to 3 atoms. One is preferably equal to or equal to 100 atoms, and is less than ', the number of children is preferably less, and less than or equal to 20 atoms is more. It is preferred that the 4G atoms are structural unit repeats of the structural unit of the thermoplastic resin. These repeated uppers (12 or (2) are represented by the combination of the formula (1) and the closed ethylene monomer. == 16 200946584 , ~j\jt 〇vj-/ii.cioc The following formula (Γ) Or formula (2,) as a representative: formula (Γ)

R CH〇=C I W

Z ❹ In the formula (Γ), R represents a hydrogen atom, a dentate atom or a monomethyl group. W represents a chain length consisting of _〇_, _Ca, 顾...s_, _cs_, substituted two, and substituted filaments, or four or more bases, greater than or equal to 4:= base. Z represents a functional group which can be bonded to the inorganic fine particles. ', 卞 & connection (2,)

R ch2=o □ V In the formula (2,), R represents a hydrogen atom and a tooth. :L stands for -0_, -CO-, -NH-. — 卞$-monomethyl-s-'-CS-alkylene and substituted or unsubstituted extended aryl group substituted or more than one group consisting of a chain length greater than or equal to 矸-selective group. The connection of the formula (1,) or the formula (2,) will not be used to limit the present invention. &Examples 17 200946584 W-l W-3 W-5 W-7 W-9 W-ll W-13 W-l 5 W-17

W-2 W-4 W-6 W-8 W-10

o

o

W-14 —ΎΗ W-l 6 , s,

o O

/-18 o v〇ip^2 W-19 -20 〇-p〇pH)a W-21 W-22

18 200946584 ^u/6〇pif,doc

(Synthesis of Thermoplastic Resin) The thermoplastic resin in the present invention may be obtained by copolymerization of a monomer represented by the formula (2) or the like and other copolymerizable monomers. The copolymerizable monomer described herein may be a monomer described in Polymer Handbook, V 2nd Edition 'J. Brandrup, Wiley Interscience (1975), Chapter 2, pages 1-483. In particular, a compound having an addition polymerizable unsaturated bond selected from the group consisting of a styrene derivative, anthracene-vinylnaphthalene, and 2-vinylnaphthalene can be exemplified. ), vinylcarbazole, acrylate, methacrylate, acrylamide, mercapto acrylamide, allyl compound, vinyl ether, vinyl ester, dialkyl itaconates And one of fumaric ❹ acid, dialkyl esters or monoalkyl esters, and suitable compounds thereof. Examples of the styrene derivative include styrene, 2,4,6-tribromostyrene, and 2-phenylstyrene. Examples of the acrylate include decyl acrylate, ethyl acrylate, propyl acrylate, n-butyl acrylate, tert-butyl acrylate, chloroethyl acrylate, 2-ethylidene acrylate, trimethylol propyl monoacrylate , benzyl acrylate, methoxy benzyl acetate, furfuryl acrylate and tetrahydrofurfuryl acrylate. 19 200946584 , v. — ^^.r.doc Examples of methacrylates include methyl methacrylate, ethyl methacrylate, propyl methacrylate, n-butyl methacrylate, and methacrylic acid Ester, chloroethyl methacrylate, 2-hydroxyethyl methacrylate, trimethylolpropane monodecyl acrylate, benzyl methacrylate, methoxypropyl methacrylate, methacrylic acid bite Benzoyl ester and tetrahydrofuran methyl methacrylate. Examples of the acrylamide include acrylamide, hydrazine-alkyl acrylamide (the alkyl group is an alkyl group having 1 to 3 carbon atoms, such as methyl, ethyl, propyl), hydrazine, hydrazine-di Alkyl acrylamide (the alkyl group is an alkyl group having 1 to 6 carbon atoms), hydrazine-hydroxyethyl-hydrazine-methacrylamide and Ν-2-acetamidoethyl- Ν-B-based acrylonitrile. Examples of the methacrylamide include mercapto acrylamide, fluorenyl-alkylmercapto acrylamide (the alkyl group is an alkyl group having 1 to 3 carbon atoms, such as methyl, ethyl, propyl) , hydrazine, hydrazine-dialkyl methacrylamide (the alkyl group is an alkyl group having 1 to 6 carbon atoms), ν-hydroxyethyl-fluorenyl-fluorenyl decyl acrylamide, and hydrazine-2 - Ethylaminoethylethylmercaptopropenylamine. Examples of the allyl compound include allyl esters (e.g., allyl acetate, allyl caproate, auyi caprate, allyl laurate, palmitic acid) Alllpaimitate, allyl stearate, aUyl benz〇ate, allyl acetoacetate, allyl lactate (9) not lactate) And propyl propyl ether (aiiyi 〇Xyethan〇i). Examples of the vinyl ether include an alkyl vinyl ether (the alkyl group is an alkyl group having from 10 to 10 carbon atoms), for example, hexyl vinyl ether, octylethylene 20 200946584 3U/«bpxf.doc ether, Mercapto vinyl ether, ethylhexyl vinyl ether, decyloxyethyl vinyl ether, ethoxyethyl vinyl ether, gas ethyl vinyl ether, 1_mercapto-2,2-dimethyl Propyl vinyl ether, 2-ethylbutyl vinyl ether, hydroxyethyl ethyl ruthenium, - ethyl ethene, dimethyl amino ethyl ether, diethyl amine Ethyl vinyl ether, butylaminoethyl vinyl ether, benzyl vinyl ether and tetrahydrofuran. Examples of the vinyl ester include vinyl butyrate, vinyl isobutyrate, trimethyl methacrylate, S, diethyl acetate, vinyl valerate, vinyl hexanoate, vinyl acetate, dichloroacetic acid. Vinyl ester, decyloxyvinyl acetate, butoxy vinyl acetate, vinyl lactate, vinyl butyl p-phenyl ester and vinyl cyclohexyl decanoate. Examples of the dialkyl itaconate include dimethyl itaconate, diethyl itaconate, and dibutyl itaconate. Examples of the dialkyl or monoalkyl fumarate include dibutyl fumarate. Further, crotonic acid, itaconic acid, acrylonitrile, mercapto acrylonitrile, and maleimonitrile are exemplified. The thermoplastic resin (dispersible polymer) used in the present invention preferably has a weight average molecular weight of 40,000 to 500,000, and more preferably 50,000 to 300,000, more preferably 50,000 to 150,000. Since the weight average molecular weight of the thermoplastic resin is less than 500,000, the workability of the resin is increased. Further, the thermoplastic resin has a weight average molecular weight of more than 〇〇〇, so that the organic-inorganic hybrid composition has sufficient mechanical strength. The "weight average molecular weight" used herein is a column having colloidal permeation chromatography according to polystyrene conversion using Tosoh Corporation's products TSK gel GMHxL, 21 200946584 doc TSK gel G4000HXL, and TSK gel G2000HXL. The molecular weight of the instrument (GPC) differential refractometer (solvent: hydroquinone). In the thermoplastic resin of the present invention, the average functional group of each polymer chain having a bond to the inorganic fine particles is preferably 〇1 to 2 ,, and more preferably 0.5 to 1 Torr, especially 丨 to 5 is especially good. When the content of the functional group of each polymer chain is 2 Å or less on average, a plurality of inorganic fine particles are coordinated, and there is a tendency to easily prevent an increase in viscosity in a solution state and a gel generation. In addition, when each of the polymer chains is official. When J or more, the thermoplastic resin which is easy to stabilize the inorganic particles has a glass transition temperature (Tg) f C to 働 C, and is preferably 13 (TC to 38 (TC is more preferable. When it is difficult to transfer the temperature of the higher surface, (10) is obtained. In addition, when a resin having a glass of 4° or less is used, there is a tendency to facilitate processing. Large; and the number of particles that can exist in the difference between the four (4) _ 2tmarng), so the composite has _ overmolding ware: this: the thermoplastic tree wax in the Ming Dynasty has good refraction, and greater than or equal to 15 The above-mentioned refractive index is obtained at a temperature of 22 200946584 jv / o^pif.doc with a thickness of 1 mm at a wavelength of 589 nm. Preferably, the thermoplastic skin has a light transmittance of greater than or equal to 80% and is preferably greater than or equal to 85%, and more preferably greater than or equal to 88%. (Illustration of Thermoplastic Resin) Hereinafter, preferred embodiments of the thermoplastic resin of the present invention will be described, but the thermoplastic resin of the present invention is not Preferred examples of these. ❹ 23 200946584 doc

Quantity average molecular weight (Μη) a/b (weight ratio) 45000 55000 80000 80000 80000 320000 99/1 〇 99/1 99/1 96/4 94/6 ❹ 99/1 24 200946584 JU/»t>pii.doc

Quantity average molecular weight (Μη) a/b (weight ratio) 85000 80000 80000 80000 98000 80000 99/1 99/1 98/2 98/2 98/2 98/2 25 200946584 r.doc CH2-* 聚合物 Polymer

X number average molecular weight (Μη) a/b (weight ratio) P-13 P-14

Ρ〇{〇Η)2 75000 80000 99/2 99/1 6 P-15 •CRrCH- 〇 0 80000 98/2 P-16 fb -CHj—C— P0{0H)2 80000 99/1

O CHa H〇aS. P-17

98000 P-18 OCH, 0 y° 丨N/X/^SiiOCH^ 80000 98/1 〇 98/2 26 200946584 /oopif.doc

Quantity average molecular weight (Μη) a/b (weight ratio) P-19

〒H3 -oh2 one c- 75000 98/2

P-20 80000 98/2 o P-21 P-22

O

80000 60000 98/2 98/2 Potential CH, P-23

P-24 0译 CE- Ϊ F 0V°v^〇^ll^s/v〇~P〇(〇H)j 50000 99/1 0 42000 99/1 P-25

80000 98/2 27 200946584 t.doc P-26 P-27 P-28 P-29 P-30 P-31

x/y/2F=88/10/2 (weight ratio) Number average molecular weight=200000 x/yz-88/10/2 (weight ratio) Number average molecular weight=80000 x/y/z=88/10/2 ( Weight ratio) number average molecular weight = 80000 x / y / z = 88/10/2 (weight ratio) number average molecular weight = 80000

x/y/z=87/10/3 (weight ratio) number average molecular weight=120000 x/y/z=88/10/2 (weight ratio) number average molecular weight=80000

28 200946584 j\j / oupif.doc P-32 P-33 P-34

a/b=98/2 (weight ratio) number average molecular weight=200000 x/y/z=50/48/2 (weight ratio) number average molecular weight=80000 x/y/z=42.8/55.0/2.2 (weight ratio) ) Quantity average molecular weight = 50000 P-35 P-36

x/y/z = 42.9/55.2/1.9 (weight ratio) Number average molecular weight = 50000 x / y / z = 42 / l . 7 / 56.3 (weight ratio) Number average molecular weight = 50000 P-37

T〇f〇4t W<S〇jNi MHMM p/q/r/s/t=33.52/29.6/15.23/2 0.42/1.23 (weight ratio) number average molecular weight=50000 [inorganic particles] " The inorganic fine particles used include, but are not limited to, oxidized fine particles, zinc oxide fine particles, titanium oxide fine particles, tin oxide fine particles, and zinc sulfide micro: second, metal oxide fine particles are preferred. Among the metal oxide fine particles, a group consisting of zinc oxide, tin oxide, and oxidized lanthanum is preferred, and is selected from the group consisting of oxidized oxidized, zinc oxide, and titanium oxide 29 Λ.άοο 200946584. Anyone is better, especially yttrium oxide particles with good light transmittance and low photocatalytic activity are the best = medium, from the point of view of refractive index, light penetration and stability, these may also be used A composite of inorganic materials. In addition, these micro-classes are classified as Class 1 elements, or in the wire bonds, or in the case of samarium coupling agents, titanium or the like. Xiao is called _ mixture agent t invention is not __ method of manufacturing inorganic particles, any 〇 = can = water:: library can use metal _ or gold as particles. The reaction money is hydrolyzed to obtain the desired oxide micro method. For example, Dream 22: f 5 obtains a sputum floating solution of oxidized astration particles or a suspension thereof; I: a method in which water is dispersed in a solvent to obtain an oxidized suspension; hydrolyzed aqueous solution to obtain oxidative displacing and then It is subjected to a super solution to obtain a wrong suspension of an oxidized suspension suspension; ^1'4 is obtained by hydrolyzing a wrong alkoxide to obtain an aqueous solution of an oxidized salt to #彳1 9 from a hydrothermal pressure, and heat treatment containing a crucible Make = materialized wrong material _ green. The responsibility of this method - salt as a synthetic zinc oxide can be zinc acetate and zinc zinc 30 200946584 ^υ/6opif.doc The synthesis method of inorganic particles is as exemplified in the Japanese Journal of Applied

Physics, Vol. 37, pp. 4603-4609 (1998) or Langmuir, vol. 16, pp. 241-246 (2000). Specifically, when the oxide nanoparticle is synthesized by a sol formation method, it may be used by dehydrogenation condensation or deflocation by a precursor such as a hydroxide, followed by an acid or a base, Thereby, a hydrogel is formed, as in the case of using titanium oxysulfate as a raw material to synthesize titanium oxide nanoparticle. For example, the prodrug of the precursor can be separated and purified by filtration and centrifugation. It is preferred to carry out this procedure from the viewpoint of the purity of the final product. For example, it is a dodecylbenzene benzoate (abbreviated as DBSR: succinyl sulphate monosodium salt (s, ch Industries, Ltd. ^^n, * «ELEMINOL JS-2M). Steep and separate it For example, it can be used in the 0-al' volume 57, 6, and 3G5 side pages (in the case of the agent described in the above, it is also possible to use the lake in the organic solution invention as an example. In this case, it is used for the raw material machine (4) Buxin,; == agent, 2-butyl', dichloromethane agent can be used alone or in two or two. These dissolves are used in this case. The invention relates to the presence of a compound on the towel. The average particle size of the material particles constituting the particles is too small, and the shame will change. On the other hand, when used in the present invention, i.doc 200946584 In the case of m, the influence of the thunder is significant, and there is a possibility that the low-surface and inorganic-aged wear rate can be mixed. Therefore, the lower limit of the average particle size of the money recorded by the threat is greater than or equal to 1 nm. Preferably, it is greater than or = 2 nm, and more preferably greater than or equal to 3 nm. The number average particle size of the inorganic particles of the present invention is preferably less than or equal to 2 () = Preferably, it is less than or equal to 15 nm, and is less than or less than i, ·, and 7 ^. Specifically, the inorganic trace amount of linbun is rich: the particle size is preferably from 1 to 20 nm, and more Preferably, the temperature is from 2 to 15 nm, and the step is preferably from 3 to 5 nm. The "number average particle diameter" referred to herein may be, for example, X (XRD) or a transmission electron microscope (ΤΕΜ). Measured at a temperature of 22. (and at a wavelength of 589 nm, for the benefit of the present invention, the particles have a refractive index of 19 to 3 G, and am? It is more preferable in the range of 1 to 2.5. When the refractive index of the particles is in the range of 3.0 _ 'the refractive index difference between the particles and the thermoplastic resin is not sag, and there is a tendency to easily suppress the sliding scattering. When the refractive index is greater than or equal to 丨.9, there is a tendency to easily achieve a high refractive index. The refractive index of the machine particles can be estimated by, for example, the following method: using an Abbé device (for example, Atag0 product DM-M4) Measuring the refraction of the transparent secret composite obtained by the combination of the inorganic and the hot brittle in the present invention, and measuring the individual resin components separately A method of converting the value of the refractive index, or measuring the refractive index of the dispersion of the particles having different concentrations of particles. 曰32 Ο ❹ 200946584 3U785pif.doc Self-light transmittance and high-folding point It should be noted that the content of the inorganic fine particles in the present invention is in mass percentage, i is good, and Γ 5% to 7G% is preferable, especially 3G% to 6〇% is more t. In addition, self-dispersible Sexual view i0: f is more and Γ: 0·.5 to... is preferred, especially ―[additive], with dispersible uniformity, fluidity during molding, release emulsification and the like From the viewpoint of the object, the above and various additives can be suitably used in the present invention.机·无观 i The blending ratio of these additives varies depending on the purpose. The percentage of the total mass of the fine particles and the resin is preferably 20%, and preferably 〇% to °%, especially 〇% (surface treatment agent): increase the score: have = or increase the weather resistance purpose) and add micro-modified ten surface treatment agent has a better 50 to = (10) 2 〇, _ and further step to 1〇, weight average of _ = soil = to 33 200946584, formula (3) The surface treatment agent preferably has a structure represented by the following formula (3)

A-B wherein A represents a surface which can be formed with the surface of the inorganic residue of the present invention. The resin of the thermoplastic resin of the main component of the present invention or a monovalent group or a compound of 1 to 30 carbon atoms which is reactive. As used herein, a chemical bond means a covalent bond, an ionic bond, a coordinate bond, a hydrogen bond or a similar chemical bond. Preferred examples of the group represented by hydrazine are the same as those exemplified for the thermoplastic resin used in the present invention. On the other hand, from the point of view of compatibility, the chemical structure of the group represented by 6 is the same as the chemical structure of the main heat of the base of the substrate. From the viewpoint of high refractive index, the chemical structure of B and the thermoplastic resin preferably has an aromatic ring. Examples of the surface treatment agent to be used in the present invention include p-octylbenzoic acid, p-propylbenzoic acid, acetic acid described, for example, in JP-A-5-221640, JP-A-9-1001li, and JP_A_2〇〇2_187921 , propionic acid, cyclopentanecarboxylic acid, diphenylmethyl phosphate, monomethylphenyl phosphate, diphenyl phosphate, di-α-naphthyl phosphate, phenyl phosphate, monophenyl phenyl phosphate, KAYAMER PM- 21 (product name, product of Nipp〇n Kayaku c〇., Ltd.), KAYAMER PM-2 (product name, product of Nippon Kayaku Co., Ltd.), benzoic acid, naphthalenesulfonic acid, p-octylbenzene Sulfonic acid and decane coupling agent. However, the surface treatment agent is not limited to the aforementioned surface treatment agents. These surface treatment agents may be used singly or as a mixture of two or more of the following: 200946584 ju / oujjif.doc. These surface treating agents are preferably added in an amount of 0.01 to 2 times the total mass of the fine particles, wherein 〇_03 to 1 times is more 隹, and 〇〇5 to 0.5 times is more preferable. (Plasticizer) ❹ ❹ When the thermoplastic resin used in the present invention has a high glass transition temperature (Tg), the molded composition may not be easy to report. Therefore, the use of an additive can be used to lower the molding temperature of the composition of the present invention. Wherein the addition of the plasticizer is preferably from 1% to 50%, preferably from 2% to 50%, especially from 3% to 2%, based on the total mass of the organic-inorganic hybrid composition. . With the addition of the invention, it is necessary to fully consider its compatibility with the resin, the resistance to gas, the plasticizing effect wire and the miscellaneous f. Since this is in the same group as the pot group, it is impossible to completely determine the best material. However, from the viewpoint of white, it is preferable to use a material having an aromatic ring, and a material having the structure of the formula (4) is a representative example. - Ο - Β 2 wherein Β 1 and car _ to 18 carbon materials ^ 18 carbon atoms of silk or one of 6: allylic alkyl groups, m is Θ or 1, X is the following group R11 - C — R12 ~S— -s〇2- Ό— and R11 and R12々A each independently represent a hydrogen atom or a group having less than or equal to 35 200946584 —ra.doc carbon atoms. In the compound represented by the formula (4), 'B1 and B2' may be selected from an alkyl group or an allylalkyl group in the range of 6 to 18 carbon atoms. When the number of carbon atoms is less than 6, the molecular weight is too low to cause the compound to boil at the melting temperature of the polymer, resulting in the generation of bubbles. On the other hand, when the number of carbon atoms exceeds 18, the compatibility of the polymer is lowered, resulting in an insufficient addition effect. And examples of B2 include a linear alkyl group such as n-hexyl, n-octyl, n-decyl, n-dodecyl, n-tetradecyl, n-hexadecyl, and decyl octadecyl; branched alkane a group such as 2-hexyldecyl and octadecyl having a fluorenyl group; and an allylalkyl group such as a benzyl group and a 2-phenylethyl group. Specific examples of the compound represented by the above formula (4) include the following compounds and, in particular, w-i (trade name: KP_L155, product of Ka〇c〇rp〇rati〇n) is preferred. W-1 c8h17-o~~^^-s〇2-<^_0—C8Hi7 ο W-2 c10h21-o~^^so2--^^〇_Ci〇h21 W-3 C8Hi7-〇-^^ S-^^〇--c8H17 36 200946584 ju/dopif.doc W-4

(Other Additives) In addition to the above composition, a mold release agent such as a modified one may be added to improve moldability. Conventional anti-deterioration agents such as an anti-corrosion type, an amine type, a phosphor type, and a thioindigo type may be appropriately added to improve dichroism and heat resistance. The preferred ratio of the mass of the additive to the solid content of the organic-inorganic hybrid composition is about 0.1% to 5%. ❿ [Manufacturing method of organic-inorganic hybrid fraction] The organic/inorganic hybrid composition used in the present invention can be produced by mixing, for example, a thermoplastic resin and inorganic fine particles. The inorganic fine particles used in the present invention have a small particle diameter and a high surface energy j:. Therefore, when these inorganic fine particles are solidly divided, it is difficult to disperse. Preferably, the inorganic fine particles and the thermoplastic resin are mixed in a state of being dispersed in the solution to form a stable dispersant. A preferred method of producing the mixture includes (1) a method of producing a mixture of inorganic fine particles and a thermoplastic resin, which comprises subjecting the inorganic fine particles to the surface-treated inorganic particles in the presence of the above surface treating agent - i.doc 200946584 A method of producing an inorganic cerium + diterpene, a mixture, and a method of using a mixture of inorganic fine particles and a thermoplastic resin. (5) Keyun > Kunhe Pharmacy Kit, description of the type. The preferred surface is located in the county 2 hot pack. If the money is difficult, if the == agent can be added, such as increase 1 when using the above method (2) 'better is used alone or with H = formula =: =, such as dimethyl di: ❹ 1-decyloxy-2-propene;, · · B" ethylene glycol monomethyl hydrazine, a mixed solvent of solvents, various; propionic acid ^ water insoluble vinegar, methyl ethyl Ketone, two η: aerobic, acetonitrile, and upper 34 polar solvent. In this case, if necessary and necessary: added from the above thermal resin separation (four) 'addition, release agent i Π ί = compound. When the inorganic fine particles are dispersed in water/sterol, the addition is higher than the water/alcohol lag point and dissolves the thermoplastic resin pro-38 200946584 ^ υ / oopif. doc agent, and then The water/methanol is concentrated and discharged, thereby substituting the dispersion of the fine particles and the polar organic solvent, and then mixing with the resin. The above surface treatment agent may be added under the condition of 'month'. The above method (10) and method (2) The money obtained_inorganic mixed composition=solution, preferably in the form of pro-cold, cold green drying, spray drying, self-destruction, granulation, etc. The solvent is removed, and the resulting solid is then subjected to a splay-kneading and molding by a conventional injection molding or compression molding, etc. In the present embodiment, when it is carried out by direct heating and then extruding, the present invention The powdery organic/inorganic hybrid composition of the towel is present in a pre-plastic (precursor) state having a specific weight and a specific shape, and the preformed preform is compression-molded to prepare, for example, a lens or the like. In the present embodiment, in order to efficiently mold a product of a specific shape, the preform can be produced with an appropriate curvature. The extrusion machine can be used for extrusion molding. In this example, That is, the energy supplied per unit volume is less than 100 MJ/m3, and the inorganic fine particles can be sufficiently dispersed in the thermoplastic resin. The energy level is preferably from IMj/m3 to 5〇Mj/m3, and further from 1 MJ/m3 to 30 MJ/m3 is preferred, and more preferably j Mj/m3 to 20 MJ/m3. The energy level referred to herein refers to the energy per unit volume, which is determined by the energy parameter and kneading of the kneading torque. Time integrated. In traditional In the organic-inorganic hybrid composition, when the energy supplied is less than 100 MJ/m3, the inorganic particles cannot be sufficiently dispersed in the heat-emitting tree and cannot achieve high light transmittance. In the organic_inorganic of the present invention In the mixed composition, even if the supplied energy is less than 1 〇〇MJ/m3, the inorganic fine particles can be sufficiently dispersed in the thermoplastic resin, and the composition still has a high light penetration rate of 39 _i.doc 200946584. When the aforementioned composition is formed into In the case of an object having a thickness of 丨cm, the light transmittance at a length of 589 nm is at least equal to 7〇%. 4 In the present invention, the means for melt-kneading may be a closed kneading device or a batch type pinch. And devices, for example, laboratory extrusions, Blavender mixers, Banbu mixers, kneaders and rolls, and the like. It is also possible to use a continuous melt kneading device such as a single extruder or a twin screw extruder. μ The organic-inorganic hybrid composition in this month can be mixed as a masterbatch into other resins. Good [Optical element] The optical element of the present invention can be produced by molding the organic-inorganic hybrid composition of the present invention. The optical element of the present invention has the refractive index and optical characteristics described in the aforementioned section on the inorganic mixed composition. In the optical element of the present invention, it is preferable that the thickness is greater than or equal to 〇 and has high folding impurities, and the + rotation is preferably from Q1 cm to 1 cm, and the thickness is from 丨cm to 3 cm. Better. In general, the solution washing method (10) uti〇ncastmeth〇d) has a thickness of the material, which is generally higher because the solvent is not easily extracted. However, in the organic-inorganic composition of the richness, the molding is very versatile, so it is easy to prepare a complex phase such as an aspherical surface. As described above, in the present invention, an optical element having a good light transmittance can be obtained by the high refractive index characteristic of the inorganic fine particles. The optical element in the present invention is produced by the organic/inorganic hybrid of the present invention. The composition of the optical element is not particularly limited. The organic-inorganic hybrid composition of the present invention is suitable for use in a lens substrate and a light warfare optical element (so-called passive light element). Examples of the optical function device of the optical component include various device devices (liquid crystal display, electro-polymer display, and the like, and similar devices), optical fiber communication, optical amplifiers, and the like. Photographic devices such as camera cameras and video recorders. The passive sound of the Lin Wei Wei device towel = examples of the lens include lenses, cymbals, cymbals, panels, films, optical waveguides, optical discs, and encapsulants of LEDs. The optical element using the organic-inorganic hybrid composition of the present invention is particularly suitable for a lens substrate. The lens substrate produced by using the inorganic mixed composition of the present invention has excellent light transmission and light weight, and is excellent in light quality. Further, the refractive index of the lens substrate can be selectively adjusted by appropriately cultivating the organic-inorganic hybrid group, the type of the constituent monomer, and the amount of the inorganic fine particles dispersed therein.

The "lens button" used in this article means a single piece of Wei Wei. The film or component may be provided on the surface of the lens substrate depending on the environment of use or the purpose of using the lens. For example, a layer of 透镜/4, an anti-reflective film, a hard coat layer or the like may be applied to the surface of the lens substrate. ^ The outer lens substrate can be mounted in a substrate holder or the like to secure it. However, these _ and the frame are elements that are added to the county in the present invention, and (d) the base of the kiln mirror itself. When the lens is made by using the lens substrate of the present invention, the lens substrate of the present invention can be used as a lens, or a film or a frame can be added, and the film or the assembly of the frame and the lens substrate can be used as a lens. The type and shape of the lens using the aforementioned lens substrate are not particularly limited. The lens substrate of the present invention is used for, for example, an eyeglass lens, a lens for an optical instrument, a lens for optoelectronics, a lens for a laser, a lens for a head, a portable lens (for example, a lens of a car camera, portable) The lens of the camera, the lens of the digital camera, the zoom lens, the progressive/regressive multi-focus lens (Progressive/Regressive Lens), the projector, and the lens for the microlens. EXAMPLES Next, the features of the present invention will be more specifically described by the following examples. In the following examples, the materials, the amounts and ratios, the details of the treatment methods, and the steps of the treatments may be appropriately modified or changed without departing from the spirit and scope of the invention. Therefore, the present invention should not be limited by the following examples. [Methods for Analysis and Evaluation] In the following examples, 'all methods of analysis and evaluation are achieved by the following methods: (1) X-ray diffraction (XRD) spectral measurement: using Rigaku Corporation's product RINT 1500 (X-ray source: copper Ka light, wavelength: 1.5418 angstrom), and the sample was measured at 23 °C. (2) Observation by a transmission electron microscope (TEM): Transmission electron microscope h-9〇〇〇42 using Hitachi, Ltd. 200946584 ^υ/oopif.doc UHR Model (acceleration voltage: 200 kV, observation Vacuum degree: about 7.6 x 10-9 Pa) Observed sample. (3) Measurement of light transmittance: The sample to be measured was molded to prepare a substrate having a thickness of 1.0 mm, and a UV-visible spectroscopy apparatus UV-3100 (product of Shimadzu Corporation) was used with 589 nm. The wavelength of the light is measured on the substrate. (4) Measurement of refractive index: A sample was measured with a light having a wavelength of 589 nm using an Abbe refractor (DR-M4, product of Atago). (5) Measurement of molecular weight: The molecular weight described here is based on the conversion of polystyrene.

Tosoh Corporation's products TSK gel GMHxL, TSK gel G4000HxL and TSK gel G2000HxL (trade name) column, molecular weight detected using a colloidal osmometer (GPC) differential refractometer (solvent: tetrahydrofuran). (6) Measurement of glass transition temperature (Tg): A glass differential was measured for each sample by using a differential differential teller card (DSC6200 'product of Seiko Instruments) and heating nitrogen at a rate of lot: per second. temperature. The glass transition temperature described herein is measured by this method. (7) Impact test: Prepare a disc sample with an outer diameter of 8 cm and a thickness of 1 cm, and place the disc sample in a loop. The weight is in the opposite direction of the appliance, and then at a height of 3 meters. It fell to the concrete floor 5 times. On the same 43 200946584, a total of 1 ¢) samples were taken in the experiment. The composition was evaluated according to the number of ruptures or damages, as follows: Good (〇): The number of samples broken or damaged is 〇. General: The number of samples broken or damaged is 1 to 3. Bad (X). The number of samples broken or damaged is greater than or equal to 4. [Preparation of Inorganic Particulate Dispersion] (1) Preparation of Oxidation Dispersion Liquid: 〇 A gas zirconia solution having a rolling degree of 50 g/liter was treated with a 48% aqueous sodium hydroxide solution to obtain hydrazine hydrate; The fresh liquid was transferred, and the ion exchange water filament was used, and the ion exchange water was used as a solvent to prepare a mass percentage. Rolling hydrazine solution. The solution was placed in an autoclave and treated at 150 atmospheres for 24 hours to obtain oxidized particles to confirm the number of oxidized particles (2) having an average particle diameter of 5 nm. Preparation of oxidized hammer / dimethyl hydrazine Amine dispersion (1): ❹ Add N,N,-dimercaptoacetamide (5 gram gram) to the above (prepared oxidized material dispersion (15% by mass aqueous dispersion) (g)) and the resulting mixture is concentrated under reduced pressure to about $(10)

Substitute for the agent. N, NL dimethyl acetamide was added to adjust the cerium oxide ceramide dispersion (2) having a concentration of 15% by mass. Earth G

[Preparation of thermoplastic resin] 〇) Thermoplastic resin (IM, 2, 4, 5, 6, 1 〇, 12, 23, 24, 26, 4, 3 〇) system 44 200946584 ^u/©opif.doc

Placcel FM (trade name, manufactured by Daicel Chemical Industries) (1 g), styrene (99 g), and polymerization initiator v-601 (trade name 'product of Wako Pure Chemical Industries) (〇.5 g) dissolved in Ethyl acetate (233.3 g) was subjected to a polymerization reaction at 75 ° C for 3 hours in nitrogen, and then poured into 2 liters of ethanol to obtain a thermoplastic resin (P-1). Ο Ο Measure the molecular weight of the resin obtained. The resin had a number average molecular weight of 55,000 and a molecular weight distribution of 1.85. The refractive index of the resin was measured with an Abbe refractor, and the refractive index at a wavelength of 589 nm was 1.59. The other resins (P-2, P-4, P-6, P-12, P-23, P-24, P-26, P-29, P-30) described in the following examples are identical. The manner was prepared, however, 'the type of monomer, the concentration of the monomer, and the starting concentration were changed. (2) Preparation of thermoplastic resin (P-37): 2,2-bis(4-indenyl)anthracene acid was prepared by the method of Japanese Patent JP-A 2004-217647 as described in Example (2). Na. A thermoplastic tree was prepared in P-37 as described in Japanese Patent Publication No. 5-222175 in Example (3), however, part of the bisphenol A diacetate (bisphen〇1 di diacetate) was 2 Substituted by sodium 2-bis(4-hydroxyphenyl)pentane sulfonate. The number average molecular weight of this resin was 50,000 as measured by GPC. Further, the refractive index of 1.61 at a wavelength of 589 nm was measured by an Abbe refractometer. Compound (3) in & Comparative Preparation of Resin (X-1, 2) (JP-A 2007-238929 45 i.doc 200946584 B-13): Thermoplastic resins X1 and X-2 are thermoplastic resins as described above P-1 was prepared in the same manner. Comparative resin (X-1): X-1 a/b = 99/l (weight ratio) Number average molecular weight = 2 〇〇〇〇 Comparative resin (X-2): X-2 -fCS2-〇E^ a/ b=94/6 (weight ratio) number average molecular weight = 20000

(4) Preparation of Comparative Resin (X-3) (Compound (D) in JP-A 2006-131736 - Ethyl decyl acrylate (100 g) and polymerization initiator V-601 (trade name, Wako Pure) Chemical Industries () 0.50 g) was added to ethyl acetate (233.3 g) and polymerized in nitrogen at 75 ° C for 3 hours, then poured into 2 liters of ethanol to pay for the sink. Resin (X-3)' in which the bond of the resin (X-3) is compared and does not contain a functional group capable of forming a bond with the fine particles. As a result of GPC measurement, the number average molecular weight of the resin is 55,000 'in addition' Abe refractive index measurement, this resin has a refractive index of 1.49. Comparative resin (X-3): 46 200946584

(5) Preparation of synthetic comparative resin (X-4): styrene (100 g) and polymerization initiator v_

The functional group of the knot. The result of the GPC system was that the average molecular weight of this resin was 58,000. Further, the resin having no functional group had a refractive index of 1.59 as measured by an Abbe refractor. Compare resin (X-4).

[Preparation of material composition and manufacture of transparent molded body] [Example 1] Thermoplastic resin P small 4-n-propylbenzoic acid (C3BA) and plasticizer Tetraphenyl sigmoid S-3103 (trade name, Matsumura Petrochemical

The product of Laboratories) was added to the above-prepared oxidized/dimercaptoacetamide dispersion, wherein the mass ratio of oxidized solid content, H, 4-propylbenzoic acid and tetraphenylether was 41.7/45.8. /8.3/4.2, and the mixture was uniformly stirred, and the dimethyl acetamide solvent was concentrated under heating under reduced pressure. The concentrated residue was dried in a vacuum pump at 902⁄4 for 2 hours to prepare a machine-inorganic mixed composition src-i of 47 -doc 200946584.

Then the 'organic-inorganic nano-composition powder NC-1 was placed in the ULT_nano (trade name, orifice diameter 3 Chumi) of the compound tester Technovel company' at the tube temperature l70 °c and the mold temperature l8 (^c The tree sorghum is melted and extruded into a transparent columnar organic-inorganic hybrid composition. The extrusion pressure is 6.1 MPa, and the energy supplied per unit volume is less than 6.1 MJ/m3. Then, the transparent column is formed. The organic-inorganic hybrid composition was cut into small pieces of 1 mm thickness to measure light transmittance and refractive index. In addition, the particle dispersion was observed by a transmission electron microscope (TEM) to observe the sample section and confirmed The inorganic fine particles are uniformly dispersed in the resin. Further, the transparent columnar organic-inorganic hybrid composition is cut into about 3.5 by hot press forming (temperature: 180 〇c, pressure: 13 7 MPa, time: 2 minutes). A preform having a thickness of millimeters to obtain a tubular transparent shaped article having a thickness of 丨 mm and a diameter Φ of 3. The foregoing sample was tested by the above-mentioned 'impact resistance test method. The composition of the organic masher mixture composition NC-1 is as Take $ Shown in Table 1, and "the results of the test are shown in Table 2.

[Examples 2 to 13] The compositions of the organic-inorganic hybrid composition NC-2矣NC 13 NC-2 to NC-13 were prepared in the same manner as in Example 1 as shown in Table 1 below. After being forced out by the extruder, the organic-inorganic mixed composition is transparent.穿透 穿透 穿透 穿透 TEM TEM TEM TEM TEM TEM TEM TEM TEM TEM TEM TEM TEM TEM TEM TEM TEM TEM TEM TEM TEM TEM TEM TEM TEM TEM TEM TEM TEM TEM TEM TEM TEM TEM TEM TEM TEM TEM TEM TEM TEM TEM TEM TEM TEM TEM TEM TEM TEM TEM [Example 14], titanium oxide fine particles were prepared according to the method described in Synthesis Example 9 of Jp-A-2003-73559. It was confirmed by X-ray diffraction (XRD) and a transmission electron microscope (TEM) that Formation of anatase-type titanium oxide fine particles (number average particle diameter of about 5 nm). The titanium oxide fine particles were suspended in 丨-butanol, followed by ultrasonic treatment for 30 minutes, followed by heating at 1 Torr (3 rc) At room temperature, ❹ The obtained milky liquid was added dropwise to a gas-like solution of a polymer dispersion P4 having a mass percentage concentration of 10% while stirring at room temperature for 5 minutes to make titanium oxide. The solid content is 40 〇/〇 (mass ratio) relative to the total solid content in the foregoing dispersion. The solvent is taken from the obtained mixed liquid and the organic-inorganic obtained after distilling in the same manner as in Example 1 The mixed composition NC-14 was extruded to obtain a column. The inorganic mixed yoke Nd4 in Example 14 was transparent after being extruded by an extruder. The cross section was observed by a transmission electron microscope (TEM) to confirm that the inorganic fine particles were uniformly dispersed in the resin. 15,16] The organic-inorganic hybrid compositions Nc_15 and NC_16 were produced in the same manner as in Example 14, except that in Examples 15 and 16, they were replaced with P-23 and P-24, respectively. The individual components are as shown in the following Table 1. In Examples 15 and 16, the inorganic mixed composition was transparent after being machined, and was observed by a transmission electron microscope (ΤΕΜ). The inorganic particles are uniformly dispersed in the resin. The test and evaluation results of the organic-inorganic hybrid composition are shown in Table 2. 49 200946584 [Comparative Examples 1 to 5] Organic-inorganic hybrid composition of the comparative example The components contained in NCX-1 to NCX-5 are as shown in the following Table 1, and were produced in the same manner as in Example 1, except that the thermoplastic resin P-1 in Example 1 was respectively compared with & Replaced by X-1 to X-4 in 1 to 5. Try to be taken out by the production method in the same way as the example. However, due to insufficient fluidity, the components NCX-1 to NCX-3 could not be extruded at an energy of 20 MJ/m3. Then, the energy supply was increased to 100 MJ/m3, but at this time, the finished product was browned and opaque. On the one hand, when the energy is supplied at 1 MJ/m3, the compositions NCX-4 and NCX-5 produce an opaque product. The cross section of the observation electron microscope (TEM) confirms that the inorganic particles are agglomerated in the resin. The test and evaluation results of the organic-inorganic hybrid compositions NCX-1 to NCX-5 are shown in Table 2. '

50 200946584 30FJU98 Bu οΓη Plasticizer! Dosage 1 (Quality Dong%) (N cs < N vs. <N Pairs ' CN «Ν 对' rs •nt fN PN <N Pairs · <N Pairs · ΓΊ 1 1 1 rs o pair · CN <N pair · I S-3103 I 1 S-3103 1 I S-3103 I S-3103 I S-3103 II S-3103 I 1 S-3103 I S-3I03 1 S -3103 I S-3103 1 S-3103 I S-3103 S-3103 1 S-3J03 S-3103 S-3103 S-3103 ; S-3103 Dosage (% by mass) ΓΟ 6 00 m od m Bu om Od r^) od ro od oo ro od m od ΓΟ 00 1 ro oo od m od od od 1 C3BA I \ C3BA I C3BA 1 C3BA I 1 C3BA | 1 C3BA | I C3BA II C3BA I 1 C3BA I C3BA I C3BA I 1 C3BA I 1 C3BA 1 1 C3BA I C3BA I 1 C3BA II C3BA I 1 C3BA | Amount of Inorganic Particles (% by mass) Bu 1 - To Bu Bu o 1 53.86 Bu··< Bu BuΓ-; Bu t- N 卜οο ο oooo 卜 Tt- 卜卜卜 inch inch 1 number average i particle size (nm) «η m •rj *Tx V» •η u-» m •Ti «Ti »n »r\ m » η 戡乡N (Ί § i N ΓΝ N (N '§ rs N cs S Γ·) § N (Ν Ν Μ IN O) rs NNN § fN § Thermoplastic resin {〇〇m (N (N in 卜 (N Os CN 〇\ 1 15.98 15.98 15.98 23.97 Γ 15.98 11.10 19.98 σ\ On 17.97 fN OO ; 15.98 m 00 CN 00 卜 (N 16.65 用量 Dosage (% by mass) 〇〇 Inch OO »ri oo oo in (N rn 00 »ri 00 »ri 0© in oo »n 00 »n oo oo ο S osos 00 *n 〇o oo «η 00 »n pair 00 j number average molecular weight 45000 55000 80000 80000 80000 80000 80000 320000 80000 , 80000 80000 120000 50000 80000 50000 42000 20000 20000 20000 J 55000 58000 Township Z < N Cu o 0, cL inch eu inch d a- cL (N cL (N cL 〇\ cs a, cL cL CU CO CM 2 r X Τ Ι X (Ν cn 7 >< glass transition temperature (°C) 〇m oo O pair · 00 om 00 Ό s O rf Os O od oo 〇0 1 O \ό as 115.0 ' Rf O om ON Ο ON Os [102.0 | 100.0 o <N 00 Ο g tri ο § -13⁄4 <^〇^ 1 NC-1 1 pNC-2 1 cn 1 U NC-4 NC-5 [NC-6 | 1 NC-7 1 fNC-SH I NC-9 1 ί NC·10 | NC-11 1 1 NC-12 丨1 NC-13 丨\ NC-14 1 j NC-15 1 [NC-16 I 1 NCX -1 | \ NCX-2 | 1 NCX-3 1 KCX-4 ] ! NCX-5 1 Example 1 Example 2 β Example 3 1 Example 4 D Example 5 | | Example 6 I i Embodiment 7 1 Embodiment 8 | Embodiment 9 ] | Embodiment ί 1 1 | Example 丨 I | Example 丨 2 1 | Example 13 ] | Example 14 I | Example 15 1 Example 16 1 |Comparative Example i | |Comparative Example 2 1 |Comparative Example 3 1 |Comparative Example 4 | 1Comparative Example 5 1 2 logf : sl.aJlagoqBq iogl-sdBJnsnstas- e-ifssIe-ssso硪铋0 & sle, 2 8&amp ;-蚪硪β4& VOG:坊200946584 .doc Table 2

❹ 〇 (4) Organic _ non-affinity composition has a good shape to be formed into (4) light transmissive shape, so it is suitable for the state of reduction supply, such as the comparison of the example +, X], 2, the organic of the hot chicks _ inorganic The mixed group secret is directly linked to Jilian County, so it cannot be forced out by the extruder under low-energy conditions, and can only be forced out at the 100 MJ/m3 of the energy supply water. However, even if it is extruded in such a high-energy state, the extruded molding will not be transparent (Comparative Example to 52 200946584 v / ον/pxf.doc 3). Even if the content of the plasticizer in NCX-2 was increased (Comparative Example 2), the fluidity could not be remarkably improved. In another aspect, the organic-inorganic hybrid composition of the present invention comprises a thermoplastic resin having a carboxyl group, wherein a carboxyl group is bonded to the main chain by a linking chain having a chain length of 4 atoms (as in P-12 in Example 9), On the other hand, it is possible to form a transparent product under the condition that the energy supply level is less than or equal to 100 MJ/m3, and the molecular weight of the resin is more than 50,000 to satisfy the impact resistance. Further, the organic-inorganic hybrid composition of the present invention comprises a thermoplastic resin having a carbonyl group in which a carboxyl group is linked to a main chain (e.g., P-10) by a chain of 5 atoms in a chain length, and its fluidity is greatly improved, and I became a better transparent article under low energy supply conditions - even though the south molecular weight of the resin had a number average molecular weight greater than 50,000 (as in Example 3). In the organic-inorganic hybrid composition of the present invention, when the molecular weight of the resin is lowered, the fluidity of the resin component is increased, but the brittleness of the molded article tends to increase. Thus, the resin having a composition has a number average molecular weight of at least 50,000 (for example, the comparative example 丨 and the heat-resistant twin from the component, the glass transition temperature of the resin is not lower than that. In general, when When the molecular weight of the resin and the glass transition temperature increase, the fluidity is lowered. However, the organic-inorganic hybrid composition of the present invention has good fluidity, although the resin therein has a number average molecular weight of not less than 5 Å, and glass. A molded product having a high-light transmittance of a polymer compound having a temperature of not less than 8 〇〇c, and a lens shape having a uniform shape can be formed with good productivity and a shape of a cast steel. The chain is not a tree (χ-3, 4) The organic-inorganic hybrid composition does not have a base bond, and the mesh produces a transparent _ object under the condition that the energy supply level is less than or equal to loc 53 .doc 200946584 = J/m (comparative example, minus , in the composition of the side of the component hI) Ar :: for the shape of the object of good transparency. Each - poly;: the number is less than or equal to 2 〇, which has a high light transmittance (implementation Examples 1 to 6, 8 to 16). Under the lower composition, from the compression molding conditions shown in Example 1, the punch or the concave _(4), =^=^=彳, 15) can be accurately transferred by the profile come. , large, transparent. Brother, and the rim of the mold is the same as described above. 'The organic _ fluidity of the invention, in the low energy supply, the attack has a good shape-shaped object, which is well made and becomes a translucent material. The superior properties of the organic-inorganic hybrid component of high quality light x month. First, the piece will benefit from the organic materials it contains. [Simple illustration] Benefits. "», [Main component symbol description] 〇 54

Claims (1)

A.doc 200946584 VII. Patent application scope: and an inorganic mixed composition comprising a plurality of inorganic fine particles and a thermoplastic resin, the thermoplastic resin having a structure, the knot forming a chemically bonded-functional surface with the inorganic fine particles by: Equivalent to 4 atoms connected to the thermoplastic ray-main ship, and the chain of the sling chain grows 3 2. The organic-I Ο e object as described in the scope of the patent application can form with the inorganic particles - The chemically bonded 'machine-to-link chain is connected to the main chain of the county, and the chain length is greater than or equal to 5 _. 3. The substance of the linking chain, wherein the organic-inorganic mixed composition OR^l 'f'OR finds Ο wherein R11, R12, R13 and Rl4 each represent a hydrogen atom, a substituted or unsubstituted alkyl group, Alternate or unsubstituted alkenyl, monosubstituted or unsubstituted; alkynyl, monosubstituted or unsubstituted aryl or an atom or group capable of forming a salt; _s〇3H or a salt thereof, _〇s 〇3H or a salt thereof, or a salt thereof, or _si(〇R, 5)m, RlVmi, wherein r1S and R each may represent a hydrogen atom, a monosubstituted or unsubstituted alkyl group, a monosubstituted or An unsubstituted dilute group, a monosubstituted or unsubstituted alkynyl group, a monosubstituted or unsubstituted aryl group or an atom or a group capable of forming a salt; and ml represents an integer of 1 to 3. 4. The organic-inorganic 55, which is described in claim 1 or claim 3, wherein the thermoplastic resin has a structural unit unit represented by the formula (1): In the structure I w Z ", R represents a hydrogen atom, a halogen atom or a -methyl group; W represents an alkyl group derived from _〇_-CO NH-, -s-, _CS-, mono- or unsubstituted, and a substituted or unsubstituted group of light or fine groups of one or more groups having a chain length greater than or equal to 4 atoms; and Z represents a functional group capable of linking to the inorganic particles 5. The organic-inorganic two, and the material described in the third paragraph or the third item, wherein the hot lion has - the early 兀 is represented by the formula (2): 〇R —〇〇❹ V 原 = and substituted or unsubstituted or unsubstituted exudates are selected from the group of the Chinese group, and the group is selected from one or more linking groups of _2 or more atoms. For example, the organic-inorganic 56 described in the scope of the patent or the third paragraph of the patent scope 2009 2009 584 υ 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 Wherein a polymerized bond of the thermoplastic resin has a content of the functional group of Q i to 2 (). The ruthenium contains a ruthenium as described in the first or third aspect of the patent scope of the patent application. The thermoplastic tree = two machines equals 50,000. The Riedin J knives are larger than or ❹ ❿ mixed range of the organic-inorganic ^2, in the third or third item, the average number of inorganic particles in the middle The diameter is from 丨 to 20 ... Please refer to the organic-synthesis G or titanium oxide described in item 1 or item 3. The inorganic particles include oxygen, tin oxide and oxygen. 10. The mixed machine group according to the scope of item i or item 3 of the patent application, the money machine-money mix 5 bis, meter and wavelength 589 奈The light transmittance of the rice is greater than or equal to the thickness of 1 centimeter. Jj. The organic ''benefit composition' of the first or third item of the patent scope of the patent, wherein the organic-inorganic hybrid composition is refracted The rate is greater than or equal to 1.60. A transparent molding, which has the organic-inorganic hybrid composition as described in any one of claims 1 to 11. An optical component having an organic-inorganic hybrid composition as described in any one of claims 1 to 1. A lens having an organic-inorganic hybrid composition as described in any one of claims 1 to 2. 57 200946584doc IV. Designated representative map: (1) The designated representative of the case: None. (2) A brief description of the component symbols of this representative figure: None. 5. If there is a chemical formula in this case, please disclose the chemical formula that best shows the characteristics of the invention: None.