TW200817176A - Display device - Google Patents

Abstract

Provided is a display device formed by using a hard transparent substrate having properties like inorganic glass and properties like plastic and having an excellent bending-resistance. The hard transparent substrate is obtained by hardening a hardening resin represented by formula (1), said hardening resin having a tight structure portion (A) having a Kp of 0.68 to 0.8 calculated from formula (2) and a loose structure portion (B) having a Kp less than 0.68, weight ration of structure portion (A)/(B) being in a range of 0.01 to 5.00, said hardening resin having at least one unsaturated coupling and having an average molecular weight of 800 to 60000. -((A)-(B)m)n- (1)(m and n are integrals equal to or more than 1) Kp=An*Vw*p/Mw(2)(An = Avogardro constant, Vw = Van der Waals volume, p = density, Mw = molecular weight, Vw = ΣVa, Va = 4π/R3 - Σ1/3πhi2(3Ra-hi), hi = Ra-(Ra2+di2-Ri2)/2di, Ra = radius of atom, Ri = radius of coupled atom, and di = distance between atoms)

Description

[Technical Field] The present invention relates to a display device in which a novel hard transparent substrate is used in place of a conventional glass substrate to laminate an electronic material for a display device, and is related to, for example, a computer or an audiovisual device. Display devices used in various fields such as mobile phones, information and communication machines, game or simulation machines, and navigation systems mounted on vehicles. [Prior Art]: With the rapid advancement of electronic technology, especially the liquid crystal display device, touch panel, and photovoltaic field are expanding. In general, photovoltaic elements are provided to various applications by forming the elements on a glass substrate having a transparent conductive layer. However, the glass substrate is heavy in weight, and when combined with a mobile device, the weight of the organic device becomes large due to the large ratio of the glass substrate. Therefore, light weight is expected, and in the case of a hard substrate which replaces a glass substrate, polyacrylic acid (ester, polyethersulfone, polycarbonate, etc.) which are excellent in strength, transparency, heat resistance, etc. are gradually used. A sheet substrate composed of plastic sheets. However, since the thickness of the wafer substrate is about 〇·1, the rigidity of the wafer substrate is less than that of the conventional glass substrate. In order to impart rigidity, it is considered that the crucible is not exhausted. However, in the case of a solvent which is generally used for obtaining a sheet substrate, in the casting method, the thickness is actually produced due to problems of foaming, planarity reduction, and residual solvent. The limit of .2mm is the limit. In addition, in order to be applied to a liquid crystal element, the birefringence of the sheet substrate usually needs to be 2 〇 nm or less, preferably less than 1 〇 nm, but when the plastic is formed, it is easy to be subjected to molecular orientation and it is difficult to manufacture low birefringence by 319624 5 200817176 - molecular orientation. The formed body. Then, for example, the optical layer of a sheet having a small birefringence layer is laminated (in the case of such a sheet, since it is a difficult plastic resin, it has a small rigidity and is extremely inferior to the drug property. Further, the optical sheet is used. In the case where the surface layer of the substrate w is coated with a curable resin (see Patent Document 2), when the sheet is cleaned on the substrate, the curable resin on the side of the sheet is swollen or dissolved depending on the solvent. Therefore, the resistance is poor, and the rigidity of the same substrate is insufficient. = In other words, in the field of photovoltaic elements, a high degree of light-preserving, gas barrier, conductivity, mechanical strength, etc. are required. = Upper layer uses an earth plate composed of a multilayer structure or a film having various functions. It has been proposed, for example, to provide a hardened coating on both sides of a plastic molded body::: a conductive film is provided on the surface, and the other surface is provided on the other side The metal oxide coating is provided in this laminate, and the properties of the layers are different from each other: ° 4 is special. Therefore, when heating, cracks and the like are likely to occur on the plastic molded body. Although the rubber sheet substrate is used as a glass substitute base, it is not only required to be lightweight, but also has to be changed in a child's manner. That is, the substrate is bent at a certain curvature (to make the bending, it is necessary There is no crack on the conductive film to ensure conductivity. However, there is a problem that the bending resistance is insufficient on the plastic substrate which is not in use. [Patent Document 1] Japanese Patent Laid-Open Publication No. 7_36〇23 [Patent [Patent Document 2] Japanese Patent Laid-Open No. Hei 6-116406 [Patent Document 3] Japanese Laid-Open Patent Publication No. Hei No. Hei. No. Hei. No. Hei. The display device i is a hard shell transparent substrate which has strength, transparency, heat resistance and dimensional stability such as inorganic glass, and also has high mobility and workability such as plastic, and excellent in flexibility. In addition, the inventors of the present invention have been working hard to obtain a new type of substrate for replacing the conventional glass substrate. In the substructure, the hardened tree is hardened by the compact structure and the loose structure, and the glass substrate and the plastic sheet substrate have excellent performance, and the bending resistance is also obtained. A hard transparent substrate, which is suitable for replacing the glass substrate used in various display devices, is completed. In the sigma, the present invention laminates the display device with electronic materials on the hard raft. a display device formed by a bright substrate; the hard transparent substrate is obtained by curing a curable resin represented by the following formula (1), and the curable resin is calculated by the following calculation formula (7) Packing c〇eff1Cient KP in the metal oxide level of 〇·68 to 〇·8 (8), and the loose structure part (Β) composed of the organic matter or organic metal oxide of the above Κρ未达〇68 At the same time, the weight ratio of the structural part (Α) / (B) is 〇〇1 to 5 〇〇, and has at least one unsaturated bond and an average molecular weight of 800 to 60,000. -ί (A)-(B)m} n- (l) 319624 200817176 - (except that m and η represent integers above 1) Κρ=Αη · Vw · p/Mw (7) (only, An = Yafoga Avogadro constant, vw=Van der Waals volume, density, Mw=molecular weight, Vw==SVa,

Va=47i/R3-El/37i:hi2(3Ra-hi),hi=Ra-(Ra2+ di2-Ri2) /2di, Ra=atomic radius, Ri=bonded atomic radius, and di=interatomic distance) In the above display device of the present invention, the compact structure portion (A) is a metal oxide portion having a three-dimensional polyhedral structure in which the organic substance portion of the following general formula (I) is removed, and the loose structure portion (B) is a general formula ( The organic matter part of the formula is composed of the following general formula (U): (RSi03/2) w(M02)x(RXSiO)y(XM〇3/2)z (1) (R3R4R5Si01/2)j(R6R7SiO)k{ R6R7XSi〇1/2}l (jj) or (c)-CH=CH2 represents an unsaturated group, an alkyl group, a cycloalkyl group, a cycloalkene group, a phenyl group, a fluorene atom, an alkoxy group, or an alkyl group. a decyloxy group, and a plurality of R in the formula (1) may be different from each other, but at least i of the groups include any one of (&), (b), and (c). Further, R1 represents an alkylene group. , an alkenyl group or a phenyl group, r 2 represents a hydrogen atom or an alkyl group, and R 3 to R 7 are an unsaturated group represented by — — (b) — R 1 — CR 2 —CH 2 or (c) — CH=CH 2 , an alkyl group, Cycloalkyl, cycloalkenyl, phenyl, hydrogen, alkoxy, or alkyl oxime 'Μ is a metal atom of ruthenium, osmium, titanium, or zirconium, χ is a halogen atom, or alkoxy group, W is an integer of 4 or more, and X, y, and ζ are integers satisfying w+x+y + z = 8. In addition, j, k, and 1 respectively represent integers above )) 319624 8 200817176 The metal oxide portion of the three-dimensional polyhedral structure skeleton in the structural unit shown by 匕-k general (work) is generated from RSiX3, MX4 Or such a mouth = (! 隹 R, ] y [and X is the same as the general formula (1)) of the hydrolysis condensate is constructed in a unit of a two-dimensional polyhedron structure of the metal oxide portion of the skeleton, or the general formula (π) The structural unit is a chain unit of a metal oxide produced by a hydrolysis condensate of R3R4R5six, R6R7si& or a mixture thereof (only, ... to r7^x is the same as general formula (8)), and bonded to a metal atom. The organic group is a preferred aspect of the present invention. In addition, in the present invention, a hydrosilyl catalyst or a radical initiator may be formulated according to the above curable resin, or may be formulated. Dream hydrogenation catalyst and free radical initiator to form a curable resin composition The hardenable resin composition is cured to obtain a hard transparent substrate. Specifically, the curable resin composition prepared as described above can be thermally cured or photohardened after being formed into a predetermined shape. a molded body (hard transparent substrate). Further, in the curable resin composition, a compound capable of hydrogenating at least one anthracene hydrogen group or a compound having an unsaturated group in a compound, or These two can be adjusted. (Effects of the Invention) The hard transparent substrate which is described by the present invention has strength, transparency, heat resistance and dimensional stability such as inorganic glass, and also has high toughness and workability such as plastic, and is resistant to bending. Since it is excellent in the properties, it can be used as a glass substrate used in a display device of various fields including a liquid crystal display device, a touch panel display device, and an organic EL display device, and the conventional glass substrate and plastic film substrate can be used. The 319624 9 200817176 - can provide the display device with better lightweight and collision resistance. [Embodiment] ~ & The present invention will be further described in detail below. The curable resin of the present invention has a molecular structure composed of a compact structure portion (A) and a loose structure portion (B) as shown in the above general formula (1), and has at least one unsaturated bond. Here, the compact structure portion (4) is a structural portion composed of a metal oxide portion having a stacking coefficient Kp of 0.68 to 〇8, and the loose structure portion (Β) is an organic tantalum portion having a stacking coefficient Κρ未达·68. Or the structural position of the organic part and the organometallic oxide site. The mouth tight structure portion (A) is preferably a metal oxide portion of the above-described general formula (the three-dimensional polyhedral structure skeleton in the structural unit shown. In the general formula (I), at least one of R should preferably have the above ( a) to (c) = the organic group of the saturated group. Further, the plurality of R systems of the general formula (1) need not be the same. The structural unit represented by the general formula (1) is composed of a three-dimensional polyhedron and R is composed of an example in which the general formula (1) is rated as 8 and X, 丫 and z are 0, w is 10, and X, y, and z are 〇, and w is 12 and X, j. Specific examples of the structure in which Z is 0 are shown in the following structural formulas (3) and (sentences and (5). The structural unit represented by the general formula (I) is not limited to such a structural formula =), (4) And (5). These structures are shown by the X-ray crystal structure analysis for a well-known specific functional group. 319624 10 200817176

The metal oxide site in the structure of the structure represented by the above formula (I) can be obtained by subjecting one or more compounds represented by RSiX3 or MX4 to hydrolysis and condensation reaction in the presence of an acid or a test medium. Here, r, X and lanthanide have the same meanings as r, X and μ of the general formula (j). It is preferable that one part of R is an unsaturated group represented by the above (a), (b) or (c), but if a preferred unsaturated group is represented by a specific example, for example, 3-methylpropene醯 丙基 propyl, 3 propylene oxypropyl, aryl, diene: 319624 11 200817176 and styryl. The hydrolyzable group of the X-based halogen atom or the alkoxy group may, for example, be a chlorine, a bromine, a methoxy group, an ethoxy group, a n-propoxy group or an isopropoxy group. Preferred examples of the compound represented by RSiX3 include, for example, trichlorodecane, decyltrichlorodecane, ethyltrichloromethane, isopropyltrichloromethane, butyl dichloride. Xishou, tertiary butyl triclosan, cyclohexyl trichlorodecane, phenyl trichlorodecane, vinyl trichlorodecane, allyl trichlorodecane, styryltrichlorodecane, cyclohexenyl Chlorodecane, trimethoxy decane, methyl dimethoxy decane, ethyl trimethoxy decane, isopropyl tridecyl decane, butyl tridecyl decane, tert-butyl butyl trimethoxy decane, Cyclohexyl dimethoxy decane, phenyl trimethoxy decane, vinyl trimethoxy decane, propyl propyl trimethoxy sulphur, styryl trimethoxy sulphur, cyclohexyl, methoxy (tetra) , triethoxy (tetra), methyl triethoxy zebra, ethyl monoethoxy zebra, isopropyl triethoxy zebra, butyl triethoxy

:Sinter, tert-butyl butyl triethoxy shixiyuan, cyclohexyl triethoxy zexiyuan, J-based di-ethyl milk base, ethylene triethoxy (tetra), allyl triethoxy methoxy vinyl Ethoxylated sulphur, cyclohexenyl triethoxy sulphur: 院, methyl tripropoxy hydroxy, ethyl tripropoxy sulphur, isopropyl dipropoxy sulphur, its - Tongmei P. butyl dipropoxy decane, tert-butyl butyl propylene tripropoxy sulphur, fluorenyl propyl: two: propylene reduction, ethoxy decane, cyclohexenyl tripropoxy US 22: the present vinyl tripropylene ethoxy money, methacrylic acid;: burnt: = (tetra) methyl - 虱 T-dimethyl dimethyl decane, 3 - methyl propyl 319624 12 200817176, dilute oxypropylene Trichlorodecane, 3-methylpropenyloxypropyltrimethoxyhydrazine, methylpropenyloxypropyltriethoxydecane, 3-propyleneoxypropyltrimethoxydecane, 3-propene醯 丙基 propyl trichloro decane and the like. In addition, the system is 矽, 锗, titanium or 鍅. Here, as a preferable example of the compound represented by μα, for example, tetrachloromethane, tetramethoxy hydride, tetraethoxy hydride, tetrahydrofuran (germane), and tetramethoxy group are mentioned. Misfired, tetraethoxy misfired, 6 titanium oxide (titaniumeth〇xide), propoxy field, titanium isopropoxide, titanium butoxide, titanium isobutoxide, cerium oxide, cerium oxide, isopropoxide Butadiene oxide, isobutyl oxidation, and the like. On the other hand, the loose structure portion (B) is a structural unit represented by the above-described general formula (4) by removing the residue (or substituent) of the three-dimensional polyhedral structural skeleton in the structural unit represented by the above general formula (1). composition. In other words, the structural unit shown by the above general formula (1) removes the structure of the compact structure portion (4) and the structural unit shown by the above general formula (π). More specifically, 'according to the following description, a mixture of R3R4R5six, R6R7six: or diterpene: (but, as long as the ruler 7 and the oxime is the same as the general formula (4)) a bond structure of a metal oxide and an organic group bonded to a metal atom in the general formula (1). In other words, a three-dimensional polyhedral structure skeleton in a structural unit represented by the general formula (I) is removed. The residue (or substituent)] composition is preferred. The above general formula (]];) is not connected to the structure of the early system, and may be one or more compounds of the compound of the genus of the genus or the genus of the genus Or a condensation reaction in the presence of a base catalyst

The R7 series has the same principle as the general formula ("...to 7"

; K to R have the same meaning. When one of R3 to R 319624 13 200817176 'is an unsaturated group, if it is represented by a preferable specific example, for example, '3-methylpropenyloxypropyl, 3-propenyloxypropyl, aryl Base, vinyl, and styryl. The X-based halogen atom or the alkoxy group may, for example, be a chlorine, a bromine, a methoxy group, an ethoxy group, a n-propoxy group or an isopropoxy group. Preferred examples of the compound represented by R3R4R5SiX include, for example, trimethylchlorodecane, vinyldimethylchlorodecane, dimethylchlorodecane, phenyldimethylchlorodecane, phenylchlorodecane, and triethyl. Chlorodecane, trivinyl chlorodecane, methyl divinyl chlorodecane, allyl dimethyl chloro decane, 3-methyl propyl propyloxypropyl monomethyl chopping, 3- propylene oxypropyl Dimethylchlorodecane, styryldimethylchlorodecane, trimethylmethoxydecane, vinyl dimethyl ethoxy decane, dimethyl decyl decane, phenyl dimethyl methoxy decane , phenyl methoxy decane, triethyl decyl decane, trivinyl methoxy decane, methyl divinyl methoxy decane, allyl dimethyl methoxy decane, 3- methacryl醯 丙基 曱 曱 甲 methoxy decane, 3 _ propylene methoxy propyl dimethyl methoxy decane, styryl dimethyl methoxy decane, trimethyl ethoxy decane, vinyl dioxime Ethoxy decane, dimethyl ethoxy decane, phenyl dimethyl ethoxy decane, phenyl ethoxy decane, triethyl ethoxy ruthenium Alkane, trivinyl ethoxy decane, methyl divinyl ethoxy decane, propyl propyl dimethyl ethane decane, 3- methacryl methoxy dimethyl methoxy decane, 3- Propylene methoxypropyl dimethyl ethoxy decane, styryl dimethyl ethoxy oxime, tridecyl propoxy decane, vinyl dimethyl propoxy decane, dimethyl propoxy decane , phenyl dimethyl propoxy decane, phenyl propoxy decane, triethyl propoxy decane, tri 319624 14 200817176 • vinyl propoxy decane, methyl divinyl propoxy decane, allylic Dimethylpropoxydecane, 3-methylpropenyloxypropyldimethylpropoxy aspartate, 3-propylenesulfonyloxypropyldimethylpropoxydecane, styryldimethylpropane Base decane, trimethyl isopropoxy decane, vinyl dinonyl isopropoxy decane, dimethyl isopropoxy decane, phenyl dimethyl isopropoxy decane, phenyl isopropoxy decane , triethylisopropoxydecane, trivinylisopropoxydecane, methyldivinylisopropoxydecane, allyldimethylisopropoxyfluorene , 3-dimethyl-oxopropyl Bing Xixi isopropoxy Silane, Bing Xixi Gamma] 3- oxopropyl dimethyl isopropoxy Silane, dimethyl styrene Silane isopropoxy and the like. Preferred examples of the compound represented by R6R7SiX2 include, for example, dimercapto chlorite, vinylmethyl chlorite, dichlorocarbazone, allyl methyl dichloride. I, methyl dichloride, methyl phenyl dichlorite, methyl ethyl dichlorite, ethyl vinyl dichlorite, ethyl propyl dichlorite, benzene Vinylmethyldichloro-I, Styryl Ethyl Chloride, 3-Methylpropenyloxypropylmethyldichlorodecane, Dimethyldimethoxydecane, Vinylmethyldimethoxy Base stone kiln, dimethoxy dimethoxy zebao, allyl methyl dimethoxy shixi, methyl dimethoxy zebao, methyl phenyl = milk base, methyl ethyl Methoxy money, ethyl vinyl dimethoate ethylallyl dimethoxy methoxy, styryl methyl dimethyl two: Xizhuo - phenylethyl ethyl dioxylate Methyl propylene oxime Γ Γ ^ ^ ^? Oxygen, dimethyldiethoxy (tetra), ethoxylate, dioxycarbazide, diethyl diethoxy sulphur, dipropylmethyldiethylene, methylene Oxy (tetra) 1 -phenylphenyldiethoxy Shi Xi Xuan, 319624 15 200817176 • 'Alkyl diethyl ethoxy decane, allyl diethoxy sulphur, phenethyl oxalate, ethyl isopropyl ethyl Diethoxylated, Q-methyl-ethyl-etheric acid, phenethyl sulphate, dimethyl A: propane 1 _methyl propylene oxypropylmethyldiethoxy (tetra), base =-: Bis = dipropoxyl material 1 phenyl phenyl 2 base 2 基 base Shi Xi 垸, B 7 7 Hagan - soil ethyl propylene oxide 垸 垸, benzene benzene ^ dipropoxy zexi, B Base propyl dipropoxy group 垸 垸 3, 3 甲 Γ 苯 苯 妇 乙基 二 ▲ & & 乳 乳 乳 乳 甲基 甲基 甲基 甲基 乳 乳 乳 乳 乳 乳 乳 乳 乳 乳 乳 乳 乳Diisopropoxyl money, base money, methylene diisopropoxy alcohol, methyl dihydroxan 1 stone = pit, f-phenyl phenylisopropoxy oxalate, methyl ethyl diisopropyl = 凡, ethyl vinyl diisopropoxy zebra, ethyl propyl propyl : Styryl methyl diisopropoxy zebra, styrene 2 Shi Xixuan and other propyl milk base stone court, 3_ methyl propyl oxypropyl methyl diisopropoxy 2 sclerosing The resin is capable of reacting the cage-reduced resin represented by the above formula (1) with the cerium oxide compound represented by the above general formula (8): the hardened bollard obtained by the above-mentioned formula has the spleen ten by the above-mentioned general formula And the molecular structure of the unsaturated bond of the structural unit represented by the above general formula (ιι) is hydrolyzed and condensed. Moreover, the stacking coefficient calculated by the free volume fraction of the curable resin is between 0.68 and 〇8 = the molded portion (4), the loose structure portion with the rock cutting coefficient of less than 0.68, and has at least one unsaturated bond. . 319624 16 200817176

The Kp system is calculated from the following formula (2) Density, Mw = min. Calculated by the stacking factor formula (2) used in the present invention. Κρ=Αη · Vw · p/Mw (only 'An=Afoga number, vw==Wandeva volume), among them, '

Vw=EVa

Va=47c/R3-El/37ihi2(3R-hi) hi=R — (R2+ di2 — Ri2)/2di (only, R=good half 彳f, Ri, junction atom radius, and when calculating the above-mentioned rockfill coefficient , the atomic radius of the atomic distance) is contained in the basics of the chemical nature of the Sakamoto Chemical Society. In other words, the atomic radius is H = 12 a, 〇 == 152 A, e = h7 A, Si = 2.14, and the distance between atoms is H - (2) A, Si-〇u63A, Si - 〇 = 1_^ ^, Bu A. For example, the glass density is 2.23 g/cm3 in terms of M = Shi Xi atom, (4), w = 2, y = 〇, and z = 一般, and the number of piles (10) is Q 747. Taking the density of octamethyl octoxide (sllsesqui〇xane) of the general formula (1) wherein R is methyl and v=8, w=〇, y=〇, and z=〇 cube structure k 1 4% / cm3 and the stacking factor is 〇697. Further, the density of the octamethylcyclotetracycline having a ring structure of the general formula (2) and the r7 smethyl group and j=〇, k=4, and dike is 0.956 g/cm 3 , and Its pile cutting coefficient is 〇·576. Similarly, the density system of octamethyltrioxane having a chain structure of 3 and R4, R5, R6 and R7 as a methyl group and j=2, k=l, and 1=0 is 〇82〇g/cm3. And its stacking coefficient is 0.521. In other words, the metal oxide having a three-dimensional polyhedral structure in which a ruthenium atom is bonded to an oxygen atom on 319624 17 200817176 is 0.69 or more, and is a compact structure portion of the present invention. Further, the packing coefficient of the compound of the chain structure is 〇 576 and Q 52 to form a loose portion of the present invention. X 2 In the curable resin of the present invention, the weight ratio (8)/(8) of the compact structure portion (A) to the loose structure portion (8) is 〇〇1 to 5〇〇, and more preferably U to 3.0. When (4)/(B) is less than 〇·〇10, the compact structure is too small, and the mechanical properties and heat resistance of the molded body obtained by molding the curable resin and curing the resin are remarkably deteriorated. Further, when the weight ratio is more than or equal to the above, the loose structural portion of the molded body is too small, and (4) is remarkably deteriorated and becomes a weak molded body. Further, the curable resin of the present invention has an average molecular weight of from 8 (8) to 6 Å. If the average molecular weight is less than _, it tends to become brittle after molding. On the contrary, if it is 6_〇, the hardening molding process becomes difficult and it may cause non-freeness in use. Further, the average molecular weight can be measured by a well-known coffee measuring device. 6 7 is an acid catalyst used for the hydrolysis and condensation of a compound represented by RSiX3 or ΜΧ4, and a compound represented by R3ws or R7SiX2, and 5', for example, hydrochloric acid and sulfuric acid. Further, these may be used in combination, and the hydrogen halide formed at the time of hydrolysis may also be used when the hydrolyzable group is a halogen atom. In the case of an alkaline catalyst used for hydrolysis and condensation, for example, a metal hydroxide such as a hydroxide clock, sodium hydroxide or barium hydroxide, or tetramethylammonium hydroxide or tetraethylammonium hydroxide can be exemplified. , tetrabutyl hydride, chlorobenzene; 319624 18 200817176 dimethylammonium hydride, phenyl hydrazinium triethylammonium hydride, especially from the point of high catalyst activity:: ammonium salt: this Wait for it. An organic solvent is usually used as an inert catalyst. Methylammonium is required to have water in the hydrolysis reaction system, but this liquid is confessed, &gt; 丌s4 λ u ? Temple has been dissolved by the water of the catalyst: ^ The amount of water is more than the hydrolysis of the hydrolyzable group. It is 1 to 15 times the theoretical amount. In the case where the curable resin is used as a curable resin group: a compound having at least a hydrogen group in a molecule prepared by a bi-type resin, the sub-form is at least "solid" An oligomer and a monomer of an atom on a ruthenium atom. An oligomer having a ruthenium atom on a shi 原子 atom 而 ^ 卞 可 可 可 可 可 可 可 可 可 可 可 可 可 可 可 可 可 可 可 可 可 可 可 可 可 可 可 可Two: a hydrogen oxy-oxygen group and a copolymer thereof, and a terminal end is a sulphur-oxygenated gas modified by dimethyl chlorite, and further, a monomer having a hydrogen atom on the lithium atom. In other words, for example, a cyclic ten-oxygen wire such as tetramethylcyclotetraoxane or pentamethylcyclopentazepine, H-oxide, trihydrogen, dihydromonodecane, or monohydrogen can be exemplified. Two or more types of decanes, dimethyl methoxy oxanes, and the like may be mixed. Further, the compound having an unsaturated group prepared by a curable resin is roughly classified into a repeating number of structural units. Reactive monomer to polymer of about 2 、, reactive monomer with low molecular weight and low viscosity. a monofunctional unsaturated compound having one unsaturated group and a polyfunctional unsaturated compound having two or more unsaturated groups. In the case of a reactive oligomer, for example, a polyvinyl siloxane, a poly Dimethylvinyl methoxy methoxy oxanes and copolymers thereof, the ends are oxiranes, epoxy acrylates, epoxidized oleic acid acrylates modified by two 19 319 624 200817176 , methyl vinyl fluorenyloxy groups , urethane acrylate, polyester and polyester, polyester acrylate, polyether acrylate, acetoacetate, polyester/thiol, oxime acrylate, polybutylene a olefin, a polystyryl styrene ethyl acrylate, etc. Among these, a monofunctional unsaturated compound and a polyfunctional unsaturated compound are contained. In the case of a reactive monofunctional monomer, for example, triethylethylene is exemplified. Ethyl-substituted sulphate, cyclohexene (such as cyclic olefins, styrene, vinyl acetate, N-vinylpyrrolidone, butyl acrylate, acrylic acid 2-) Ethylhexyl ester, n-hexyl acrylate, cyclohexyl acrylate, N-decyl enoate, isobornyl acrylate (isoborny 1), dicyclopentenyloxyethyl acrylate, phenoxyethyl acrylate, trifluoroethyl methacrylate, etc. In the case of reactive polyfunctional monomers, For example, an ethylene-substituted fluorene compound such as tetravinylsulfonium or divinyltetradecyldioxane, tetramethyltetramine/vinylcyclotetraoxane or pentadecylpentavinylcyclopentanyloxy Ethylene and other ethylene-substituted cyclic hydrazine compounds, bis(trimethyl decyl) acetylene, diphenyl acetylene and other acetylene bamboo organisms 'n〇rb〇rnadiene, dicyclopentadiene, cyclooctadiene, etc. Vinyl-substituted cyclic olefins such as polyenes, vinylcyclohexene, divinylbenzenes, diacetylenylbenzenes, trimethylolpropane diallyl ether, pentaerythritol triallyl ether, Tripropylene glycol dipropionate, 1,6-hexanediol diacrylate, bisphenol aglycidyl ether diacrylate, tetraethylene glycol diacrylate, hydroxypivalic acid ( Pivalic acid) neopentyl glycol diacrylate, trioxane propane tripropylene 20 319624 200817176 The purpose of the acid is: pentaerythritol triacetic acid vinegar, pentaerythritol tetra (tetra) (tetra), perylenetetraol hexaacrylate, and the like. In the case of a compound having an unsaturated group in the substituent, various reactive oligomers and monomers can be produced other than those exemplified above. Further, the oligomer and the monomer may be used alone or in combination of two compounds having at least a hydrogen group in the molecule used in the present invention, and a compound having an unsaturated group in the molecule may be used alone or in combination. More than 2 types are available. (In the present invention, the curable resin or the radical initiator may be adjusted in a curable resin, or both may be blended to obtain a curable resin. After the absence, the curable resin composition may be thermally hardened. Or Guangwei, to obtain a hard transparent substrate by chlorination and free radical polymerization. In addition, a compound of at least j chlorinated groups in the molecule may be added by adding a catalyst and a radical initiator. Further, the compound having an unsaturated group is further blended to obtain a curable resin composition. In other words, the cured resin is cured to obtain a hard transparent (the purpose of the substrate and the purpose of improving the physical properties of the obtained cured transparent substrate) to promote the reaction. The additive is formulated with a Lixi hydrogenation catalyst, a silking starter, a photopolymerization initiator, a photoinitiator, a sensitizer, etc. to obtain a hardened composition. Once the compound is added, the Shixi hydrogenation catalyst is taken The amount is preferably in the range of from 1 to 1 ppm, more preferably from 2 to 5 ppm, relative to the weight of the curable resin. When blending with a photopolymerization initiator or heat Aggregation = J When it is a radical initiator, it is added in an amount relative to the hardenability tree, so that it is in the range of 0.1 to 5 parts by weight, and is in the range of 319 319 624 21 2008 17176 to 3 parts by weight. More on the right. ~ Add this summer dissatisfaction 0. 1 Re-deployment, the hardening is insufficient, and the strength and rigidity of the formed body obtained by the knives are reduced. ^More than 5 parts by weight on the right side In addition, it is possible to use two or more types of the coloring of the molded body. The chlorinated catalyst may be, for example, chlorinated or gas (CM〇r_t surface). Acid), chloropropanoic acid and alcohol, disk, § the same complex (4) and hydrazine complex, _ ethylene oxy-combustion complex, two carbon base, chlorinated deficiency (four), (four) touch metal In this right, from the point of view of the activity of the catalyst, it is preferable to use a chlorine (10), a chloroauric acid plate, a fine compound, a complex compound, and a vinyl compound. These may be used alone or in combination of two or more. Photopolymerization used in the case of a photocurable composition As the starting agent, a compound such as acetaminophen, azulene (b_in), diphenylketone or 嗟_(10) can be suitably used, and a compound such as th_) or a phosphinyl oxide can be used. For example, trichloroacetamidine, diethoxyacetic acid benzene, benzyl-2-methyl propyl ketone, p-cyclohexyl phenyl ketone, 2-methyl-H4_methyl. thiophene (10). ))_2_吗淋基丙-1-酉, benzoin methyl scale, benzyl ketal (ketai), diphenyl ketone, oxime, oxidized 2,4,6•trimethylbenzene Formic acid diphenylphosphine, acetonic acid (gly〇xy (tetra)methyl benzene vinegar, camphor sputum (camph〇rquin〇ne), benzoin, oxime, ketone (Michier, sketne) and the like. In addition, it is also possible to use a combination of a photopolymerization initiator and a priming agent and a sensitizer. 0 319624 22 200817176 It is a hydrogen peroxide system, a peroxidation-based system, a bismuth peroxide system, Peroxydi-alkane various organic peroxides. With a heartfelt (4), such as restrictions. : Foreign: 1:, 2-B (four), but not used in combination. (,, w initiator can be used alone or in two kinds of modified resin compositions, can be used in various applications such as J: r plus various additives. Various additives are examples, A foaming agent: a crystal component, etc. U colorant, a crosslinking agent, a dispersing aid, a resin, such as the above-mentioned hard transparent substrate of the present invention, which can contain any one of the radical polymerization initiators, or both It is formed into a predetermined shape, and then, by heating or light irradiation, 1, 2, ί, :::, when manufacturing a copolymer (hard transparent substrate), 2 2 The agent and the accelerator can be selected from room temperature to the wide range. In this case, the hard transparent substrate of the desired shape can be obtained by combining the inside of the mold and the steel strip. More specifically, the injection molding and extrusion General forming processing for press forming, boring, I 钿 forming, transfer forming, cal-forming, casting (injection molding) 319624 23 200817176 - The method can be applied. Photopolymerization by light irradiation to produce a hard transparent substrate, with a purple wavelength of 1.0 to 400 nm The line and the visible light of 4 〇〇 to the hard transparent substrate can be obtained. The wavelength of the light used is not particularly limited, but it is more suitable to use the near-line of the wavelength 200 i 4 〇〇 nm. For the source lamp, for example, a low-pressure mercury lamp (output: 0.4 to sample/cm), a high-dust mercury lamp (4〇 to l6〇w; _, an ultra-high pressure mercury lamp (10) i 435w/cm), a metal-based lamp (10) to 160 W/cm), pulsed xenon lamp (8 〇 to 12 〇 w/cm), electrodeless discharge/lamp (80 to l2 〇 W/cm) f. These ultraviolet lamps are selected according to the type of photoinitiator used, since they have their own knowledge of the spectroscopic cloth. In the method of obtaining a hard transparent substrate by light irradiation, it is exemplified that a curable resin composition is formed in a mold having a Cavity shape and is made of a transparent material such as quartz glass, and the ultraviolet ray is further formed. a method of producing a hard transparent substrate of a desired shape by demolding the lamp from the outer line of the lamp, and using a doctor blade on the private steel V in the case where the mold is not used. Or a roll-form coating = a method of forming a hard transparent resin composition of the present invention, which is formed by hardening the above-mentioned ultraviolet lamp to produce a sheet-like rigid transparent substrate. Further, in the present invention, a method of obtaining a hard transparent substrate by heating and light irradiation may be used in combination. The hard transparent substrate obtained by hardening the hardening resin in the present invention is excellent, especially the light transmittance of light having a wavelength of 55 〇 nm is 319624 24 200817176 • at 80% or more, Since the birefringence is 2 Å or less, it is possible to obtain various display devices by laminating electronic materials for various display devices. In other words, if the light transmittance is less than 8〇%, when color or the like is displayed, it is difficult to use because the surface is darkened, so there is a tendency to use it only for applications such as a monochrome display element, and if the birefringence is larger than When m is used as a display panel, there is a tendency for color unevenness to occur on the surface. However, since the hard transparent substrate of the present invention has the above-described characteristics, it is obtained by various display devices. The thickness of the hard transparent substrate varies depending on the type of display device. For example, the liquid crystal display device is in a phase of 〇1〇 to 2〇〇. If it is less than O.Hhnm, it is easy to bend due to the weight of the substrate itself, and the manufacturing process of the liquid crystal display device using the conventional glass substrate cannot be used. On the other hand, if it exceeds 2. 〇〇mm, the weight becomes the same as that of the conventional glass substrate of 15 to 0.7 mm, and the weight is reduced. The preferred embodiment of the present invention will be described below using the drawings. The first drawing is a cross-sectional view of a liquid crystal display device using an electronic material for various display devices and a hard transparent substrate of the present invention, and is a more suitable example of a hard-shell transparent substrate using the present invention. In this case, the display device uses an electronic material such as a transparent electrode, an alignment film, a liquid crystal layer, a color filter, a ruthenium film transistor, a polarizing plate, and a backlight, and a color filter and a transparent electrode are laminated on the hard transparent substrate. And the liquid crystal i-th member of the alignment film and the second member in which the thin film transistor and the alignment film are laminated on the hard transparent substrate sandwich the liquid crystal layer so that the alignment films face each other, and are hard in the liquid crystal first member A polarizing plate is disposed outside the transparent substrate, and a polarizing plate and a backlight are disposed outside the hard transparent substrate of the liquid crystal second structure 319624 25 200817176. Here, a gas barrier film may be provided on both surfaces of the above-mentioned hard transparent substrate. In the case of a liquid crystal display device, the transparent electrode may, for example, be a conductive material such as indium oxide, tin oxide, gold, silver, copper or nickel. These may be used alone or in combination of two or more. In view of the balance between transparency and conductivity, indium tin oxide usually consisting of a mixture of 99 to 90% of indium oxide and 2 to 1% by weight of tin oxide (hereinafter referred to as It is especially ideal for "IT〇". The method of forming the transparent electrode can be carried out by a conventional vacuum vapor deposition method, a sputtering method, an ion plating method, or a chemical vapor deposition method. Among them, the sputtering method is preferable from the viewpoint of adhesion. The thickness of the above transparent electrode is usually in the range of 500 to 2000 A from the viewpoint of the balance of transparency and conductivity. Fig. 2 is a cross-sectional view showing a touch panel display device formed using an electronic material of various display devices and a hard transparent substrate of the present invention. For the Lu's 'display device', the electronic materials include at least a transparent electrode, a dot spacer, a polarizing plate, and a liquid crystal display, and a Japanese yen coin. One of the transparent % poles is such that the touch panel member sandwiches the dot spacers 1 so that the transparent electrodes are placed on each other (four faces), and the polarizing plate is disposed on each of the touch panel structures = at the same time The control panel member is disposed in addition to the polarizing plate, and is mainly provided with a liquid crystal display device. Here, a gas barrier film can be disposed on both sides of the hard transparent substrate. : Transparency: The cross section of the organic EL display device formed by the substrate is more than a transparent electrode, 319624 26 200817176 - a hole transport layer, a light emitting layer, an electron transport layer, a metal electrode, and a gas barrier film, On the hard transparent substrate, a transparent electrode, a hole injection layer, an electric layer, a light-emitting layer, an electron transport layer, and a metal electrode are laminated. Here, J can be integrally sealed by a gas barrier film outside the drawing. , can also be transparent substrate The gas barrier film is provided on both sides of the organic EL display device. For example, the illuminant layer is made of zinc sulfide, sulphide, or metal electrode. ^ f The electronic material for the display device is laminated on the hard transparent substrate. The gas barrier film which is disposed between the hard transparent substrate and the display j as needed may be, for example, an inorganic oxide film or a = copolymer ((4) 'EVAL quotient. Hunger, s. Diethyl = and gas tree (4) 'But the ideal inorganic oxide film. The second, refers to the metal, non-metal, sub-metal: chemical, oxidized ore, oxidation: zinc: oxidation record, indium oxide, oxygen, turn, oxidation Free of two emulsified iron, copper oxide, nickel oxide, chemical, antimony oxide, etc.: oxygen: Dihua town, oxidation chain, oxidation pin, oxygen can contain trace metals: not 1 inch is not ideal. Oxide, in addition, for the method of metal monomer or chlorine oxide to form a gas barrier film, "may == may suitably contain carbon or fluorine. Form = inorganic oxide (8);: film = tree: etc. ::Method, * method, CVD method using a vacuum base shovel to form a coating Conventionally known methods γ, - splashing method, ion battery method, 319624 27 200817176 There is no particular limitation on the thickness of the gas barrier film, although it varies depending on the type of the gas barrier film, but the oxygen gas barrier property is removed. In addition to the water vapor barrier property, if the economy is considered, the film thickness is preferably 5 to 5 Qnm. If the film thickness is less than 5, the film may be island-shaped and the film may not be formed. The tendency of the uniform film is not so good. In order to further obtain high oxygen gas barrier properties and water vapor barrier properties, the film thickness may be increased, but if it exceeds 5 Onm, productivity is poor and the cost is increased, and transparency is also associated with evil. Therefore, it is not preferable. The following shows an example of the present invention. Further, the curable resin used in the following examples is obtained by the method shown in the following synthesis example. (Synthesis Example) A 4-liter 4-liter flask equipped with a stirrer and a dropping funnel was charged with 300 mL of isopropyl alcohol, 600 mL of toluene, and 22.37 g of a 2% w% aqueous solution of tetramethylammonium hydroxide (tetramethylammonium hydroxide 4 55 g). / 〇〇5m〇i, water 0.99mol). A mixed solution of vinyltrimethoxyoxane 0·3^η〇1 and isopropyl alcohol 5〇mL was placed in a dropping funnel, and the reaction vessel was stirred while dropping at room temperature for 3 hours. After the end of the drip, it will disturb 3 hours without heating. After stirring for 3 hours, the stirring was stopped and the reaction solution was allowed to heat at room temperature for 18 hours. The reaction solution was added to 〇·1M aqueous citric acid solution π and neutralized, and washed with water to neutrality, and then anhydrous magnesium sulfate was added for dehydration. After removing anhydrous magnesium sulfate, it was concentrated under reduced pressure. The concentrate was dissolved in 2 mL of dehydrated tetrahydrofuran, and placed in a 4-liter flask equipped with a stirrer and a dropping funnel. Add dehydrated pyridine h00mL to the reaction vessel and add dimercapto dichloride 319624 28 200817176 to the dropping funnel, decane 3.2g / 〇. 〇 25m 〇: I, trimethylchloro decane 2 7g / 〇〇 25m 〇 [With 30 mL of tetrahydrofuran, the reaction vessel was stirred while flowing under a nitrogen stream while dropping at room temperature for 3 hours. After the completion of the dropwise addition, the mixture was stirred for 3 hours without heating. After 3 hours of disruption, after adding 3 〇〇 mL of toluene, the reaction solution was washed with water to neutrality, and then anhydrous magnesium sulfate was added for dehydration. After removing anhydrous magnesium sulfate, it was concentrated under reduced pressure to give 27.1 g of a sclerosing resin (general formula (1)) as a colorless transparent liquid. In the 1H-NMR of the curable resin, a sharp signal of a vinyl group was observed, and it was confirmed that the hydrolyzed condensate hydrolyzed from vinyltrimethoxy decane was a cage structure. Therefore, the compact structure portion (A) of the three-dimensional polyhedral structure composed of a metal oxide, that is, cerium oxide, can be assumed to be composed of eight austenite atoms and twelve oxygen atoms (Si〇3/2). 8 represents the cube structure, and the derived Kp# G.73. Further, the portion other than the (A) of the curable resin is a vinyl group of (H2C=CH-Si〇3/2)8 and a loose structure portion of (MhSiO/2) and (MejiO). ), from this, the ratio/weight ratio [(A)/(B)] is 1.3〇2. In addition, the average molecular 罝Μη from Gpc is 5200. Further, when Κρ of the compact structure portion (A) is calculated, (SA/2)8 is a part of (4) and it is impossible to obtain Kp* directly as a part existing in the resin of the general formula (1). Therefore, (HSiC^2)8 was used as the compound having the least influence on Kp and the closest approximation. (Example 1) 100 parts by weight of the curable resin obtained in the synthesis example and monocumyl peroxide ( Japan Oil & Fat Co., Ltd. percumyl weight 319624 29 200817176 • The parts are mixed until uniform to obtain a hardenable resin composition. This is poured into a mold which is combined into a glass plate to have a thickness of 〇.2 mm, heated in lOOt: hour, at In 120 ° C, hour, 14 〇t, 1 hour, 16 generations; small dry, and 18 〇t: 2 hours to obtain a molded body (hard transparent substrate). (Example 2) will be synthesized 58 parts by weight of the curable resin obtained in the example, 42 parts by weight of a terminal trimethyl decyl group-modified polymethylhydroquinone oxy-fired (HMS-992 manufactured by Azmax Co., Ltd.), and a trans-vinyl oxalate complex. No., Co., Ltd. 8ΙΡ6830·3)〇·5 weight The mixture was mixed until uniform to obtain a curable resin composition, and this was poured into a mold which was combined with a glass plate to have a thickness of 0.2 mm, and was heated at 10 (rc for 1 hour, at 12 Torr. 〇 hour, at 14 〇) A molded body (hard transparent substrate) was obtained in 1 hour, 1 hour in the middle, and 18 hours in a crucible. (Example 3) 58 parts by weight of the curable resin obtained in the synthesis example, and the end 3) formazan-based modified polymethylhydrogen oxide (HMS-992, manufactured by Azmax Co., Ltd.) 2 parts by weight, dicumyl peroxide (Japanese oil company has limited company PERCUMYL D) 2 parts by weight And a mixture of 5 parts by weight of fluorene-vinyl oxo-oxygenate (SIp683 〇.3, manufactured by Azmax Co., Ltd.) was uniformly mixed to obtain a curable resin composition. This was poured into a glass plate: a synthetic mold. The thickness was 0.2 mm. The molded body was obtained by heating at 10 (rc for 1 hour, at 12 °C for 1 hour, at 14 °C for 1 hour, at 16 (TC for 1 hour, and at 180t for 2 hours). (Hard transparent substrate). On the hard transparent substrate obtained in Examples 1 to 3, respectively, 319624 30 200817 176. First, a gas barrier film composed of tantalum oxide having a thickness of 1 〇nm is formed by sputtering, and then an ITO film (transparent electrode) having a thickness of 150 nm is formed on the gas barrier film by a sputtering method to obtain a hard transparent substrate. The test laminate was provided with a transparent electrode, and the obtained test laminate was evaluated by the following method: &lt;Heat resistance&gt; In the Vicat Softening test, the indenter sectional area 1.0mm, load 5Kg, temperature rise rate 50 °C / hr under the measurement conditions, below 120 ° C, the indenter enters 〇. 4mm or more, marked as X, enter /, 0.2 to 0.4mm, marked as △, at 0· Substantially less than 1mm is not marked as Ο. <Birefringence> The birefringence in the plane was measured at a wavelength of 400 to 80 nm using a phase difference measuring device (manufactured by Nikon, NPDM-1000). &lt;Light Transmittance&gt; The transmittance at a wavelength of 550 nm was measured using a spectrophotometer of Hitachi, Ltd. v &lt; Roughness (Ra) of surface of ITO film &gt; Surface roughness measurement by AFM. The measurement range was 10 // m, and the measurement was performed under tapping mode. &lt;Flexibility&gt; The test laminate was wound with a mandrel having a diameter of 25 mm, and when it was bent at 90 degrees, the crack was marked as 〇 and the crack was marked as X. Evaluation of heat resistance, birefringence, light transmittance, surface roughness of ITO film, and bendability of the laminated body for testing obtained in Examples 1 to 3 31 319624 200817176 • The evaluation results are shown in Table 1. [Table 1]

Further, the test laminated body obtained in the first to third embodiments is used on the side of the touch-sensitive type panel member, and the other side touch panel member is used on the glass substrate in the same manner as described above. Forming transparent conductive, 溥 film. The two touch panel members are disposed as a touch panel test body via the epoxy beads having a diameter of 30 #m so that the transparent conductive films face each other. The touch panel test body obtained in this way was evaluated in the following manner. (Comparative Example 1) A spear-type measuring body was produced in the same manner as in Examples 1 to 3 except that the poly-glycolic acid ethylene diester was used in the same manner as in the first to third embodiments. 1) Heat-resistant discoloration: If there is no change in the hot air circulation of 12〇°C, it will be marked as ^When the combined touch panel test body is treated for 120 hours, the color change of the substrate and the coloration of yellowing are confirmed. For X. 2) Pen slip test: 250 g of crushed stone horse was hung on a polyacetal pen (tip shape: 0.8 mmR) 319624 32 200817176 A sliding test of 200,000 times was performed. No whitening was observed in the sliding portion, and no abnormality was observed in the ON resistance, and 标示, whitening, and on-resistance were observed as abnormalities. Guide 3) Button test: hang 25 〇g on the polyacetal pen (tip shape: 0.8mmR) and perform 1 million key test. If there is no abnormality at 0N resistance, the indication ', ' is observed as X. .....

The results of the film formability, the two-color discoloration, the pen slip test, and the button test of the touch panel test body obtained by using the laminated system obtained in the above Examples i to 3 and Comparative Example J are as shown in the watch factory. ..., [Table 2] No.

BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a cross-sectional view showing a liquid crystal display device formed using an electronic material for a display device and a hard substrate of the present invention. Fig. 2 is a view showing an electronic material for a display device and a hard surface of the present invention. BenQ, a cross-sectional view of the formed touch panel display device. Fig. 3 is an organic EL sea (1) hard shell through the electronic material of the display device and the hard substrate of the present invention. Sectional diagram of the device is not installed. 319624 33

Claims (1)

200817176, Shen Qing patent range ·············································································· The Japanese type 2 is obtained by the 'the above-mentioned curable resin is a metal oxide having a different coefficient KP. (10) to. .8 into a tight child, a structural part (A), and a loose structural part (Β) composed of the above-mentioned Kp* · organic matter or organic matter and an organometallic oxide, π Rtfc &amp; A) / (B) weight ratio, · 5.0 〇, and has at least one unsaturated bond and an average molecular weight of 800 to 60,000, -{(A) ~ (B)m} η- (1) (only, m and η are integers above 1) Kp=An - yw . p/Mw (7) Molecular weight, Vw=SVa, Va=47c/R3 —sl/3; ihi2(3Ra—μ), hi=Ra—(Ra2+di2 ~ Ri2)/2di, Ra = atomic radius, Ri = bonding atom radius, and di = atomic distance). (Only 'An = Yafo's number of turns, Vw = Van der Waals volume, p = density, Mw = / such as the patent | &amp; surrounding the first item of the display device, wherein the tight structure part (A) has removed The metal oxide portion of the three-dimensional polyhedral structure of the organic substance portion of the following general formula (I), the loose structure portion (B) is composed of the organic substance portion of the general formula (I) and the following general formula (1): (RSi03/ 2) w(M02)x(RXSi〇)y(XM〇3/2)z (1) (R3R4R5Si01/2)j(R6R7si〇)k { R6R7xsi〇1/2} j (Π) (only, R is (a) — R1 — 〇c〇~ CR2=CH2, (b) — R1 — 319624 34 .200817176 .CR2=CH2 or (4)—CH=CH2 represents an unsaturated group, a fluorenyl group, a cycloalkyl group, a cycloalkene a group, a phenyl group, a hydrogen atom, an alkoxy group, or an alkyloxy group; and a plurality of R in the formula (1) may be different from each other, but at least one of the groups includes (a), (b), (4) In addition, R1 represents an alkyl group, a decyl group or a phenyl group, and R2 represents hydrogen or a thio group, and R3 to r7 are as (4)-rI _ 0C0 — CR2=CH2, (8) _ Rl — cr2=cH2 Or (4) - CH=CH2 represents an unsaturated group, an alkyl group, a cycloalkyl group, a ring a group, a phenyl group, a hydrogen atom, an alkoxy group, or an alkyloxy group, M is a metal atom of ruthenium, osmium, titanium, or zirconium, X is an atom of an atom, or an alkoxy group, ... is 4 or more The integers, X, y, and z are integers satisfying w+x+y+zg8; and j, k, and 1 respectively represent integers above )). 3. The display device of claim 2, wherein The structural unit of (A) in the general formula (1) is a general formula of a hydrolysis condensate obtained from RSiX3, MX4 or this mixture (except that R, M and X are the same as in the general formula (1)) The metal oxide portion of the three-dimensional polyhedral structure skeleton in the structural unit shown in I). 4. The display device according to the second aspect of the patent application, wherein the general structural unit is a chain unit of a metal oxide represented by the general formula (π) produced by a hydrolysis condensate of R3R4R5SiX, R6R7SiX2 or a mixture thereof (except for R7&amp;x and the general formula (8)), and a general formula (1) The organic base of the metal atom bond contained in the structure shown. 5. The display device according to any one of the items of the present invention, wherein the curable resin composition is obtained by formulating a catalyzed catalyst and/or a radical from the curable resin to obtain a curable resin composition. The curable resin composition is shaped 'and thermally cured or photohardened (four) to a rigid transparent substrate. 6. The display device of claim 5, wherein the further compounding 'has at least! A compound of a hydrogen group and a compound having an unsaturated group are used to obtain a curable resin composition. 7. The display device of any one of the patents to the sixth to the sixth, wherein the display device is a liquid crystal display device, wherein the display device uses at least a transparent electrode, an alignment film, a liquid crystal layer, a color filter, a film, a crystal, a polarizing plate, and a backlight. The liquid crystal display device is provided with a color filter, a transparent electrode, and an alignment film on a hard shell transparent substrate, and is transparent and transparent. A thin film transistor and a liquid crystal second member are laminated on the substrate such that the alignment film faces each other with the surface layer and the outer surface of the hard transparent substrate of the liquid crystal first member is disposed opposite to the second liquid crystal. 2 members of the hard f transparent substrate outside the polarizer and backlight. 1 8.=Please display the display H of any one of items 1 to 6 of the patent range as an organic rainbow display, wherein the display electronic material has at least a transparent electrode, a light-emitting layer for a hole, an electron transport layer, The metal electric θ A / the same transport layer, the EL display device is in the hard transparent plate; the gas film, and the organic:: the main entry layer, the hole transport layer, the luminescent layer, the electron transport layer: the electrode, and the gas barrier The film is sealed and sealed. The main genus 9. The second patent application scope! The display device of any one of the items to the sixth item is a touch panel display, wherein the display device 319624 36 200817176 'the electronic material has at least a transparent electrode, and the display device is touched. The control panel display 2: a polarizing plate, and a transparent electrode formed on the liquid crystal-to-touch; =^ hard transparent substrate working panel member, so that the transparent electric and the face-to-face manner sandwich the point spacer, and A polarizing plate is disposed on the outer side of the touch panel member, and a liquid crystal display device is further disposed on the outer side of the touch panel member. The display device according to any one of the items 7 to 9, wherein a gas barrier film is further disposed between the hard transparent substrate and the transparent electrode. i 37 319624