JP4920364B2 - Display device - Google Patents

Description

  The present invention is a display device in which electronic materials for a display device are laminated using a novel hard transparent substrate in place of a conventional glass substrate, for example, a personal computer, an AV device, a mobile phone, an information communication device, a game or a simulation The present invention relates to a display device used in various fields such as a device and a vehicle-mounted navigation system.

  With the rapid advancement of electronics technology, the fields of liquid crystal display devices, touch panels, and optoelectronics are expanding. In general, a photoelectronic element is used for various applications by forming the element on a glass substrate having a transparent conductive layer. However, the glass substrate has a large weight, and when incorporated in a portable device, there is a problem that the weight of the device increases due to the large specific gravity of the glass substrate. Therefore, weight reduction is strongly desired, and a sheet substrate made of plastic sheets such as polyarylate, polyethersulfone, polycarbonate, etc., which is relatively excellent in strength, transparency, heat resistance, etc., is adopted as a hard substrate to replace the glass substrate. It is being done.

  However, since these present sheet substrates have a thickness of about 0.1 mm, they lack rigidity compared to conventional glass substrates. In order to give rigidity, the film thickness can be increased, but the solvent casting method generally used to obtain a sheet substrate is actually thick due to foaming, poor planarity, and residual solvent. The production of about 0.2 mm is the limit. In addition, for application to liquid crystal elements, the birefringence of the sheet substrate is usually 20 nm or less, preferably 10 nm or less. It is difficult to manufacture the body. Therefore, for example, an optical plastic sheet in which two sheets having a low birefringence index are laminated has been proposed (see Patent Document 1). However, since such a sheet is a thermoplastic resin, its rigidity is small and chemical resistance is also low. There is a drawback of being greatly inferior. In addition, an optical sheet in which a surface layer of a base material sheet is coated with a curable resin has been proposed (see Patent Document 2). In such a sheet, the curable resin on the side surface of the sheet is swollen by a solvent during substrate cleaning. In addition to being inferior in chemical resistance, there is a problem that the rigidity of the substrate is not sufficient.

  In particular, in the field of optoelectronic devices, since higher optical properties, gas barrier properties, electrical conductivity, mechanical strength, etc. are required, a substrate having a multilayer structure composed of multiple layers or films having each function is actually used. It has been. For example, a laminate in which a cured film is provided on both sides of a plastic molded body, a conductive film is provided on one side, and a metal oxide film is provided on the other side has been proposed. However, this laminated body has a problem that cracks are easily generated in the plastic molded body during heating due to a difference in properties of each layer and a problem of adhesion.

On the other hand, it is a plastic sheet substrate useful as a glass substitute substrate, but in order to increase the utility value, it is necessary to have not only light weight but also flexibility. That is, when the substrate is bent (bent) with a certain curvature, it is necessary to maintain electrical conductivity without cracking the conductive film. However, the conventional plastic sheet substrate has a problem that its bending resistance is insufficient.
JP 7-36023 A JP-A-6-116406 Japanese Patent Laid-Open No. 2-5308

  The object of the present invention is a hard material having strength, transparency, heat resistance, and dimensional stability like inorganic glass, high toughness and workability like plastic, and excellent flex resistance. An object of the present invention is to provide a display device using a transparent substrate and laminating various electronic materials for display devices.

  As a result of intensive studies to obtain a new substrate in place of the conventional glass substrate, the present inventors have found that a curable resin having a dense structure portion and a sparse structure portion having different free volume fractions in the molecular structure. By curing, it is possible to obtain a hard transparent substrate that has both the excellent performance of a glass substrate and a plastic sheet substrate, and also has excellent bending resistance. The present invention was completed by finding it suitable as an alternative to the glass substrate used in the apparatus.

That is, the present invention is a display device formed by laminating electronic materials for display devices on a hard transparent substrate, and the hard transparent substrate cures a curable resin represented by the following general formula (1). The obtained curable resin has a dense structure portion (A) composed of a metal oxide having a packing coefficient Kp of 0.68 to 0.8 calculated by the following calculation formula (2). And a sparse structural part (B) composed of an organic substance or an organic substance having an Kp of less than 0.68 and an organic metal oxide, and the weight ratio of the structural part (A) / (B) is 0.01. A display device having a molecular weight of 800 to 60,000, having at least one unsaturated bond.
− {(A) − (B) _m } _n − (1)
(However, m and n represent an integer of 1 or more.)
Kp = An · Vw · p / Mw (2)
(However, An = Avogadro number, Vw = Vandee Waals volume, p = Density, Mw = Molecular weight, Vw = ΣVa, Va = 4π / R ³ −Σ1 / 3πhi ² (3Ra-hi), hi = Ra− (Ra ² + di ² −R i ² ) / 2di, Ra = atomic radius, Ri = bonding atomic radius, and di = interatomic distance.

In the present invention, the dense structural part (A) is a metal oxide part having a three-dimensional polyhedral structure excluding the organic part of the following general formula (I), and the sparse structural part (B) The above-mentioned display device comprising an organic part of the formula (I) and the following general formula (II).
(RSiO _3/2 ) _w (MO ₂ ) _x (RXSiO) _y (XMO _3/2 ) _z (I)
(R ³ R ⁴ R ⁵ SiO _1/2 ) _j (R ⁶ R ⁷ SiO) _k {R ⁶ R ⁷ XSiO _1/2 } _l (II)
(Wherein, R represents ^{(a) -R 1 -OCO-CR} 2 = CH 2, (b) -R 1 -CR 2 = CH 2 or (c) an unsaturated group represented by -CH = CH _2, alkyl group , A cycloalkyl group, a cycloalkenyl group, a phenyl group, a hydrogen atom, an alkoxyl group, or an alkylsiloxy group, and a plurality of R in the formula (I) may be different from each other, but at least one of (a ), (B), or (c), R ¹ represents an alkylene group, an alkylidene group, or a phenylene group, R ² represents hydrogen or an alkyl group, and R ^{3 to} R ⁷ represent (a) —R ¹ —OCO—CR ² ═CH ₂ , (b) —R ¹ —CR ² ═CH ₂ or (c) an unsaturated group represented by —CH═CH ₂ , an alkyl group, a cycloalkyl group, a cycloalkenyl group , Phenyl group, hydrogen atom, alkoxyl group, or alkylsiloxy group M is a metal atom of silicon, germanium, titanium, or zirconium, X is a halogen atom, or an alkoxyl group, w is an integer of 4 or more, and x, y, and z are integers that satisfy w + x + y + z ≧ 8 J, k, and l are each an integer of 0 or more.)

Here, the metal oxide part which is a three-dimensional polyhedral structure skeleton in the structural unit represented by the general formula (I) is RSiX ₃ , MX ₄ or a mixture thereof (provided that R, M and X are represented by the general formula ( It is the same as (I)) in the structural unit resulting from the hydrolytic condensate), or the structural unit represented by the general formula (II) is a R ³ R ⁴ R ⁵ SiX, R ⁶ R ⁷ SiX ₂ or a mixture thereof (provided that R ^{3 to} R ⁷ and X are the same as those in the general formula (II)). The organic group bonded to the chain unit and the metal atom is a preferred embodiment of the present invention.

  In the present invention, the curable resin is blended with a hydrosilylation catalyst or a radical initiator, or both a hydrosilylation catalyst and a radical initiator are blended to form a curable resin composition, and then the curing is performed. The transparent resin composition may be cured to obtain a hard transparent substrate. Specifically, the curable resin composition blended as described above may be molded into a predetermined shape and then thermoset or photocured to obtain a molded body (hard transparent substrate). Further, the curable resin composition may contain a hydrosilylatable compound having at least one hydrosilyl group in the molecule, or a compound having an unsaturated group in the molecule, or both of them. May be.

  The hard transparent substrate obtained by the present invention has strength, transparency, heat resistance, and dimensional stability like inorganic glass, and has high toughness and workability like plastic, and also has bending resistance. Because of its superiority, it can be used in place of glass substrates used in display devices in various fields, including liquid crystal display devices, touch panel display devices, and organic EL display devices, to demonstrate the performance of conventional glass substrates and plastic sheet substrates. However, it is possible to provide a display device that is further excellent in light weight and impact resistance.

Hereinafter, the present invention will be described more specifically.
The curable resin of the present invention has a molecular structure composed of a dense structural part (A) and a sparse structural part (B) as represented by the general formula (1), and has at least one unsaturated component. Have a bond. Here, the dense structural part (A) is a structural part composed of metal oxide parts having a packing coefficient Kp of 0.68 to 0.8, and the sparse structural part (B) has a packing coefficient Kp of 0. It is a structural part composed of an organic part or organic part less than 68 and an organic metal oxide part.

  The dense structural part (A) is preferably a metal oxide part which is a three-dimensional polyhedral structural skeleton in the structural unit represented by the general formula (I). In the general formula (I), at least one of R is preferably an organic group having an unsaturated group represented by the above formulas (a) to (c). Note that the plurality of R in the general formula (I) may not all be the same.

The structural unit represented by the general formula (I) is composed of a three-dimensional polyhedral structure and R. As an example, w in the general formula (I) is 8 and x, y, and z are 0. In the case, w is 10 and x, y and z are 0, and a specific example of a structure in which w is 12 and x, y and z are 0 is represented by the following structural formulas (3), (4) and ( Shown in 5). However, the structural unit represented by the general formula (I) is not limited to those shown in the structural formulas (3), (4) and (5). These structures are publicly known and have been shown by X-ray crystal structure analysis for specific functional groups.

The metal oxide moiety in the structural unit represented by the general formula (I) is subjected to hydrolysis and condensation reaction of one or more compounds represented by RSiX ₃ or MX ₄ in the presence of an acid or base catalyst. Can be obtained at Here, R, X and M have the same meaning as R, X and M in formula (I).

  A part of R is preferably an unsaturated group represented by the above (a), (b) or (c), but a specific example of a preferable unsaturated group is a 3-methacryloxypropyl group. , 3-acryloxypropyl group, aryl group, vinyl group, and styryl group.

  X is a hydrolyzable group of a halogen atom or an alkoxyl group. Specific examples include chlorine, bromine, methoxy group, ethoxy group, n-propoxyl group, and i-propoxyl group.

Preferred examples of the compound represented by RSix ₃ include trichlorosilane, methyltrichlorosilane, ethyltrichlorosilane, isopropyltrichlorosilane, butyltrichlorosilane, t-butyltrichlorosilane, cyclohexyltrichlorosilane, phenyltrichlorosilane, and vinyltrichlorosilane. Allyltrichlorosilane, styryltrichlorosilane, cyclohexenyltrichlorosilane, trimethoxysilane, methyltrimethoxysilane, ethyltrimethoxysilane, isopropyltrimethoxysilane, butyltrimethoxysilane, t-butyltrimethoxysilane, cyclohexyltrimethoxysilane, Phenyltrimethoxysilane, vinyltrimethoxysilane, allyltrimethoxysilane, styryltrimethoxysilane, cyclo Hexenyltrimethoxysilane, triethoxysilane, methyltriethoxysilane, ethyltriethoxysilane, isopropyltriethoxysilane, butyltriethoxysilane, t-butyltriethoxysilane, cyclohexyltriethoxysilane, phenyltriethoxysilane, vinyltriethoxysilane Allyltriethoxysilane, styryltriethoxysilane, cyclohexenyltriethoxysilane, tripropoxysilane, methyltripropoxysilane, ethyltripropoxysilane, isopropyltripropoxysilane, butyltripropoxysilane, t-butyltripropoxysilane, cyclohexyltri Propoxysilane, phenyltripropoxysilane, vinyltripropoxysilane, allyltripropoxysilane, still Tripropoxysilane, cyclohexenyltripropoxysilane, methacryloxymethyltriethoxysilane, methacryloxymethyltrimethoxysilane, 3-methacryloxypropyltrichlorosilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, Examples include 3-acryloxypropyltrimethoxysilane and 3-acryloxypropyltrichlorosilane.

M is silicon, germanium, titanium, or zirconium. Here, preferable examples of the compound represented by MX ₄ are tetrachlorosilane, tetramethoxysilane, tetraethoxysilane, tetrachlorogermane, tetramethoxygermane, tetraethoxygermane, titanium ethoxide, titanium propoxide, titanium isoform. Examples thereof include propoxide, titanium butoxide, titanium isobutoxide, zirconium ethoxide, zirconium propoxide, zirconium isopropoxide, zirconium butoxide, zirconium isobutoxide and the like.

On the other hand, the sparse structural part (B) is represented by the residue (or substituent) excluding the three-dimensional polyhedral structural skeleton in the structural unit represented by the general formula (I) and the general formula (II). Consisting of structural units. In other words, it consists of a part obtained by removing the dense structural part (A) from the structural unit represented by the general formula (I) and the structural unit represented by the general formula (II). More specifically, as described below, R ³ R ⁴ R ⁵ SiX, R ⁶ R ⁷ SiX ₂ or a mixture thereof (provided that R ^{3 to} R ⁷ and X are the same as those in formula (II)). ) And a metal oxide chain structure represented by the general formula (II) obtained from the hydrolysis condensate of the organic group bonded to the metal atom in the general formula (I) [that is, the general formula (I) And a residue (or substituent) excluding the three-dimensional polyhedral structure skeleton in the structural unit represented by

The structural unit represented by the general formula (II) is obtained by hydrolysis and condensation of one or more compounds represented by R ³ R ⁴ R ⁵ SiX or R ⁶ R ⁷ SiX ₂ in the presence of an acid or base catalyst. Obtained by carrying out the reaction. Here, R < ³ > -R < ⁷ > has the same meaning as R < ³ > -R < ⁷ > of general formula (II). When a part of R ^{3 to} R ⁷ is an unsaturated group, a preferred specific example includes a 3-methacryloxypropyl group, a 3-acryloxypropyl group, an aryl group, a vinyl group, and a styryl group. X is a halogen atom or an alkoxyl group, and specific examples include chlorine, bromine, methoxy group, ethoxy group, n-propoxyl group, and i-propoxyl group.

Preferred examples of the compound represented by R ³ R ⁴ R ⁵ SiX are trimethylchlorosilane, vinyldimethylchlorosilane, dimethylchlorosilane, phenyldimethylchlorosilane, phenylchlorosilane, triethylchlorosilane, trivinylchlorosilane, methyldivinylchlorosilane, allyldimethylchlorosilane. , 3-methacryloxypropyldimethylchlorosilane, 3-acryloxypropyldimethylchlorosilane, styryldimethylchlorosilane, trimethylmethoxysilane, vinyldimethylmethoxysilane, dimethylmethoxysilane, phenyldimethylmethoxysilane, phenylmethoxysilane, triethylmethoxysilane, trivinyl Methoxysilane, methyldivinylmethoxysilane, allyldimethylmethoxysilane, 3-methacrylic Xylpropyldimethylmethoxysilane, 3-acryloxypropyldimethylmethoxysilane, styryldimethylmethoxysilane, trimethylethoxysilane, vinyldimethylethoxysilane, dimethylethoxysilane, phenyldimethylethoxysilane, phenylethoxysilane, triethylethoxysilane, trivinylethoxysilane , Methyldivinylethoxysilane, allyldimethylethoxysilane, 3-methacryloxypropyldimethylethoxysilane, 3-acryloxypropyldimethylethoxysilane, styryldimethylethoxysilane, trimethylpropoxysilane, vinyldimethylpropoxysilane, dimethylpropoxysilane, phenyldimethyl Propoxysilane, phenylpropoxysilane, triethylpropoxysilane, Vinylpropoxysilane, methyldivinylpropoxysilane, allyldimethylpropoxysilane, 3-methacryloxypropyldimethylpropoxysilane, 3-acryloxypropyldimethylpropoxysilane, styryldimethylpropoxysilane, trimethylisopropoxysilane, vinyldimethylisopropoxysilane, dimethyl Isopropoxysilane, phenyldimethylisopropoxysilane, phenylisopropoxysilane, triethylisopropoxysilane, trivinylisopropoxysilane, methyldivinylisopropoxysilane, allyldimethylisopropoxysilane, 3-methacryloxypropyldimethylisopropoxysilane, 3 -Acryloxypropyldimethylisopropoxysilane, styryldimethylisopropoxysilane And the like.

Preferred examples of the compound represented by R ⁶ R ⁷ SiX ₂ include dimethyldichlorosilane, vinylmethyldichlorosilane, divinyldichlorosilane, allylmethyldichlorosilane, methyldichlorosilane, methylphenyldichlorosilane, methylethyldichlorosilane, Ethylvinyldichlorosilane, ethylallyldichlorosilane, styrylmethyldichlorosilane, styrylethyldichlorosilane, 3-methacryloxypropylmethyldichlorosilane, dimethyldimethoxysilane, vinylmethyldimethoxysilane, divinyldimethoxysilane, allylmethyldimethoxysilane, methyldimethoxy Silane, methylphenyldimethoxysilane, methylethyldimethoxysilane, ethylvinyldimethoxysilane, ethylallyldimethoxysilane, styryl Methyldimethoxysilane, styrylethyldimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, dimethyldiethoxysilane, vinylmethyldiethoxysilane, divinyldiethoxysilane, allylmethyldiethoxysilane, methyldiethoxysilane, methylphenyldiethoxy Silane, methylethyldiethoxysilane, ethylvinyldiethoxysilane, ethylallyldiethoxysilane, styrylmethyldiethoxysilane, styrylethyldiethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, dimethyldipropoxysilane, vinylmethyl Dipropoxysilane, divinyldipropoxysilane, allylmethyldipropoxysilane, methyldipropoxysilane, methylphenyldipropoxysilane, methylethyl Rudipropoxysilane, ethylvinyldipropoxysilane, ethylallyldipropoxysilane, styrylmethyldipropoxysilane, styrylethyldipropoxysilane, 3-methacryloxypropylmethyldipropoxysilane, dimethyldiisopropoxysilane, vinylmethyldiisopropoxy Silane, divinyldiisopropoxysilane, allylmethyldiisopropoxysilane, methyldiisopropoxysilane, methylphenyldiisopropoxysilane, methylethyldiisopropoxysilane, ethylvinyldiisopropoxysilane, ethylallyldiisopropoxysilane, styryl Examples thereof include methyldiisopropoxysilane, styrylethyldiisopropoxysilane, and 3-methacryloxypropylmethyldiisopropoxysilane.

  The curable resin of the present invention can be obtained by reacting the cage siloxane resin represented by the general formula (I) with the silicone compound represented by the general formula (II). The functional resin has a molecular structure in which unsaturated bonds of the structural units represented by the general formula (I) and the general formula (II) are condensed by crosslinking or hydrolysis condensation. The curable resin includes a dense structural portion (A) having a packing coefficient calculated from a free volume fraction of 0.68 to 0.8 and a sparse structural portion having a packing coefficient of less than 0.68 (B And at least one unsaturated bond.

The packing coefficient Kp used in the present invention is calculated from the following calculation formula (2).
Kp = An ・ Vw ・ p / Mw (2)
(However, An = Avogadro number, Vw = Vandee Waals volume, p = Density, Mw = Molecular weight.)
Vw = ΣVa
Va = 4π / R ³ −Σ1 / 3πhi ² (3R-hi)
hi = R- (R ² + di ² -Ri ² ) / 2di
Where R = atomic radius, Ri = bonded atomic radius, and d = interatomic distance.

In the calculation of the packing coefficient, the values described in the revised 3rd edition of the Chemical Handbook of Chemical Society of Japan were used for the atomic radius and interatomic distance. In other words, atomic radii are H = 1.2 mm, O = 1.52 mm, C = 1.7 mm, Si = 2.14 mm, interatomic distances are HC = 1.08 mm, CC = 1.541 mm, Si-C = 1.863 mm and Si-O = 1.609 mm. For example, the density of the glass that can be represented by M = silicon atom, v = 0, w = 2, y = 0, and z = 0 in the general formula (1) is 2.23 g / cm ³ and the packing coefficient is 0. 747. The density of octakismethylsilsesquioxane having a cubic structure in which R in the general formula (1) is a methyl group and v = 8, w = 0, y = 0, and z = 0 is 1.49 g / cm ³ and packing The coefficient is 0.697. In addition, the density of octamethylcyclotetrasiloxane having a cyclic structure in which R ⁶ and R ^{7 in} the general formula (2) are methyl groups and j = 0, k = 4, and l = 0 is 0.996 g / cm ³ . The packing factor is 0.576. Similarly, the density of octamethyltrisiloxane having a chain structure in which R ³ and R ⁴ , R ⁵ , R ⁶ , and R ⁷ are methyl groups and j = 2, k = 1, and l = 0 is 0.820 g. / cm ³ and the packing coefficient is 0.521. That is, the packing coefficient of a metal oxide having a three-dimensional polyhedral structure in which silicon atoms are bonded to three or more oxygen atoms is 0.69 or more, which is a dense structural portion in the present invention. The packing coefficients of the compounds having a cyclic and chain structure are 0.576 and 0.521, which is a sparse structural site in the present invention.

  In the curable resin of the present invention, the constituent weight ratio (A) / (B) of the dense structural part (A) and the sparse structural part (B) is 0.01 to 5.00, preferably 0.5 to 3. .00. When (A) / (B) is smaller than 0.01, the dense structure is too small, and the mechanical properties and heat resistance of a molded product obtained by molding and curing a curable resin are significantly deteriorated. Moreover, in the case of 5.00 or more, there are too few sparse structure parts which give a softness | flexibility to a molded object, and toughness will deteriorate remarkably and will become a weak molded object.

  The curable resin of the present invention has an average molecular weight of 800 to 60000. If the average molecular weight is less than 800, it tends to become brittle after molding, while if it exceeds 60,000, it may be difficult to cure and process, and it may cause inconvenience in handling. The average molecular weight can be measured with a known GPC measuring device.

Acid catalysts used for the hydrolysis and condensation of the compound represented by RSiX ₃ or MX ₄ and the compound represented by R ³ R ⁴ R ⁵ SiX or R ⁶ R ⁷ SiX ₂ include hydrochloric acid and sulfuric acid. It is done. Moreover, these can also be used in mixture, and when a hydrolyzable group is a halogen atom, you may utilize the hydrogen halide produced | generated at the time of hydrolysis.

  Basic catalysts used for hydrolysis and condensation include alkali metal hydroxides such as potassium hydroxide, sodium hydroxide, cesium hydroxide, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrabutylammonium hydroxide, Examples thereof include ammonium hydroxide salts such as benzyltrimethylammonium hydroxide and benzyltriethylammonium hydroxide. Among these, tetramethylammonium hydroxide is preferably used because of its high catalytic activity. The basic catalyst is usually used as an aqueous solution.

  In the hydrolysis reaction, the presence of water is essential, but this can be supplied from an aqueous solution of the catalyst or may be added as water separately. The amount of water is not less than an amount sufficient to hydrolyze the hydrolyzable group, preferably 1.0 to 1.5 times the theoretical amount.

  When the curable resin is made into a curable resin composition, the compound having at least one hydrosilyl group in the molecule blended in the curable resin is present on at least one hydrosilylatable silicon atom in the molecule. These are oligomers and monomers having hydrogen atoms. Examples of the oligomer having a hydrogen atom on a silicon atom include polyhydrogensiloxanes, polydimethylhydroxysiloxanes and copolymers thereof, and siloxanes whose ends are modified with dimethylhydrosiloxy. Examples of monomers having a hydrogen atom on a silicon atom include cyclic siloxanes such as tetramethylcyclotetrasiloxane and pentamethylcyclopenta, dihydrodisiloxanes, trihydromonosilanes, dihydromonosilanes, and monohydromonosilanes. And dimethylsiloxysiloxanes, and two or more of these may be mixed.

  In addition, the compound having an unsaturated group to be blended in the curable resin is roughly classified into a reactive oligomer which is a polymer having a structural unit repeating number of about 2 to 20, and a reactive monomer having a low molecular weight and a low viscosity. Is done. Moreover, it divides roughly into the monofunctional unsaturated compound which has one unsaturated group, and the polyfunctional unsaturated compound which has two or more.

  Examples of reactive oligomers include polyvinylsiloxanes, polydimethylvinylsiloxysiloxanes and copolymers thereof, siloxanes modified with dimethylvinylsiloxy at the ends, epoxy acrylates, epoxidized oil acrylates, urethane acrylates, unsaturated polyesters, Examples thereof include polyester acrylate, polyether acrylate, vinyl acrylate, polyene / thiol, silicone acrylate, polybutadiene, and polystyrylethyl methacrylate. These include monofunctional unsaturated compounds and polyfunctional unsaturated compounds.

  Examples of reactive monofunctional monomers include vinyl-substituted silicon compounds such as triethylvinylsilane and triphenylvinylsilane, cyclic olefins such as cyclohexene, styrene, vinyl acetate, N-vinylpyrrolidone, butyl acrylate, 2-ethylhexyl acrylate, n- Examples include hexyl acrylate, cyclohexyl acrylate, n-decyl acrylate, isobornyl acrylate, dicyclopentenyloxyethyl acrylate, phenoxyethyl acrylate, trifluoroethyl methacrylate, and the like.

  Examples of reactive polyfunctional monomers include vinyl-substituted silicon compounds such as tetravinylsilane and divinyltetramethyldisiloxane, vinyl-substituted cyclic silicon compounds such as tetramethyltetravinylcyclotetrasiloxane and pentamethylpentavinylcyclopentasiloxane, and bis (trimethylsilyl). ) Acetylene derivatives such as acetylene and diphenylacetylene, cyclic polyenes such as norbornadiene, dicyclopentadiene, cyclooctadiene, vinyl-substituted cyclic olefins such as vinylcyclohexene, divinylbenzenes, diethynylbenzenes, trimethylolpropane diallyl ether, penta Erythritol triallyl ether, tripropylene glycol diacrylate, 1,6-hexanediol diacrylate, bisphenol A Glycidyl ether diacrylate, tetraethylene glycol diacrylate, hydroxypivalic acid neopentyl glycol diacrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, it can be exemplified dipentaerythritol hexaacrylate.

  As the compound having an unsaturated group in the molecule, various reactive oligomers and monomers other than those exemplified above can be used. These reactive oligomers and monomers may be used alone or in combination of two or more.

  The compound having at least one hydrosilyl group in the molecule and the compound having an unsaturated group in the molecule may be used alone or in combination of two or more.

  In this invention, you may make it mix | blend a hydrosilylation catalyst or a radical initiator with curable resin, or mix | blend both and obtain a curable resin composition. And a hard transparent substrate can be obtained by thermosetting or photocuring this curable resin composition and carrying out hydrosilylation or radical polymerization. Further, in addition to the hydrosilylation catalyst and the radical initiator, a compound having at least one hydrosilyl group or a compound having an unsaturated group in the molecule may be further blended to obtain a curable resin composition. That is, for the purpose of curing a curable resin to obtain a hard transparent substrate, and for the purpose of improving the physical properties of the obtained hard transparent substrate, hydrosilylation catalyst, thermal polymerization initiator, thermal polymerization accelerator as additives for promoting the reaction. A curable resin composition is obtained by blending a photopolymerization initiator, a photoinitiation assistant, a sharpening agent, and the like.

  When the hydrosilylation catalyst is blended, the addition amount is preferably 1 to 1000 ppm, more preferably 20 to 500 ppm as a metal atom with respect to the weight of the curable resin. When blending a photopolymerization initiator or a thermal polymerization initiator as a radical initiator, the amount added is preferably in the range of 0.1 to 5 parts by weight with respect to the curable resin, and in the range of 0.1 to 3 parts by weight. More preferably. If this addition amount is less than 0.1 parts by weight, curing will be insufficient and the strength and rigidity of the resulting molded product will be low. On the other hand, when it exceeds 5 parts by weight, there is a possibility that problems such as coloring of the molded product may occur. Further, the hydrosilylation catalyst and the radical initiator may be used alone or in combination of two or more.

  Hydrosilylation catalysts include platinum chloride, chloroplatinic acid, chloroplatinic acid and alcohol, aldehyde, ketone complexes, chloroplatinic acid and olefin complexes, platinum and vinylsiloxane complexes, and dicarbonyldichloroplatinum. And platinum group metal catalysts such as palladium catalysts and rhodium catalysts. Among these, from the viewpoint of catalytic activity, chloroplatinic acid, a complex of chloroplatinic acid and olefins, and a complex of platinum and vinylsiloxane are preferable. These may be used alone or in combination of two or more.

  As the photopolymerization initiator used when the curable resin composition is a photocurable composition, it is preferable to use an acetophenone-based, benzoin-based, benzophenone-based, thioxanthone-based, acylphosphine oxide-based compound, or the like. it can. Specifically, trichloroacetophenone, diethoxyacetophenone, 1-phenyl-2-hydroxy-2-methylpropan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1- (4-methylthiophenyl) -2 -Morpholinopropan-1-one, benzoin methyl ether, benzyldimethyl ketal, benzophenone, thioxanthone, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, methylphenylglyoxylate, camphorquinone, benzyl, anthraquinone, Michler's ketone, etc. can do. Moreover, the photoinitiator adjuvant and the sharpening agent which show an effect in combination with a photoinitiator can also be used together.

  Examples of the thermal polymerization initiator used for the above purpose include ketone peroxides, peroxyketals, hydroperoxides, dialkyl peroxides, diacyl peroxides, peroxydicarbonates, peroxyesters, etc. Various organic peroxides can be suitably used. Specifically, cyclohexanone peroxide, 1,1-bis (t-hexaperoxy) cyclohexanone, cumene hydroperoxide, dicumyl peroxide, benzoyl peroxide, diisopropyl peroxide, t-butylperoxy-2-ethyl Although hexanoate etc. can be illustrated, it is not restrict | limited at all to this. These thermal polymerization initiators may be used alone or in combination of two or more.

  Various additives can be added to the curable resin composition of the present invention within a range not departing from the object of the present invention. Various additives include organic / inorganic fillers, plasticizers, flame retardants, heat stabilizers, antioxidants, light stabilizers, UV absorbers, lubricants, antistatic agents, mold release agents, foaming agents, nucleating agents, colorants, Crosslinking agents, dispersion aids, resin components and the like can be exemplified.

  As described above, the hard transparent substrate of the present invention is formed by forming a curable resin composition containing either or both of a hydrosilylation catalyst and a radical polymerization initiator into a predetermined shape and curing it by heating or light irradiation. Can be manufactured. When a copolymer (hard transparent substrate) is produced by heating, the temperature can be selected from a wide range from room temperature to around 200 ° C., depending on the selection of a thermal polymerization initiator and an accelerator. In this case, a hard transparent substrate having a desired shape can be obtained by polymerization and curing in a mold or on a steel belt. More specifically, all of general molding methods such as injection molding, extrusion molding, compression molding, transfer molding, calendar molding, and cast (casting) molding are applicable.

  Moreover, when manufacturing a hard transparent substrate by photocopolymerization by light irradiation, a hard transparent substrate can be obtained by irradiating the ultraviolet rays with a wavelength of 1.0-400 nm and the visible light with a wavelength of 400-700 nm. The wavelength of the light to be used is not particularly limited, but near ultraviolet light having a wavelength of 200 to 400 nm is particularly preferably used. The lamps used as ultraviolet light sources include low-pressure mercury lamps (output: 0.4 to 4 W / cm), high-pressure mercury lamps (40 to 160 W / cm), ultra-high pressure mercury lamps (173 to 435 W / cm), metal halide lamps (80 ˜160 W / cm), pulse xenon lamp (80 to 120 W / cm), electrodeless discharge lamp (80 to 120 W / cm), and the like. Each of these ultraviolet lamps is characterized by its spectral distribution, and is therefore selected according to the type of photoinitiator used.

  As a method for obtaining a hard transparent substrate by light irradiation, for example, a curable resin composition is injected into a mold having an arbitrary cavity shape and made of a transparent material such as quartz glass, and ultraviolet rays are emitted from the above ultraviolet lamp. The method of producing a hard transparent substrate of a desired shape by performing polymerization and curing by irradiating with a mold, or when not using a mold, for example, a doctor blade or roll on a moving steel belt A method of producing a sheet-like hard transparent substrate can be exemplified by applying the curable resin composition of the present invention using a coater and polymerizing and curing with the above-described ultraviolet lamp. 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 curing the curable resin in the present invention is excellent in transparency, specifically, the light transmittance at a light wavelength of 550 nm is 80% or more, and the birefringence is 20 nm. Since it is the following, various display apparatuses can be obtained by laminating various electronic materials for display apparatuses. That is, when the light transmittance is less than 80%, in the case of color display or the like, the screen becomes dark and difficult to use and tends to be used only for applications such as monochrome display elements, and the birefringence is larger than 20 nm. In the case of a display panel, there is a tendency that color unevenness of the display screen occurs. However, the hard transparent substrate of the present invention is suitable for obtaining various display devices because it has the above characteristics.

  The thickness of the hard transparent substrate varies depending on the type of display device, but for example, in the case of a liquid crystal display device, it is preferably 0.10 to 2.00 mm. If it is less than 0.10 mm, it is easy to bend by the weight of the substrate, and there is a possibility that a manufacturing process of a liquid crystal display device using a conventional glass substrate cannot be used. On the other hand, when it exceeds 2.00 mm, it will become the same weight as the conventional glass substrate of 1.5-0.7 mm, and will remove | deviate from the objective of weight reduction.

Hereinafter, preferred embodiments of the present invention will be described with reference to the accompanying drawings.
FIG. 1 is a cross-sectional explanatory view of a liquid crystal display device formed using various electronic materials for display devices and the hard transparent substrate of the present invention, and is a preferred example using the hard transparent substrate of the present invention. In this case, the electronic material for the display device is, for example, a transparent electrode, an alignment film, a liquid crystal layer, a color filter, a thin film transistor, a polarizing plate, and a backlight, and the color filter, the transparent electrode, and the alignment film are stacked on a hard transparent substrate. The liquid crystal first member and the liquid crystal second member in which the thin film transistor and the alignment film are stacked on the hard transparent substrate sandwich the liquid crystal layer so that the alignment films face each other, and the liquid crystal first member A polarizing plate is disposed outside the hard transparent substrate, and a polarizing plate and a backlight are disposed outside the hard transparent substrate of the liquid crystal second member. Here, a gas barrier film may be provided on both surfaces of the hard transparent substrate.

  In the case of a liquid crystal display device, examples of the transparent electrode include conductive materials such as indium oxide, tin oxide, gold, silver, copper, and nickel. These may be used alone or as a mixture of two or more thereof. In general, indium tin oxide (hereinafter referred to as “ITO”) made of a mixture of 99 to 90% indium oxide and 1 to 10% tin oxide is transparent. It is particularly preferable from the viewpoint of balance of conductivity. The method for forming the transparent electrode can be performed using a conventionally known vacuum deposition method, sputtering method, ion plating method, chemical vapor deposition method or the like. Of these, the sputtering method is preferable from the viewpoint of adhesion. The thickness of the above transparent electrode is usually preferably in the range of 500 to 2000 mm from the viewpoint of balance between transparency and conductivity.

  FIG. 2 is a cross-sectional explanatory view of a touch panel display device formed using various electronic materials for display devices and the hard transparent substrate of the present invention. That is, the electronic material for a display device is at least a transparent electrode, a dot spacer, a polarizing plate, and a liquid crystal display device, and a pair of touch panel members in which a transparent electrode is formed on a hard transparent substrate are opposed to each other. Hold the dot spacer. A polarizing plate is disposed outside each touch panel member, and a display device such as a liquid crystal display device is disposed outside any one of the touch panel members in addition to the polarizing plate. Here, a gas barrier film may be provided on both surfaces of the hard transparent substrate.

  FIG. 3 is a cross-sectional explanatory view of an organic EL display device formed using various display device electronic materials and the hard transparent substrate of the present invention. That is, the electronic material for a display device is at least a transparent electrode, a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, a metal electrode, and a gas barrier film, and the transparent electrode and the hole are formed on the hard transparent substrate. An injection layer, a hole transport layer, a light emitting layer, an electron transport layer, and a metal electrode are laminated. Here, the whole may be sealed with a gas barrier film not shown. Moreover, you may make it provide a gas barrier film on both surfaces of the said hard transparent substrate. In the case of this organic EL display device, for example, zinc sulfide, cadmium sulfide, zinc selenide or the like is used for the light emitting layer, and aluminum or the like is used for the metal electrode.

  When laminating the display device electronic material on the hard transparent substrate, the gas barrier film provided between the hard transparent substrate and the display device electronic material may be an inorganic oxide film or an ethylene-vinyl alcohol copolymer. Gas barrier resin layers such as coalesced (for example, Eval brand names Eval, Soarnol), vinylidene chloride and the like can be mentioned, and an inorganic oxide film is preferable. Inorganic oxides are metal, non-metal, and sub-metal oxides. Specific examples include aluminum oxide, zinc oxide, antimony oxide, indium oxide, calcium oxide, cadmium oxide, silver oxide, gold oxide, and chromium oxide. , Silicon oxide, cobalt oxide, zirconium oxide, tin oxide, titanium oxide, iron oxide, copper oxide, nickel oxide, platinum oxide, palladium oxide, bismuth oxide, magnesium oxide, manganese oxide, molybdenum oxide, vanadium oxide, barium oxide, etc. And silicon oxide is particularly preferred. The inorganic oxide may contain trace amounts of metals, non-metals, sub-metals alone or their hydroxides, and carbon or fluorine as appropriate in order to improve flexibility. Examples of the method for forming the gas barrier film include a method of coating a resin or the like, and a method of forming a vapor deposition film made of an inorganic oxide. As a method for forming the deposited film, a conventionally known method such as a vacuum deposition method, a vacuum sputtering method, an ion plating method, a CVD method, or the like can be used.

  The thickness of the gas barrier film is not particularly limited, and may vary depending on the type of components of the gas barrier film. However, in consideration of the oxygen gas barrier property and the water vapor barrier property as well as the economy, the thickness of the film is 5 to 50 nm. preferable. If the thickness of the film is less than 5 nm, there is a possibility that a portion where the film is not formed is formed because the film is in an island shape, and there is a tendency that a uniform film cannot be obtained. In order to obtain a higher oxygen gas barrier property and water vapor barrier property, the thickness of the film may be increased. However, if it exceeds 50 nm, the productivity is poor, the cost is increased, and the transparency is deteriorated.

  Examples of the present invention will be described below. In addition, the curable resin used for the following Example was obtained by the method shown to the following synthesis example.

[Synthesis example]
A 2 L 4-neck flask equipped with a stirrer and a dropping funnel was charged with 300 mL of isopropyl alcohol and 600 mL of toluene, 22.37 g of a 20 w% tetramethylammonium hydroxide aqueous solution (4.55 g / 0.055 mol of tetramethylammonium hydroxide, 17.82 g / water). 0.99 mol) was charged. A mixed solution of 44.4 g / 0.30 mol of vinyltrimethoxysilane and 50 mL of isopropyl alcohol was charged into the dropping funnel, and the mixture was added dropwise at room temperature over 3 hours while stirring the reaction vessel. After completion of dropping, the mixture was stirred for 3 hours without heating. After stirring for 3 hours, stirring was stopped and the reaction solution was aged at room temperature for 18 hours. The reaction solution was neutralized by adding to 1 L of 0.1 M citric acid aqueous solution and further washed with water until neutral, and then anhydrous magnesium sulfate was added for dehydration. Anhydrous magnesium sulfate was filtered off and concentrated under reduced pressure. The concentrate was dissolved in 200 mL of dehydrated tetrahydrofuran and charged into a 1 L 4-neck flask equipped with a stirrer and a dropping funnel. Add 1.00 mL of dehydrated pyridine to the reaction vessel and 3.2 g / 0.025 mol of dimethyldichlorosilane, 2.7 g / 0.025 mol of trimethylchlorosilane, and 30 mL of tetrahydrofuran to the dropping funnel, and stir the reaction vessel under a nitrogen stream. The solution was added dropwise at room temperature over 3 hours. After completion of dropping, the mixture was stirred for 3 hours without heating. After stirring for 3 hours, 300 mL of toluene was added, and the reaction solution was washed with water until neutral, and dehydrated with anhydrous magnesium sulfate. Anhydrous magnesium sulfate was filtered off and concentrated under reduced pressure to obtain 27.1 g of a curable resin [general formula (1)] as a colorless and transparent liquid.

In 1H-NMR of this curable resin, a sharp vinyl group signal was observed, confirming that the hydrolysis condensate from vinyltrimethoxysilane has a cage structure. Therefore, the dense structure portion (A), which is a three-dimensional polyhedral structure composed of metal oxide, that is, silicon oxide, is composed of 8 silicon atoms and 12 oxygen atoms (SiO _3/2 It can be assumed that the cubic structure can be represented by ₈ , and the derived Kp was 0.73. Further, a site other than (A) of the curable resin is a vinyl group which is a residue of _{(H 2 C = CH-SiO} 3/2) 8 (Me 3 SiO 1/2) and (Me ₂ SiO) It was a sparse structural part (B), and the weight ratio [(A) / (B)] determined from these was 1.302. Moreover, the number average molecular weight Mn by GPC was 5200. When calculating the Kp of the dense structural part (A), (SiO _3/2 ) ₈ is a part of (A) and cannot be taken out because it exists as a part in the general formula (I) resin. So Kp cannot be obtained directly. Therefore, calculation was performed using (HSiO _3/2 ) ₈ as a compound that can be approximated with the least influence on Kp.

  100 parts by weight of the curable resin obtained in the synthesis example and 2 parts by weight of dicumyl peroxide (Nippon Yushi Co., Ltd., Park Mill D) were mixed until uniform to obtain a curable resin composition. This is poured into a mold made of glass plates to a thickness of 0.2 mm and heated at 100 ° C. for 1 hour, 120 ° C. for 1 hour, 140 ° C. for 1 hour, 160 ° C. for 1 hour, and 180 ° C. for 2 hours. Thus, a molded body (hard transparent substrate) was obtained.

  58 parts by weight of the curable resin obtained in the synthesis example, 42 parts by weight of terminal trimethylsilyl-modified polymethylhydrosiloxane (HMS-992 manufactured by AMAX Co., Ltd.), and platinum-vinylsiloxane complex (SIP6830.3 manufactured by AMAX Co., Ltd.) 5 parts by weight were mixed until uniform to obtain a curable resin composition. This is poured into a mold made of glass plates to a thickness of 0.2 mm and heated at 100 ° C. for 1 hour, 120 ° C. for 1 hour, 140 ° C. for 1 hour, 160 ° C. for 1 hour, and 180 ° C. for 2 hours. Thus, a molded body (hard transparent substrate) was obtained.

  58 parts by weight of the curable resin obtained in the synthesis example, 21 parts by weight of terminal trimethylsilyl modified polymethylhydrosiloxane (AMS Co., Ltd. HMS-992), 2 parts by weight of dicumyl peroxide (Nippon Yushi Co., Ltd. Park Mill D), And 0.5 parts by weight of a platinum-vinylsiloxane complex (AIPMAX Co., Ltd. SIP6830.3) were mixed until uniform to obtain a curable resin composition. This is poured into a mold made of glass plates to a thickness of 0.2 mm and heated at 100 ° C. for 1 hour, 120 ° C. for 1 hour, 140 ° C. for 1 hour, 160 ° C. for 1 hour, and 180 ° C. for 2 hours. Thus, a molded body (hard transparent substrate) was obtained.

  A gas barrier film made of silicon oxide having a thickness of 10 nm was previously formed on the hard transparent substrates obtained in Examples 1 to 3 by a sputtering method, and then an ITO film having a thickness of 150 nm on the gas barrier film by a sputtering method ( Transparent electrode) was formed to obtain a test laminate including a transparent electrode on a hard transparent substrate. The obtained test laminate was evaluated by the following method.

<Heat resistance>
In the bigat softening test, x, 0.2 to 0.4 mm when the indenter entered 0.4 mm or more at 120 ° C. or less under measurement conditions of an indenter cross-sectional area of 1.0 mm, a load of 5 kg, and a heating rate of 50 ° C./hr. The one that entered was Δ, and the one that was less than 0.1 mm and hardly entered was rated ○.
<Birefractive index>
An in-plane birefringence index was measured at a wavelength of 400 to 800 nm using a phase difference measuring device (NPDM-1000 manufactured by Nikon).
<Light transmittance>
The transmittance at a wavelength of 550 nm was measured using a spectrophotometer manufactured by Hitachi, Ltd.
<Roughness (Ra) of ITO film surface>
Surface roughness was measured by AFM. The measurement range was 10 μm, and measurement was performed under tapping mode conditions.
<Flexibility>
When the test laminate was wound with a core rod having a diameter of 25 mm and bent 90 degrees, the case where cracks did not occur was evaluated as ◯, and the case where cracks were generated was rated as x.
Table 1 shows the evaluation results of heat resistance, birefringence, light transmittance, ITO film surface roughness, and flexibility of the test laminates obtained in Examples 1 to 3.

  Moreover, what used the laminated body for a test obtained in Examples 1-3 for one touch panel member, and formed the 150-nm transparent conductive thin film by the method similar to the above on the glass substrate as the other touch panel member. Using. The two touch panel members were arranged via epoxy beads having a diameter of 30 μm so that the transparent conductive thin film faced to prepare a touch panel specimen. The obtained touch panel specimen was evaluated by the following method.

[Comparative Example 1]
A touch panel specimen was prepared in the same manner as in Examples 1 to 3, except that polyethylene terephthalate having a thickness of 0.188 mm was used instead of the hard transparent substrate.

1) Heat-resistant discoloration:
The assembled touch panel specimen was treated in a hot air circulating oven at 120 ° C. for 120 hours to confirm discoloration of the substrate. When there was no change, it was marked with ○, and when there was coloring such as yellowing, it was marked with ×.
2) Pen sliding test:
A sliding test was conducted 200,000 times by applying a weight of 250 g to a polyacetal pen (tip shape: 0.8 mmR). If no whitening was observed in the sliding part and there was no abnormality in the ON resistance, it was rated as “◯”.
3) Keystroke test:
A polyacetal pen (tip shape: 0.8 mmR) was applied with a weight of 250 g and subjected to a keystroke test 1 million times. If there was no abnormality in the ON resistance, it was marked as ◯.
Table 2 shows the evaluation results of the film moldability, heat discoloration, pen sliding test, and keystroke test of the touch panel specimens prepared using the test laminates obtained in Examples 1 to 3 and Comparative Example 1. .

FIG. 1 is a cross-sectional explanatory view of a liquid crystal display device formed using an electronic material for a display device and the hard transparent substrate of the present invention. FIG. 2 is a cross-sectional explanatory view of a touch panel display device formed using the display device electronic material and the hard transparent substrate of the present invention. FIG. 3 is a cross-sectional explanatory view of an organic EL display device formed using the display device electronic material and the hard transparent substrate of the present invention.

Claims (9)

A display device in which an electronic material for a display device is formed by being laminated on a hard transparent substrate, and the hard transparent substrate is obtained by curing a curable resin represented by the following general formula (1). The curable resin has a dense structural part (A) composed of a metal oxide having a packing coefficient Kp of 0.68 to 0.8 calculated from the following calculation formula (2), and the Kp is 0.00. It has a sparse structure part (B) composed of less than 68 organic substances or organic substances and organometallic oxides, and this dense structure part (A) excludes organic substance parts of the following general formula (I) Further, the metal oxide part having a three-dimensional polyhedral structure, and the sparse structure part (B) is composed of an organic substance part of the general formula (I) and the following general formula (II), and these structural parts (A) / (B) has a weight ratio of 0.01 to 5.00, and the curable resin is small. A display device having at least one unsaturated bond and having a number average molecular weight Mn measured by GPC of 800 to 60000.
− {(A) − (B) _m } _n − (1)
(However, m and n represent an integer of 1 or more.)
Kp = An · Vw · p / Mw (2)
(However, An = Avogadro number, Vw = Vandee Waals volume, p = Density, Mw = Molecular weight, Vw = ΣVa, Va = 4π / R ³ −Σ1 / 3πhi ² (3Ra-hi), hi = Ra− (Ra ² + di ² −R i ² ) / 2di, Ra = atomic radius, Ri = bonding atomic radius, and di = interatomic distance.
(RSiO _3/2 ) _w (MO ₂ ) _x (RXSiO) _y (XMO _3/2 ) _z (I)
(R ³ R ⁴ R ⁵ SiO _1/2 ) _j (R ⁶ R ⁷ SiO) _k {R ⁶ R ⁷ XSiO _1/2 } _l (II)
(Wherein, R represents ^{(a) -R 1 -OCO-CR} 2 = CH 2, (b) -R 1 -CR 2 = CH 2 or (c) an unsaturated group represented by -CH = CH _2, alkyl group , A cycloalkyl group, a cycloalkenyl group, a phenyl group, a hydrogen atom, an alkoxyl group, or an alkylsiloxy group, and a plurality of R in the formula (I) may be different from each other, but at least one of (a ), (B), or (c), R ¹ represents an alkylene group, an alkylidene group, or a phenylene group, R ² represents hydrogen or an alkyl group, and R ^{3 to} R ⁷ represent (a) ^{-R 1 -OCO-CR 2 = CH} 2, unsaturated group represented by ^{(b) -R 1 -CR 2 =} CH 2 or (c) -CH = CH _2, alkyl group, cycloalkyl group, cycloalkenyl group , Phenyl group, hydrogen atom, alkoxyl group, or alkylsiloxy group M is a metal atom of silicon, germanium, titanium, or zirconium, X is a halogen atom, or an alkoxyl group, w is an integer of 4 or more, and x, y, and z are integers that satisfy w + x + y + z ≧ 8 J, k, and l are each an integer of 0 or more.) The structural unit represented by (A) in the general formula (1) is a hydrolytic condensation of RSiX ₃ , MX ₄ or a mixture thereof (where R, M and X are the same as those in the general formula (I)). The display device according to claim 1, comprising a metal oxide portion that is a three-dimensional polyhedral structure skeleton in a structural unit represented by the general formula (I) obtained from a product . The structural unit represented by (B) in the general formula (1) is R ³ R ⁴ R ⁵ SiX, R ⁶ R ⁷ SiX ₂ or a mixture thereof (provided that R ^{3 to} R ⁷ and X are represented by the general formula ( The same as in II).) The chain unit of the metal oxide represented by the general formula (II) and the metal atom contained in the structure represented by the general formula (I). The display device according to claim 1, wherein the display device comprises an organic group bonded to . Claims: A curable resin composition is obtained by adding a hydrosilylation catalyst and / or a radical initiator to a curable resin, and then the curable resin composition is molded and thermally cured or photocured to obtain a rigid transparent substrate. Item 4. The display device according to any one of Items 1 to 3 . The display device according to claim 4, further comprising a compound having at least one hydrosilyl group and / or a compound having an unsaturated group in the molecule to obtain a curable resin composition . The electronic material for the display device is at least a transparent electrode, an alignment film, a liquid crystal layer, a color filter, a thin film transistor, a polarizing plate, and a backlight, and a liquid crystal in which a color filter, a transparent electrode, and an alignment film are stacked on a hard transparent substrate The first member and the liquid crystal second member in which the thin film transistor and the alignment film are stacked on the hard transparent substrate sandwich the liquid crystal layer so that the alignment films face each other, and the liquid crystal first member rigid transparent substrate 6. The liquid crystal display device according to claim 1, wherein a polarizing plate is disposed outside the liquid crystal, and a polarizing plate and a backlight are disposed outside the hard transparent substrate of the liquid crystal second member . Display device. The electronic material for the display device is at least a transparent electrode, a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, a metal electrode, and a gas barrier film, a transparent electrode, a hole injection layer on a hard transparent substrate, The display device according to claim 1, which is an organic EL display device in which a hole transport layer, a light emitting layer, an electron transport layer, and a metal electrode are laminated and sealed with a gas barrier film . The electronic material for the display device is at least a transparent electrode, a dot spacer, a polarizing plate, and a liquid crystal display device, and a pair of touch panel members in which a transparent electrode is formed on a hard transparent substrate are arranged so that the transparent electrode faces each other. 6. A touch panel display device in which a polarizing plate is disposed outside each touch panel member, and a liquid crystal display device is further disposed outside one touch panel member. The display apparatus in any one . The display device according to claim 6, further comprising a gas barrier film disposed between the hard transparent substrate and the transparent electrode .

Images