KR20080034078A - Display device - Google Patents

Abstract

A display device is provided to harden thermosetting resins by using a hard transparent substrate so as to increase strength and transparency as well as folding endurance of the device. A display device is formed by depositing electron materials for the device on a hard transparent substrate. A hard transparent substrate hardens thermosetting resins. The thermosetting resins have a dense structure area constituted with metal oxide in which a packing coefficient is 0.68 to 0.8, and a loose structure area constituted with organic compounds in which a packing coefficient is less than 0.68, or organic compounds and organic metal oxide. A weight ratio of the structure areas is 0.01 to 5.00. The average molecular weight is 800 to 600,000 in the structure areas. Thereby, the strength, transparency, and folding endurance of the device increase.

Description

Display device {DISPLAY DEVICE}

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention is a display device formed by stacking electronic materials for display devices using a novel rigid transparent substrate instead of a conventional glass substrate, and is, for example, a PC, 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 navigation system.

BACKGROUND With the rapid advance of electronic technology, the liquid crystal display, touch panel, and photoelectronics fields are expanding in particular. In general, photoelectronic devices have been provided for various applications by forming devices on a glass substrate having a transparent conductive layer. However, a glass substrate has a big weight, and when attached to a portable apparatus, there exists a problem that the weight of an apparatus becomes large because of the large specific gravity of a glass substrate. Therefore, the weight reduction is strongly demanded, and as a rigid substrate which replaces a glass substrate, the sheet substrate which consists of plastic sheets, such as polyarylate, polyether sulfone, polycarbonate, which is comparatively excellent in strength, transparency, heat resistance, etc., is employ | adopted.

However, these sheet substrates in the current state have a thickness of about 0.1 mm, and thus lack rigidity as compared with conventional glass substrates. Although the film thickness of a film is considered in order to provide rigidity, in the solvent cast method generally employed when obtaining a sheet | seat board | substrate, manufacture with a thickness of about 0.2 mm is a limitation because of foaming, a fall of planarity, and a problem of residual solvent. In addition, although the birefringence of a sheet | seat board | substrate is normally 20 nm or less, Preferably it is 10 nm or less for application to a liquid crystal element, it is difficult to produce a low birefringent molded object easily to receive molecular orientation at the time of plastic molding. Then, for example, although the optical plastic sheet which laminated | stacked two layers of sheets with small birefringence is proposed (refer patent document 1), this sheet is a thermoplastic resin, and since it is a thermoplastic resin, its rigidity is small and it is inferior also in chemical-resistance significantly. There is this. Moreover, although it is proposed to coat curable resin on the surface layer of a base sheet as an optical sheet (refer patent document 2), such a sheet | seat has a possibility that the curable resin of a sheet side surface may swell or melt | dissolve by a solvent at the time of a board | substrate washing | cleaning. As a result, the chemical resistance is inferior, and the rigidity of the substrate is not sufficient.

In particular, in the field of photoelectronic devices, since a higher degree of optical characteristics, gas barrier properties, electrical conductivity, mechanical strength, and the like are required, a substrate having a laminated structure composed of a plurality of layers or films having respective functions is actually used. For example, a laminated body in which a cured film is formed on both surfaces on a plastic molded body, a conductive film is formed on one side, and a metal oxide film is formed on the other side is proposed. However, this laminate has a problem such that cracks are likely to occur in the plastic molded body at the time of heating due to differences in the properties of the layers, adhesion problems, and the like.

On the other hand, although it is a plastic sheet substrate useful as a glass replacement substrate, in order to raise utilization value, it is necessary not only to be lightweight but also to have flexibility. That is, when the substrate is bent (curved) with a predetermined curvature, cracks are not formed in the conductive film, and it is necessary to maintain electrical conductivity. However, in the conventional plastic sheet substrate, there exists a problem that the bending resistance is inadequate.

[Patent Document 1] Japanese Patent Application Laid-Open No. 7-36023

[Patent Document 2] Japanese Unexamined Patent Publication No. 6-116406

[Patent Document 3] Japanese Unexamined Patent Application Publication No. 2-5308

An object of the present invention is to provide various display devices using a rigid transparent substrate having the same strength, transparency, heat resistance, and dimensional stability as inorganic glass, high toughness and processability such as plastic, and excellent bending resistance. The present invention provides a display device formed by stacking materials.

MEANS TO SOLVE THE PROBLEM As a result of earnestly examining in order to obtain the new board | substrate which replaces the conventional glass substrate, the present inventors hardened a glass substrate and a plastic sheet board | substrate by hardening | curing curable resin which has a dense structural part and loose structural part in which a free volume fraction differs in molecular structure. The present invention is completed by discovering that a rigid transparent substrate having both excellent performance and excellent bending resistance can be obtained, and this rigid transparent substrate is preferable as a replacement for glass substrates used in various display devices. did.

That is, this invention is a display apparatus by which the electronic material for display apparatuses is laminated | stacked and formed on a hard transparent substrate, Comprising: A hard transparent substrate is obtained by hardening curable resin represented by following General formula (1), The said curable resin is a following formula Dense structural site A consisting of a metal oxide having a packing coefficient Kp calculated from (2) of 0.68 to 0.8, and a loose structure site B consisting of an organic material having an Kp of less than 0.68 or an organic material and an organic metal oxide. ), The weight ratio of the structural sites (A) / (B) is 0.01 to 5.00, and at least one unsaturated bond, and the average molecular weight is 800 to 60000.

-{(A)-(B) _m } _n- (1)

(Where m and n represent an integer of 1 or more)

Kp = AnVwp / Mw (2)

(Where, An = Avogadro's number, Vw = van der Waals volume, p = density, Mw = molecular weight, Vw = ΣVa, Va = 4 Π / R 3 -Σ1 / 3 Π hi 2 (3Ra-hi), hi = Ra -(Ra ² + di ² -Ri ² ) / 2di, Ra = atomic radius, Ri = bonding atom radius and di = atomic distance.)

In addition, according to the present invention, the dense structural part (A) is a metal oxide part having a three-dimensional polyhedral structure except for the organic part of the general formula (I), and the loose structural part (B) is an organic part of the general formula (I). And said display device which consists of 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 is an unsaturated group represented by (a) -R ¹ -OCO-CR ² = CH ₂ , (b) -R ¹ -CR ² = CH ₂ or (c) -CH = CH ₂ , an alkyl group or a cyclo It is an alkyl group, a cycloalkenyl group, a phenyl group, a hydrogen atom, an alkoxyl group, or an alkylsiloxy group, and some R in Formula (I) may mutually differ, but at least 1 is (a), (b), ( and 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- Unsaturated group, alkyl group, cycloalkyl group, cycloalkenyl group, phenyl group, hydrogen atom, alkoxyl group represented by CR ² = CH ₂ , (b) -R ¹ -CR ² = CH ₂ or (c) -CH = CH ₂ or Is an 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 represent w + x + y + z ≧ 8 And j, k and l are respectively An integer greater than or equal to zero.)

Here, the metal oxide moiety which is the three-dimensional polyhedral structural skeleton in the structural unit represented by general formula (I) is RSiX ₃ , MX ₄ or a mixture thereof (wherein R, M and X are the same as general formula (I)). R ³ R ⁴ R ⁵ SiX, R ⁶ R ⁷ which is a metal oxide moiety that is a three-dimensional polyhedral structural skeleton in the structural unit generated from the hydrolyzed condensate, or represented by the general formula (II) SiX ₂ or a mixture thereof (wherein R ³ to R ⁷ and X are the same as general formula (II)) is an organic group bonded to chain units and metal atoms of metal oxides prepared from hydrolysis condensates. It is a preferred form of the present invention.

Moreover, in this invention, a hydrosilylation catalyst or a radical initiator is mix | blended with the said curable resin, or both a hydrosilylation catalyst and a radical initiator are mix | blended, and a curable resin composition is formed, and this curable resin composition is hardened and hardened | cured. A transparent substrate may be obtained. Specifically, the curable resin composition blended as described above may be molded into a predetermined shape and then thermally cured or photocured to obtain a molded body (hard transparent substrate). In addition, the curable resin composition may mix | blend the compound which can be hydrosilyl group which has at least 1 hydrosilyl group in a molecule | numerator, the compound which has an unsaturated group in a molecule | numerator, or may mix | blend both.

The rigid transparent substrate obtained by the present invention has the same strength, transparency, heat resistance, and dimensional stability as that of inorganic glass, and also has high toughness and processability such as plastic, and is excellent in flex resistance. By replacing the glass substrates used in display devices in various fields including touch panel display devices, organic EL display devices, and the like, performances of conventional glass substrates and plastic sheet substrates can be exhibited, and the light weight and impact resistance can be further improved. It is possible to provide an excellent display device.

Hereinafter, the present invention will be described in more detail.

As shown by the said General formula (1), curable resin of this invention has the molecular structure which consists of a dense structural site | part (A) and a loose structural site | part (B), and has at least 1 unsaturated bond. Here, the dense structural part (A) is a structural part composed of a metal oxide part having a packing coefficient (Kp) of 0.68 to 0.8, and the loose structural part (B) is an organic part or organic part having a packing coefficient (Kp) of less than 0.68. And an organic metal oxide moiety.

The dense structural site (A) is preferably a metal oxide site that is a three-dimensional polyhedral structural skeleton in the structural unit represented by the general formula (I). In 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). In addition, some R of general formula (I) does not need to be the same at all.

The structural unit represented by general formula (I) is comprised by the three-dimensional polyhedral structure and R. As an example, when w in general formula (I) is 8 and x, y, and z are 0, w is 10. And x, y and z are 0, and specific examples of the structure where w is 12 and x, y and z are 0 are shown in the following structural formulas (3), (4) and (5). However, the structural unit represented by general formula (I) is not limited to what is shown to this structural formula (3), (4) and (5). In addition, these structures are well-known and are shown by X-ray crystal structure analysis about what is a specific functional group.

Metal oxide part of the structural unit shown by the general formula (I) may be obtained by carrying out the hydrolysis and condensation reaction at least one kind of compound represented by RSiX ₃ or MX ₄ the presence of an acid or base catalyst revered. Here, R, X and M have the same meaning as R, X and M in general formula (I).

It is preferable that a part of R is an unsaturated group represented by said (a), (b) or (c), but when a specific example of a preferable unsaturated group is shown, 3-methacryloxypropyl group, 3-acryloxypropyl group, aryl Group, vinyl group, and steel group.

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

Preferable examples of the compound represented by RSiX ₃ include trichlorosilane, methyltrichlorosilane, ethyltrichlorosilane, isopropyltrichlorosilane, butyltrichlorosilane, t-butyltrichlorosilane, cyclohexyltrichlorosilane, Phenyltrichlorosilane, vinyltrichlorosilane, allyltrichlorosilane, styryl trichlorosilane, cyclohexenyltrichlorosilane, trimethoxysilane, methyltrimethoxysilane, ethyltrimethoxysilane, isopropyltrimethoxy Silane, butyltrimethoxysilane, t-butyltrimethoxysilane, cyclohexyltrimethoxysilane, phenyltrimethoxysilane, vinyltrimethoxysilane, allyltrimethoxysilane, styryltrimethoxysilane, cyclohex Senyltrimethoxysilane, Triethoxysilane, Methyltriethoxysilane, Ethyltriethoxysilane, Isopropyltriethoxysilane, Butyltriethoxysilane, t-butyltriethoxy Silane, cyclohexyltriethoxysilane, phenyltriethoxysilane, vinyltriethoxysilane, allyltriethoxysilane, styryltriethoxysilane, cyclohexenyltriethoxysilane, tripropoxysilane, methyltripro Foxysilane, Ethyltripropoxysilane, Isopropyltripropoxysilane, Butyltripropoxysilane, t-butyltripropoxysilane, Cyclohexyltripropoxysilane, Phenyltripropoxysilane, Vinyltripropoxysilane, Allyl Tripropoxysilane, styryl tripropoxysilane, cyclohexenyltripropoxysilane, methacryloxymethyltriethoxysilane, methacryloxymethyltrimethoxysilane, 3-methacryloxypropyltrichlorosilane, 3- Methacryloxypropyl trimethoxysilane, 3-methacryloxypropyl triethoxysilane, 3-acryloxypropyl trimethoxysilane, 3-acryloxypropyl trichlorosilane, etc. are mentioned.

In addition, M is silicon, germanium, titanium or zirconium. Preferred examples of the compound represented by MX ₄ here include tetrachlorosilane, tetramethoxysilane, tetraethoxysilane, tetrachlorogerman, tetramethoxygerman, tetraethoxygerman, titanium ethoxide and titanium pro. Fox seed, titanium isopropoxide, titanium butoxide, titanium isobutoxide, zirconium ethoxide, zirconium propoxide, zirconium isopropoxide, zirconium butoxide, zirconium isobutoxide and the like.

On the other hand, the loose structural part (B) consists of a residue (or substituent) except the three-dimensional polyhedral structural skeleton in the structural unit represented by the said general formula (I), and a structural unit represented by the said general formula (II). In other words, it consists of the site | part except the dense structural site | part (A) from the structural unit represented by said general formula (I), and the structural unit represented by 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 in general formula (II). The chain structure of the metal oxide represented by the general formula (II) obtained from the hydrolysis condensate of the organic group and the organic group bonded to the metal atom in the general formula (I) (that is, the structural unit represented by the general formula (I)) Residues (or substituents) other than the three-dimensional polyhedral structural skeleton in the compound].

The structural unit represented by the general formula (II) is obtained by subjecting at least one of the compounds represented by R ³ R ⁴ R ⁵ SiX or R ⁶ R ⁷ SiX ₂ to a hydrolysis and condensation reaction in the presence of an acid or a base catalyst. Obtained. Here, R ³ ~ R ⁷ have the same meaning as that of R ³ ~ R ⁷ in the formula (Ⅱ). When some of R <^3> -R <^7> is an unsaturated group, if a preferable specific example is shown, 3-methacryloxypropyl group, 3-acryloxypropyl group, an aryl group, a vinyl group, and a styryl group will be mentioned. X is a halogen atom or an alkoxy group, and specific examples thereof 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 include trimethylchlorosilane, vinyldimethylchlorosilane, dimethylchlorosilane, phenyldimethylchlorosilane, phenylchlorosilane, triethylchlorosilane, trivinylchlorosilane, methyl Divinylchlorosilane, allyldimethylchlorosilane, 3-methacryloxypropyldimethylchlorosilane, 3-acryloxypropyl dimethylchlorosilane, styryldimethylchlorosilane, trimethylmethoxysilane, vinyldimethylmethoxysilane, dimethylmethoxy Silane, phenyldimethylmethoxysilane, phenylmethoxysilane, triethylmethoxysilane, trivinylmethoxysilane, methyldivinylmethoxysilane, allyldimethylmethoxysilane, 3-methacryloxypropyldimethylmethoxysilane, 3 -Acryloxypropyldimethylmethoxysilane, styryldimethylmethoxysilane, trimethylethoxysilane, vinyldimethylethoxysilane, dimethylethoxysilane, phenyldi Methylethoxysilane, phenylethoxysilane, triethylethoxysilane, trivinylethoxysilane, methyldivinylethoxysilane, allyldimethylethoxysilane, 3-methacryloxypropyldimethylethoxysilane, 3-acryloxy Propyldimethylethoxysilane, styryldimethylethoxysilane, trimethylpropoxysilane, vinyldimethylpropoxysilane, dimethylpropoxysilane, phenyldimethylpropoxysilane, phenylpropoxysilane, triethylpropoxysilane, trivinylpropoxy Silane, methyldivinylpropoxysilane, allyldimethylpropoxysilane, 3-methacryloxypropyldimethylpropoxysilane, 3-acryloxypropyldimethylpropoxysilane, styryldimethylpropoxysilane, trimethylisopropoxysilane, vinyl Dimethyl isopropoxy silane, dimethyl isopropoxy silane, phenyl dimethyl isopropoxy silane, phenyl isopropoxy silane, triethyl isopropoxy silane, trivinyl Propoxysilane, methyldivinylisopropoxysilane, allyldimethylisopropoxysilane, 3-methacryloxypropyldimethylisopropoxysilane, 3-acryloxypropyldimethylisopropoxysilane, styryldimethylisopropoxysilane, etc. Can be mentioned.

Preferred examples of the compound represented by R ⁶ R ⁷ SiX ₂ include dimethyldichlorosilane, vinylmethyldichlorosilane, divinyldichlorosilane, allylmethyldichlorosilane, methyldichlorosilane, methylphenyldichlorosilane, methylethyldichlorosilane, ethyl Vinyldichlorosilane, ethylallyldichlorosilane, styrylmethyldichlorosilane, styrylethyldichlorosilane, 3-methacryloxypropylmethyldichlorosilane, dimethyldimethoxysilane, vinylmethyldimethoxysilane, divinyldimethoxysilane, allylmethyl Dimethoxysilane, methyldimethoxysilane, methylphenyldimethoxysilane, methylethyldimethoxysilane, ethylvinyldimethoxysilane, ethylallyldimethoxysilane, styrylmethyldimethoxysilane, styrylethyldimethoxysilane, 3-methacryl Oxypropylmethyldimethoxysilane, dimethyldiethoxysilane, vinylmethyldiethoxysilane, divinyldiethoxysilane, allylmethyldi Methoxysilane, methyl diethoxysilane, methylphenyl diethoxysilane, methyl ethyl diethoxy silane, ethyl vinyl diethoxy silane, ethyl allyl diethoxy silane, styryl methyl diethoxy silane, styryl ethyl diethoxy silane, 3-methacryloxy Propylmethyldiethoxysilane, dimethyldipropoxysilane, vinylmethyldipropoxysilane, divinyldipropoxysilane, allylmethyldipropoxysilane, methyldipropoxysilane, methylphenyldipropoxysilane, methylethyldipropoxy Silane, ethylvinyldipropoxysilane, ethylallyldipropoxysilane, styrylmethyldipropoxysilane, styrylethyldipropoxysilane, 3-methacryloxypropylmethyldipropoxysilane, dimethyldiisopropoxysilane , Vinyl methyl diisopropoxy silane, divinyl diisopropoxy silane, allyl methyl diisopropoxy silane, methyl diisopropoxy silane, methylphenyl diisopropoxy silane, methyl ethyl diisoprop Silane, ethyl vinyl diisopropoxy silane, ethyl allyl diisopropoxy silane, styryl methyl diisopropoxy silane, styryl ethyl diisopropoxy silane, 3-methacryloxypropyl methyl diisopropoxy silane, etc. Can be mentioned.

The curable resin of the present invention can be obtained by reacting a cage-type siloxane resin represented by the general formula (I) with a silicone compound represented by the general formula (II), but the obtained curable resins are represented by the general formulas (I) and The unsaturated bond of the structural unit represented by general formula (II) has the molecular structure condensed by crosslinking or hydrolytic condensation. And this curable resin has the compact structural site | part (A) whose packing coefficient computed from a free volume fraction is 0.68-0.8, the loose structural site | part (B) whose packing factor is less than 0.68, and has at least 1 unsaturated bond. .

Calculation of the packing coefficient Kp used by this invention is computed from the following formula (2).

Kp = AnVwp / Mw (2)

(Where An = Avogadro's number, Vw = Van der Waals volume, p = density, and Mw = molecular weight.)

Vw = ΣVa,

Va = 4 _Π / R ³ -Σ1 / 3 _Π hi ² (3R-hi),

hi = R- (R ² + di ² -Ri ² ) / 2di

Where R = atomic radius, Ri = bond atomic radius and di = atomic distance.

In the calculation of the packing coefficient, the atomic radius and the interatomic distance used numerical values described in the third edition of the Japanese Chemical Society. That is, in the atomic radius, H = 1.2 kPa, O = 1.52 kPa, C = 1.7 kPa, Si = 2.14 kPa, and the distance between atoms is HC = 1.08 kPa, CC = 1.541 kPa, Si-C = 1.863 kPa, Si- O = 1.609 ms was used. For example, the density of glass represented by M = silicon atom, v = 0, w = 2, y = 0 and z = 0 in General Formula (1) is 2.23 g / cm 3, and its packing coefficient is 0.747. do. R in general formula (1) is a methyl group, the density of octakismethylsilsesquioxane having a cubic structure of v = 8, w = 0, y = 0 and z = 0 is 1.49 g / cm 3 and packing coefficient is 0.697 do. Further, the density of the octamethylcyclotetrasiloxane having a cyclic structure in which R ⁶ and R ^{7 in} the general formula (2) is a methyl group and j = 0, k = 4 and l = 0 is 0.956 g / cm 3, and its packing coefficient is 0.576. Becomes 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 has j = 2, k = 1 and l = 0 is 0.820 g / cm 3, and the packing factor Becomes 0.521. That is, the packing coefficient of the metal oxide having a three-dimensional polyhedral structure bonded to an oxygen atom having three or more silicon atoms is 0.69 or more, which is a dense structural site in the present invention. Moreover, the packing coefficients of the compound which has cyclic and chain structure are 0.576 and 0.521, and become a loose structure site | part in this invention.

The curable resin of this invention has a structural weight ratio (A) / (B) of a dense structural site | part (A) and a loose structural site | part (B) of 0.01-5.00, Preferably it is 0.5-3.00. When (A) / (B) is smaller than 0.01, there are too few dense structures, and the mechanical property and heat resistance of the molded object obtained by shape | molding and hardening curable resin will deteriorate remarkably. Moreover, when it is 5.00 or more, there are too few loose structural parts which give flexibility to a molded object, toughness remarkably deteriorates, and it becomes a soft molded object.

Moreover, curable resin of this invention is 800-60000 in average molecular weight. If the average molecular weight is less than 800, it is liable to recede after molding, whereas if it exceeds 60000, hard molding may become difficult and cause inconvenient handling. In addition, an average molecular weight can be measured by a well-known GPC measuring apparatus.

Hydrochloric acid and sulfuric acid are mentioned as an acidic catalyst 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 . Moreover, these may be mixed and used, and when the hydrolyzable group is a halogen atom, the hydrogen halide produced | generated at the time of hydrolysis may be used.

As a basic catalyst used for hydrolysis and condensation, alkali metal hydroxides, such as potassium hydroxide, sodium hydroxide, and cesium hydroxide, or tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrabutylammonium hydroxide, benzyl trimethylammonium hydroxide Ammonium hydroxide salts, such as a seed and benzyl triethylammonium hydroxide, are illustrated. Among them, tetramethylammonium hydroxide is preferably used in view of high catalytic activity. Basic catalysts are usually used as an aqueous solution.

Although the presence of water is essential for the hydrolysis reaction, this can be supplied from an aqueous solution of the catalyst and may be added as separate water. The amount of water is at least an amount sufficient to hydrolyze the hydrolyzable group, preferably 1.0 to 1.5 times the theoretical amount.

In the case where the curable resin is used as the curable resin composition, the compound having at least one hydrosilyl group in the molecule to be blended with the curable resin includes oligomers and monomers having hydrogen atoms on at least one hydrosilyzable silicon atom in the molecule. to be. Examples of the oligomer having a hydrogen atom on the silicon atom include polyhydrogen siloxanes, polydimethylhydrosiloxysiloxanes and copolymers thereof, and siloxanes whose ends are modified with dimethylhydroxyoxy. As the monomer having a hydrogen atom on the silicon atom, cyclic siloxanes such as tetramethylcyclotetrasiloxane and pentamethylcyclopenta, dihydrogensiloxanes, trihydromonosilanes, dihydromonosilanes and monohydromono Silanes, dimethyl siloxysiloxanes, etc. can be illustrated, You may mix these two or more types.

Moreover, the compound which has an unsaturated group mix | blended with curable resin is divided roughly into the reactive oligomer whose repeating number of a structural unit is about 2-20 polymer, and the low molecular weight, low viscosity reactive monomer. Moreover, it is divided roughly into the monofunctional unsaturated compound which has one unsaturated group, and the polyfunctional unsaturated compound which has two or more.

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

As the reactive monofunctional monomer, vinyl substituted silicon compounds such as triethyl vinyl silane and triphenyl vinyl silane, cyclic olefins such as cyclohexene, styrene, vinyl acetate, N-vinylpyrrolidone, butyl acrylate and 2-ethyl Hexyl acrylate, n-hexyl acrylate, cyclohexyl acrylate, n-decyl acrylate, isobornyl acrylate, dicyclopentenyl oxyethyl acrylate, phenoxyethyl acrylate, trifluoroethyl methacrylate, etc. It can be illustrated.

Examples of reactive polyfunctional monomers include vinyl substituted silicon compounds such as tetravinylsilane and divinyl tetramethyldisiloxane, vinyl substituted cyclic silicon compounds such as tetramethyltetravinylcyclotetrasiloxane, pentamethylpentavinylcyclopentasiloxane, and bis (trimethylsilyl Acetylene derivatives such as acetylene and diphenyl acetylene, cyclic polyenes such as norbornadiene, dicyclopentadiene and cyclooctadiene, vinyl substituted cyclic olefins such as vinylcyclohexene, divinylbenzene, diethylbenzene, Trimetholpropane diallyl ether, pentaerythritol triallyl ether, tripropylene glycol diacrylate, 1,6-hexanediol diacrylate, bisphenol A diglycidyl ether diacrylate, tetraethylene glycol diacrylate, and hydroxide Loxypivalic acid neopentylglycol diacrylate, trimetholpropane triacrylate, pentae Listhritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, etc. can be illustrated.

As the compound having an unsaturated group in the molecule, various reactive oligomers and monomers can be used in addition to those exemplified above. In addition, these reactive oligomers and monomers may be used independently, respectively, or may mix and use two or more types.

The compound which has an at least 1 hydrosilyl group in the molecule | numerator used by this invention, and the compound which has an unsaturated group in a molecule | numerator may be used individually, or may be used in mixture of 2 or more types.

In this invention, you may mix | blend a hydrosilylation catalyst or a radical initiator with curable resin, or may mix | blend both and get curable resin composition. And a hard transparent board | substrate can be obtained by thermosetting or photocuring and hydrosilylation and radical polymerization of this curable resin composition. Moreover, you may add a hydrosilylation catalyst and a radical initiator, and further mix | blend the compound which has at least 1 hydrosilyl group, or the compound which has an unsaturated group in a molecule | numerator, and may be made to obtain curable resin composition. That is, a hydrosilylation catalyst, a thermal polymerization initiator, a thermal polymerization accelerator, a photopolymerization initiator, and a photoinitiator are used as additives for promoting the reaction from the purpose of curing the curable resin to obtain a hard transparent substrate and improving the physical properties of the obtained hard transparent substrate. , A dye or the like is blended to obtain a curable resin composition.

When mix | blending a hydrosilylation catalyst, it is preferable to add the addition amount as a metal atom with respect to the weight of curable resin in 1-1000 ppm, More preferably, it is 20-500 ppm. When mix | blending a photoinitiator or a thermal polymerization initiator as a radical initiator, it is preferable to make the addition amount into the range of 0.1-5 weight part with respect to curable resin, and it is more preferable to set it as 0.1-3 weight part. When this addition amount is less than 0.1 weight part, hardening will become inadequate and the strength and tolerance of the molded object obtained will become low. On the other hand, when it exceeds 5 weight part, there exists a possibility that a problem, such as coloring of a molded object, may arise. In addition, a hydrosilylation catalyst and a radical initiator may be used independently, and may be used in combination of 2 or more types.

Examples of hydrosilylation catalysts include chloroplatinum chloride, chloroplatinic acid, chloroplatinic acid and alcohols, aldehydes, ketone complexes, chloroplatinic acid and olefin complexes, platinum and vinylsiloxane complexes, dicarbonyldichloro platinum and palladium-based catalysts. And platinum group metal catalysts such as rhodium-based catalysts. Among these, chloroplatinic acid, a complex of chloroplatinic acid and olefins, and a complex of platinum and vinylsiloxane are preferable from the viewpoint of catalytic activity. In addition, these may be used independently and may be used together two or more types.

As a photoinitiator used when making curable resin composition a photocurable composition, compounds, such as an acetophenone type, a benzoin type, a benzophenone type, a thioxanthone, an acylphosphine oxide type, can be used preferably. Specifically, trichloroacetophenone, diethoxyacetophenone, 1-phenyl-2-hydroxy-2-methylpropan-1-one, 1-hydroxycyclohexylphenyl ketone, 2-methyl-1- (4- Methylthiophenyl) -2-morpholinopropane-1-one, benzoin methyl ether, benzyl dimethyl ketal, benzophenone, thioxanthone, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, methylphenylglyoxylate , Camphor quinone, benzyl, anthraquinone, Michler's ketone and the like. Moreover, the photoinitiator and the preservative 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 various organic peroxides such as ketone peroxide, peroxy ketal, hydroperoxide, dialkyl peroxide, diacyl peroxide, peroxydicarbonate, and peroxy ester. Can be preferably used. Specifically, cyclohexanone peroxide, 1, 1-bis (t-hexaperoxy) cyclohexanone, cumene hydroperoxide, dicumyl peroxide, benzoyl peroxide, diisopropyl peroxide, t-butyl peroxy-2 Although ethyl hexanoate etc. can be illustrated, it is not limited to this at all. In addition, these thermal polymerization initiators may be used independently, or may mix and use 2 or more types.

Various additives can be added to curable resin composition of this invention in the range which does not deviate from the objective of this invention. Examples of the various additives include organic / inorganic fillers, plasticizers, flame retardants, heat stabilizers, antioxidants, light stabilizers, ultraviolet absorbers, lubricants, antistatic agents, mold release agents, foaming agents, nucleating agents, colorants, crosslinking agents, dispersing aids, resin components, and the like. .

As described above, the rigid transparent substrate of the present invention can be produced by molding a curable resin composition containing one or both of a hydrosilylation catalyst or a radical polymerization initiator into a predetermined shape and curing by heating or light irradiation. Can be. When manufacturing a copolymer (hard transparent substrate) by heating, the temperature can be selected from the wide range from room temperature to around 200 degreeC according to 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 the general molding processing methods, such as injection molding, extrusion molding, compression molding, transfer molding, calender molding, and cast (molding) molding, are applicable.

Moreover, when manufacturing a rigid transparent substrate by photopolymerization by light irradiation, a rigid transparent substrate can be obtained by irradiating the ultraviolet-ray of wavelength 1.0-400 nm and visible light of the wavelength 400-700 nm. Although the wavelength of the light to be used is not specifically limited, Especially near-ultraviolet ray of wavelength 200-400 nm is used preferably. As a lamp used as an ultraviolet ray generating source, a low pressure mercury lamp (output: 0.4 to 4 W / cm), a high pressure mercury lamp (40 to 160 W / cm), an ultra high pressure mercury lamp (173 to 435 W / cm), and a metal halide lamp (80 to 160 W) / Cm), a pulse xenon lamp (80-120W / cm), an electrodeless discharge lamp (80-120W / cm), etc. can be illustrated. These ultraviolet lamps are selected according to the kind of photoinitiator to be used because they are characterized by their spectral distribution.

As a method of obtaining a rigid transparent substrate by light irradiation, the curable resin composition is inject | poured into the metal mold | die which consists of transparent materials, such as quartz glass, and arbitrary cavity shape, for example, irradiates an ultraviolet-ray with said ultraviolet lamp, and performs superposition | polymerization hardening. By performing mold release from the mold, and when the mold is not used, or when the mold is not used, for example, a curable resin composition of the present invention using a doctor blade or a roll-shaped coater on a moving steel belt. The method of manufacturing a sheet-like hard transparent board | substrate, etc. can be illustrated by apply | coating and polymerizing-hardening with said ultraviolet lamp. Moreover, in this invention, you may use combining the method of obtaining a rigid transparent substrate by heating and light irradiation.

The rigid transparent substrate obtained by hardening curable resin in this invention is excellent in transparency, specifically, the light transmittance in the wavelength of 550 nm light is 80% or more, and the birefringence is 20 nm or less Various display devices can be obtained by laminating electronic materials for display devices. That is, when the light transmittance is less than 80%, in the case of color display or the like, the screen is dark and difficult to be used, so it tends to be used only for use as a monochrome display element or the like. When the birefringence is larger than 20 nm, the display panel is used. In one case, color deviation of the display screen tends to occur, but since the rigid transparent substrate of the present invention has the above characteristics, it is preferable in that various display devices are obtained.

The thickness of the rigid transparent substrate also varies depending on the type of display device. For example, in the case of a liquid crystal display device, the thickness is preferably 0.10 to 2.00 mm. If it is less than 0.10 mm, it may be bent by the weight of the board | substrate itself, and there exists a possibility that the manufacturing process of the liquid crystal display device using the 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 deviate from the objective of weight reduction.

EMBODIMENT OF THE INVENTION Hereinafter, preferred embodiment of this invention is described using attached drawing.

BRIEF DESCRIPTION OF THE DRAWINGS It is sectional explanatory drawing of the liquid crystal display device formed using the electronic material for various display devices, and the hard transparent substrate of this invention, and is a preferable example using the hard transparent substrate of this invention. In this case, the electronic material for a display device is a transparent electrode, an alignment film, a liquid crystal layer, a color filter, a thin film transistor, a polarizing plate, and a backlight, for example, The liquid crystal 1 in which the color filter, a transparent electrode, and an alignment film were laminated | stacked on the rigid transparent substrate. The member and the liquid crystal second member in which the thin film transistor and the alignment film are laminated on the rigid transparent substrate sandwich the liquid crystal layer so that the alignment film faces each other, and the polarizing plate is disposed outside the hard transparent substrate of the liquid crystal first member, The polarizing plate and the backlight are disposed outside the hard transparent substrate of the liquid crystal second member. Here, the gas barrier film may be formed on both surfaces of the rigid transparent substrate.

In the case of a liquid crystal display device, conductive materials, such as indium oxide, tin oxide, gold, silver, copper, nickel, are mentioned as a transparent electrode. These may be used alone or in combination of two or more thereof. Usually, indium tin oxide (hereinafter referred to as "ITO") composed of a mixture of 99 to 90% of indium oxide and 1 to 10% of tin oxide has a balance of transparency and conductivity. It is especially preferable at the point of view. The method of forming a transparent substrate can be performed using the well-known vacuum vapor deposition method, sputtering method, ion plating method, chemical vapor deposition method, etc. conventionally. Among these, a sputtering method is preferable at the point of adhesiveness. The thickness of the above-mentioned transparent electrode is usually preferable in the range of 500-2000 GPa from a balance of transparency and electroconductivity.

2 is a cross-sectional explanatory diagram of a touch panel display device formed by using various electronic materials for display devices and the rigid 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 which formed the transparent electrode on a hard transparent board | substrate sandwich a dot spacer so that a transparent electrode may mutually oppose each other. And a polarizing plate is arrange | positioned at the outer side of each touch panel member, and the display apparatus including a liquid crystal display device other than a polarizing plate is arrange | positioned at the outer side of either touch panel member. Here, the gas barrier film may be formed on both surfaces of the rigid transparent substrate.

3 is an explanatory cross-sectional view of an organic EL display device formed by using various electronic materials for display devices and the rigid 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 a transparent electrode, a hole injection layer, a hole transport layer, a light emitting layer, an electron on a hard transparent substrate The transport layer and the metal electrode are laminated. Here, the whole may be sealed by a gas barrier film not shown. Further, a gas barrier film may be formed on both surfaces of the rigid transparent substrate. In 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 an electronic material for a display device on a rigid transparent substrate, an inorganic oxide film or an ethylene-vinyl alcohol copolymer (for example, a gas barrier film formed between the rigid transparent substrate and the display device electronic material as needed) Although gas barrier resin layers, such as Eval brand name Eval, a sonomol), and vinylidene chloride, are mentioned, Preferably it is an inorganic oxide film. An inorganic oxide is an oxide of a metal, a nonmetal, and a submetal, and specific examples thereof include aluminum oxide, zinc oxide, antimony oxide, indium oxide, calcium oxide, cadmium oxide, silver oxide, gold oxide, chromium oxide, silicon oxide, cobalt oxide, and 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 and the like, and silicon oxide is particularly preferred. In addition, the inorganic oxide may contain a small amount of metals, nonmetals, submetals alone, hydroxides thereof, and carbon or fluorine as appropriate in order to improve flexibility. As a method of forming a gas barrier film, the method of coating resin etc. and the method of forming the vapor deposition film which consist of inorganic oxides are mentioned. As a method of forming a vapor deposition film, conventionally well-known methods, such as a vacuum vapor deposition method, a vacuum sputtering method, an ion plating method, and a CVD method, can be used.

There is no restriction | limiting in particular about the thickness of this gas barrier film | membrane, Although it changes also with the kind of component of a gas barrier film | membrane, in consideration of economy other than oxygen gas barrier property and water vapor barrier property, 5-50 nm of film thickness is preferable. If the thickness of the film is less than 5 nm, there is a possibility that the film becomes island-like and there is a possibility that a portion where the film is not formed may occur, so that a uniform film may not be obtained. In order to obtain higher oxygen gas barrier properties and water vapor barrier properties, the thickness of the film may be increased. However, if the thickness exceeds 50 nm, the productivity is worsened, the cost is high, and the transparency is also deteriorated.

Hereinafter, the Example of this invention is shown. In addition, curable resin using the following Example is obtained by the method shown to the following synthesis examples.

Synthesis Example

Into a 2 L four-necked flask equipped with a stirrer and a dropping lot, 300 mL of isopropyl alcohol and 600 mL of toluene, 22.37 g of a 20w% aqueous tetramethylammonium hydroxide solution (4.55 g / 0.05 mol tetramethylammonium hydroxide, 17.82 g / 0.99 mol of water) were charged. did. A mixture solution of 44.4 g / 0.30 mol of vinyltrimethoxysilane and 50 mL of isopropyl alcohol was charged into the dropping lot, and the reaction vessel was added dropwise at room temperature over 3 hours while stirring. It stirred for 3 hours, without heating, after completion | finish of dripping. After stirring for 3 hours, stirring was stopped and the reaction solution was aged at room temperature for 18 hours. The reaction solution was added to 1 L of 0.1 M citric acid aqueous solution and neutralized. The reaction solution was washed with water until neutral, and anhydrous magnesium sulfate was added to dehydrate. 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 four-necked flask equipped with a stirrer and a dropping lot. 1.00 mL of dehydrated pyridine and dropping lot were added to 3.2 g / 0.025 mol of dimethyldichlorosilane, 2.7 g / 0.025 mol of trimethylchlorosilane and 30 mL of tetrahydrofuran to the reaction vessel, and stirred at 3 ° C. at room temperature while stirring the reaction vessel under a stream of nitrogen. It was dripped over time. It stirred for 3 hours, without heating, after completion | finish of dripping. After stirring for 3 hours, 300 mL of toluene was added, and then the reaction solution was washed with water until neutral, and anhydrous magnesium sulfate was added to dehydrate. The inorganic magnesium sulfate was collected by filtration and concentrated under reduced pressure to obtain 27.1 g of a curable resin [General Formula (1)] as a colorless transparent liquid.

In the 1H-NMR of this curable resin, the sharp signal of the vinyl group was observed, and it was confirmed that the hydrolysis-condensation product from vinyl trimethoxysilane has a cage structure. In this regard, for the dense structural part (A), which is a three-dimensional polyhedral structure composed of a metal oxide, that is, silicon oxide, it is a cube structure represented by (SiO _3/2 ) ₈ composed of eight silicon atoms and twelve oxygen atoms. It can be assumed that the derived Kp was 0.73. In addition, the portion other than the (A) of the curable resin _{(H 2 C = CH-SiO} 3/2) , and a vinyl group and (Me ₃ SiO _1/2) and (Me ₂ SiO) a residue of ₈ loose structural moiety ( B), and the weight ratio [(A) / (B)] determined from these was 1.302. In addition, the number average molecular weight (Mn) by GPC was 5200. In addition, when deriving the Kp of the dense structural site (A), since (SiO _3/2 ) ₈ is part of (A) and exists as part of the general formula (I) resin, it is impossible to withdraw and directly Kp. Cannot be obtained. Therefore, it calculated using (HSiO3 / ₂ ) ₈ as a compound which can be approximated the least with the influence on Kp.

Example 1

100 weight part of curable resin obtained by the synthesis example, and 2 weight part of dicumyl peroxide (Percumyl D by Nippon Oil Co., Ltd.) were mixed until it became uniform, and the curable resin composition was obtained. This was poured into a mold composed of a glass plate so as to have 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 to form a molded article (hard transparent substrate). )

Example 2

58 weight part of curable resin obtained by the synthesis example, 42 weight part of terminal trimethylsilyl-modified polymethyl hydrosiloxane (HMS-992 by Azmax Corporation), and 0.5 weight of platinum-vinylsiloxane complex (SIP 6830.3 by Azmax Corporation) The parts were mixed until uniform, thereby obtaining a curable resin composition. This was poured into a mold composed of a glass plate until it became 0.2 mm, and heated at 100 ° C for 1 hour at 120 ° C for 1 hour, at 140 ° C for 1 hour, at 160 ° C for 1 hour and at 180 ° C for 2 hours to form a molded product (hard transparent substrate). )

Example 3

58 parts by weight of curable resin obtained in the synthesis example, 21 parts by weight of terminal trimethylsilyl-modified polymethylhydrosiloxane (HMS-992 manufactured by Azmax Corporation) and 2 parts by weight of dicumyl peroxide (Percumyl D, manufactured by Nippon Oil Industries, Ltd.) And 0.5 weight part of platinum-vinylsiloxane complex (Azmax Corporation SIP 6830.3) until it became uniform, and obtained curable resin composition. This was poured into a mold composed of a glass plate until it became 0.2 mm, and heated at 100 ° C for 1 hour at 120 ° C for 1 hour, at 140 ° C for 1 hour, at 160 ° C for 1 hour and at 180 ° C for 2 hours to form a molded product (hard transparent substrate). )

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

<Heat resistance>

In the vignette softening test, the indenter entered 0.4 mm or more at 120 degrees C or less under the measurement conditions of 1.0 mm of indenter cross-sectional area, 5 kg of load, and the temperature increase rate of 50 degree-C / hr. ○ that there was almost no entry below 0.1 mm.

<Birefringence>

In-plane birefringence was measured with the wavelength of 400-800 nm using the granularity difference measuring apparatus (made by Nikon, NPDM-1000).

<Light transmittance>

The transmittance | permeability in wavelength 550nm was measured using the spectrophotometer of Hitachi Seisakusho.

<Roughness of surface of ITO film (Ra)>

The surface roughness was measured by AFM. The measuring range was 10 micrometers and it measured on the conditions of tapping mode.

<Flexibility>

(Circle) and the thing which cracked were made into what the gold did not generate | occur | produce when it wound around the test laminated body by the core rod of diameter 25mm, and was bent 90 degrees.

Table 1 shows the evaluation results of the heat resistance, birefringence, light transmittance, roughness and bendability of the surface of the ITO film of the test laminates obtained in Examples 1 to 3.

In addition, the test laminated body obtained in Examples 1-3 was used for one touch panel member, and the other thing which formed the 150 nm transparent conductive thin film on the glass substrate as the other touch panel member by the same method as the above was used. did. These two touch panel members were arrange | positioned through the epoxy beads of 30 micrometers in diameter so that a transparent conductive thin film may oppose, and the touch panel test body was produced. The following method was evaluated about this obtained touch panel test body.

Comparative Example 1

A touch panel test body was produced in the same manner as in Examples 1 to 3 except that a polyethylene terephthalate having a thickness of 0.188 mm was used instead of the rigid transparent substrate.

1) Heat discoloration:

The laminated touch panel test body was processed in 120 degreeC hot air circulation oven for 120 hours, and discoloration of the board | substrate was confirmed. When there was no change and it had coloring, such as (circle) and yellowing, it was set as x.

2) pen sliding test:

A weight of 250 g was added to the polyacetal pen (tip shape: 0.8 mm R), and 200,000 sliding tests were performed. When whitening was not seen in a sliding part and there was no abnormality in ON resistance, it was set as x when abnormality was seen in (circle) and whitening and ON resistance.

3) Targun Test:

The weight of 250 g was added to the polyacetal pen (tip shape: 0.8 mmR), and 1 million times of keystroke tests were done. (Circle) when there was no abnormality in an ON resistance, and it turned into x when an abnormality was seen in ON resistance.

Table 2 shows the evaluation results of film formability, heat discoloration, pen sliding test, and keying test of the touch panel test body produced using the test laminate obtained in Examples 1 to 3 and Comparative Example 1.

1 is a cross-sectional explanatory diagram of a liquid crystal display device formed by using an electronic material for a display device and the rigid transparent substrate of the present invention.

2 is a cross-sectional explanatory diagram of a touch panel display device formed using an electronic material for a display device and the rigid transparent substrate of the present invention.

3 is an explanatory cross-sectional view of an organic EL display device formed using an electronic material for a display device and the rigid transparent substrate of the present invention.

Claims (10)

A display device in which an electronic material for display device is laminated on a hard transparent substrate, wherein the hard transparent substrate is obtained by curing the curable resin represented by the following general formula (1), and the curable resin is calculated from the following formula (2) In addition to having a dense structural part (A) consisting of a metal oxide having a packing coefficient (Kp) of 0.68 to 0.8, an organic material having a Kp of less than 0.68, or a loose structural part (B) consisting of an organic material and an organic metal oxide. And the weight ratio of the structural moiety (A) / (B) is 0.01 to 5.00, and has one or more unsaturated bonds and an average molecular weight of 800 to 60000. -[(A)-(B) _m ] _n- (1) (Where m and n represent an integer of 1 or more) Kp = AnVwp / Mw (2) (Where, An = Avogadro's number, Vw = van der Waals volume, p = density, Mw = molecular weight, Vw = ΣVa, Va = 4 Π / R 3 -Σ1 / 3 Π hi 2 (3Ra-hi), hi = Ra -(Ra ² + di ² -Ri ² ) / 2di, Ra = atomic radius, Ri = bonding atom radius and di = atomic distance.) 2. The dense structural part (A) is a metal oxide moiety having a three-dimensional polyhedral structure excluding the organic part of the following general formula (I), and the loose structural part (B) is an organic material of general formula (I). A display device comprising the part 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 is an unsaturated group represented by (a) -R ¹ -OCO-CR ² = CH ₂ , (b) -R ¹ -CR ² = CH ₂ or (c) -CH = CH ₂ , an alkyl group or a cyclo It is an alkyl group, a cycloalkenyl group, a phenyl group, a hydrogen atom, an alkoxyl group, or an alkylsiloxy group, and some R in Formula (I) may mutually differ, but one or more is (a), (b), (c And 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. Unsaturated group, alkyl group, cycloalkyl group, cycloalkenyl group, phenyl group, hydrogen atom, alkoxyl group or alkyl represented by ² = CH ₂ , (b) -R ¹ -CR ² = CH ₂ or (c) -CH = CH ₂ Is a siloxy 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 satisfy w + x + y + z ≧ 8 And j, k and l are each 0. It shows on the whole number.) The structural unit represented by (A) in general formula (1) is a valence of RSiX ₃ , MX ₄ or a mixture thereof, wherein R, M and X are the same as general formula (I). A display device comprising a metal oxide moiety that is a three-dimensional polyhedral structural skeleton in a structural unit represented by formula (I) obtained from a decomposition condensate. 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 (wherein R ³ to R ⁷ and X are Is the same as general formula (II).) And the chain unit of the metal oxide represented by the general formula (II) prepared from the hydrolysis condensate of general formula (II) and the metal atom contained in the structure represented by the general formula (I) A display device comprising an organic group present. The curable resin composition is obtained by blending a hydrosilylation catalyst and / or a radical initiator with the curable resin to obtain a curable resin composition, and then the curable resin composition is molded and thermosetted or photocured. A hard transparent substrate is obtained, The display apparatus characterized by the above-mentioned. The display device according to claim 5, 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 a 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 color filter and a transparent electrode on a rigid transparent substrate. And the liquid crystal first member having the alignment film laminated thereon and the liquid crystal second member having the thin film transistor and the alignment film laminated on the rigid transparent substrate sandwiching the liquid crystal layer so that the alignment films face each other, and further comprising a hard transparent substrate of the liquid crystal first member. A polarizing plate is disposed outside and a liquid crystal display device comprising a polarizing plate and a backlight disposed outside the hard transparent substrate of the liquid crystal second member. 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 is transparent on a rigid transparent substrate. A display device comprising an organic EL display device in which an electrode, a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, and a metal electrode are stacked and sealed by a gas barrier film. 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, The pair of touch panel members which formed the transparent electrode on the rigid transparent substrate It is a touch panel display device which inserts a dot spacer so that a transparent electrode may oppose each other, a polarizing plate is arrange | positioned on the outer side of each touch panel member, and the liquid crystal display device is further arrange | positioned at the outer side of any one touch panel member, It is characterized by the above-mentioned. Display device. The display device according to any one of claims 7 to 9, further comprising a gas barrier film disposed between the rigid transparent substrate and the transparent electrode.

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