JP2009241520A - Transparent substrate - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a transparent substrate which has excellent gas barrier properties against water vapor or the like and is high in surface smoothness. <P>SOLUTION: The transparent substrate includes a transparent laminated sheet 1 which is manufactured by impregnating a glass fiber substrate with a resin composition adjusted to have a refractive index close to that of glass fibers by mixing a high refractive index resin having a refractive index higher than that of the glass fibers with a low refractive index resin having a refractive index lower than that of the glass fibers and curing the resin composition. A transparent gas barrier layer 2 having gas barrier properties and a transparent gas absorption layer 3 having gas absorption properties are laminated on the transparent laminated sheet 1. The permeation of gas can be intercepted by the gas barrier layer 2, and gas which passed through the gas-barrier layer 2 can be absorbed by the gas absorption layer 3, improving an effect to intercept the gas permeation. The unevenness of the surface of the transparent laminated sheet 1 is filled with the gas barrier layer 2 and the gas absorption layer 3 to flatten the surface so that the smoothness of the surface can be improved. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a transparent substrate used for a liquid crystal display or the like.

  A transparent substrate formed of a transparent laminated plate has been studied as a material to replace a glass plate in flat panel displays such as a liquid crystal display, a plasma display, and an EL display (for example, Patent Document 1).

  As an example of such a transparent laminate used as a transparent substrate, a prepreg is prepared by impregnating a substrate made of glass fiber such as glass cloth with a transparent thermosetting resin having a refractive index similar to that of glass fiber. What was produced by heat-press-molding can be mentioned. An epoxy resin is generally used as the transparent thermosetting resin. In order to approximate the refractive index of the resin to the refractive index of the glass fiber, an epoxy resin having a higher refractive index than the glass fiber and a refractive index higher than that of the glass fiber are used. A resin composition is used in which a small epoxy resin is mixed and the mixing ratio is adjusted so that the refractive index approximates the refractive index of the glass fiber. Thus, by combining the refractive index of the glass fiber of the base material and the matrix resin, the refraction of light in the transparent laminate can be suppressed and used as a transparent substrate of a display excellent in visibility.

FIG. 3 shows an example of a schematic configuration of a liquid crystal display produced using a transparent substrate A formed by such a transparent laminated plate. A pair of transparent substrates A are arranged in parallel, and the space between the transparent substrates A is shown. The drive element 10 is mounted on the board. The drive element 10 includes a pixel electrode 11 and TFT 12 provided on one transparent substrate A, a common electrode 13 provided on the other transparent substrate A, and liquid crystal molecules 14 filled between the transparent substrates A. It is what is done.
JP 2004-307851 A

  In the liquid crystal display as described above, if the distance between the transparent substrates A arranged opposite to each other is non-uniform, the thickness of the liquid crystal molecules 14 filled becomes non-uniform, and the orientation of the liquid crystal molecules 14 May be partially disturbed and light scattering may occur. Further, the liquid crystal molecules 14 are liable to deteriorate when water vapor, oxygen, or the like acts on them, and the life of the liquid crystal display may be shortened by the action of water vapor or the like.

  However, the transparent substrate A is formed by a transparent laminated plate produced by impregnating and curing a resin on a glass substrate, and has a high gas barrier property like a glass plate because the resin is used as a matrix. is not. Therefore, when such a transparent substrate A is used as a substrate for a liquid crystal display, it is not possible to completely block gas such as water vapor or oxygen from passing through the transparent substrate A, and water vapor or oxygen acts on the liquid crystal molecules 14. There was a problem that it may deteriorate.

  Further, since the transparent substrate A is formed by a transparent laminated plate prepared by impregnating and curing a resin on a glass base material, it is difficult to form a surface with high smoothness like a glass substrate. The unevenness of the glass substrate formed by cloth or the like appears on the surface, and the smoothness tends to be lowered. Accordingly, when such a transparent substrate A is used as a substrate for a liquid crystal display, the interval between the transparent substrates A arranged opposite to each other becomes non-uniform, and the alignment of the liquid crystal molecules 14 that are filled is disturbed. There is a problem that scattering may occur and a clear image may not be obtained.

  The present invention has been made in view of the above points, and an object of the present invention is to provide a transparent substrate having a high barrier property against gas such as water vapor and a high surface smoothness.

  The transparent substrate according to the present invention is a mixture of a high refractive index resin having a refractive index larger than that of glass fiber and a low refractive index resin having a refractive index smaller than that of glass fiber so that the refractive index approximates that of glass fiber. A transparent laminate 1 prepared by impregnating and curing a glass fiber base material with the resin composition prepared in the above, a transparent gas barrier layer 2 having gas barrier properties and a transparent gas absorbing layer 3 having gas absorbability Are laminated on the transparent laminated plate 1.

  According to the present invention, the gas barrier layer 2 can block the passage of gas such as water vapor, and the gas absorption layer 3 can absorb the permeated gas such as water vapor. In addition, the surface of the transparent laminate 1 can be flattened with the gas barrier layer 2 and the gas absorption layer 3 to improve the surface smoothness. It is something that can be done.

  Further, the present invention is characterized in that, when a display driving element is mounted on a transparent substrate, the gas barrier layer 2 is arranged on the side farther from the driving element 10 than the gas absorbing layer 3. is there.

  According to the present invention, even if a gas such as water vapor passes through the gas barrier layer 2, the gas can be reliably prevented from being absorbed by the gas absorption layer 3 and acting on the driving element 10.

  In the present invention, the gas absorption layer 3 is formed by containing a gas absorption component, and the gas absorption component is made of an organometallic compound. The gas absorption layer 3 has a high gas absorptivity such as water vapor. The layer 3 can be formed.

  In the present invention, the organometallic compound contained in the gas absorption layer 3 contains a divalent or higher metal, and the metal is a compound having a chemical bond with oxygen. The gas absorption layer 3 having high gas absorbability such as water vapor can be formed.

  In the present invention, the organometallic compound is a compound obtained by a reaction between an alkylaluminum and a polysiloxane having a silanol group. The gas-absorbing layer 3 having a high gas-absorbing property such as water vapor. Can be formed.

  In the present invention, the organometallic compound is a trivalent metal-dialkyl oxide-monoethyl acetoacetate, and forms a gas absorption layer 3 having high gas absorbency such as water vapor. It is something that can be done.

  In the present invention, the trivalent metal is at least one selected from aluminum, lanthanum, yttrium, and gallium, and forms the gas absorption layer 3 having high gas absorbability such as water vapor. It is something that can be done.

  In the present invention, the organometallic compound is a tetravalent metal-dialkyl oxide-diethyl acetoacetate, and can form the gas absorption layer 3 having high gas absorbency such as water vapor. It can be done.

  In the present invention, the tetravalent metal is at least one selected from germanium and silicon, and can form the gas absorption layer 3 having high gas absorbency such as water vapor. It is.

  In the present invention, the organometallic compound includes a compound in which a carboxylate group is coordinated to three trivalent metals of a (3-valent metal-oxygen-) 6-membered ring, and (-3valent metal-oxygen-). Forming at least one compound selected from compounds in which a phenoxy group is coordinated to three trivalent metals having a six-membered ring, and forming a gas absorption layer 3 having a high gas absorbency such as water vapor It is something that can be done.

  In the present invention, the trivalent metal is aluminum, and can form the gas absorption layer 3 having high gas absorbency such as water vapor.

  Moreover, in this invention, the gas absorption layer 3 is covered with the 2nd gas barrier layer 4 interrupted | blocked from external air, It is characterized by the above-mentioned.

  According to the present invention, the second gas barrier layer 4 can prevent the gas absorption layer 3 from directly absorbing a gas such as water vapor from the outside air and becoming saturated in a short period of time, and the gas blocking performance can be extended for a long time. It can be maintained over time.

  In the present invention, the second gas barrier layer 4 is characterized by being transparent. Even when the second gas barrier layer 4 is covered with the gas absorption layer 3, the second gas barrier layer 4 can be used as a transparent substrate. It can maintain transparency.

  Further, the present invention is characterized in that at least one of the transparent gas barrier layer 2 and the transparent gas absorption layer 3 is formed in a plurality of layers, and gas blocking and absorption can be performed in a plurality of layers, High gas shutoff performance can be obtained.

  In the present invention, the surface formed by the gas barrier layer 2 and the gas absorption layer 3 has a roughness (Ra) of 20 nm or less.

  When the smoothness of the surface of the transparent substrate is less than or equal to the roughness (Ra) 20 nm, the liquid crystal molecules are more effectively prevented from being disturbed in alignment when the transparent substrates are arranged in parallel and filled with the liquid crystal molecules. Light scattering can be prevented and a clear image can be obtained.

  Further, the present invention is characterized in that the second gas barrier layer 4 disposed in the outermost layer is peelable, and the gas absorption layer is formed by the second gas barrier layer 4 before using the transparent substrate. When the transparent substrate is assembled to a display substrate or the like, the second gas barrier layer 4 can be used in a peeled state.

  According to the present invention, gas such as water vapor can be blocked from passing through the gas barrier layer 2, and gas such as water vapor that can pass through can be absorbed by the gas absorption layer 3. A high effect of blocking gas permeation can be obtained. Moreover, the unevenness | corrugation of the surface of the transparent laminated board 1 can be filled with these gas barrier layers 2 and the gas absorption layer 3, and can be made flat, and the smoothness of the surface can be improved.

  Hereinafter, the best mode for carrying out the present invention will be described.

  First, the transparent laminated board used in this invention is demonstrated. This transparent laminate is adjusted so that the refractive index approximates the refractive index of the glass fiber by mixing a high refractive index resin having a higher refractive index than that of the glass fiber and a low refractive index resin having a lower refractive index than that of the glass fiber. The resin composition prepared is impregnated into a glass fiber substrate and cured.

  It is preferable to use a cyanate ester resin as a resin having a higher refractive index than the glass fiber. The cyanate ester resin is obtained by polymerization of a cyanate ester compound having two or more cyanate groups in one molecule by generating a triazine ring by trimerization. Examples of the cyanate ester compound include 2,2-bis ( Aromatic cyanate ester compounds such as 4-cyanatophenyl) propane, bis (3,5-dimethyl-4-cyanatophenyl) methane, 2,2-bis (4-cyanatophenyl) ethane, and derivatives thereof Can be used. These may be used alone or in combination of a plurality of types. This cyanate ester resin has a rigid molecular skeleton, and therefore imparts a high glass transition temperature to the cured product. Further, since cyanate ester resin is solid at normal temperature, it becomes easy to dry by touch when preparing a prepreg by impregnating a resin composition into a glass fiber substrate and drying it as described later. The prepreg is easy to handle.

  Here, when the refractive index of the glass fiber is, for example, 1.562, the cyanate ester resin used as the high refractive index resin preferably has a refractive index of around 1.6. When the refractive index of the glass fiber is n, n + 0 It is desirable that it is in the range of 0.03 to n + 0.06. In the present invention, the refractive index of the resin refers to the refractive index in the state of the cured resin, and is a value tested by ASTM D542.

  On the other hand, as the resin having a lower refractive index than the glass fiber, any epoxy resin can be used as long as it has a low refractive index, but it is preferable to use a hydrogenated bisphenol type epoxy resin. When the refractive index of the glass fiber is 1.562, for example, the low refractive index epoxy resin preferably has a refractive index of around 1.5, where n−0.04, where n is the refractive index of the glass fiber. It is desirable to be in the range of ˜n−0.08.

  In the low refractive index hydrogenated bisphenol type epoxy resin, as the bisphenol type, bisphenol F type, bisphenol S type and the like can be used in addition to the bisphenol A type.

  Further, as the hydrogenated bisphenol type epoxy resin having a low refractive index, it is preferable to use a solid type hydrogenated bisphenol type epoxy resin that is solid at room temperature. Liquid type hydrogenated bisphenol type epoxy resin that is liquid at room temperature can be used, but when preparing the prepreg, it can only be dried to a sticky state with the touch, and the prepreg is easy to handle. Since it becomes worse, it is preferable to use a solid-type hydrogenated bisphenol-type epoxy resin. Furthermore, it is possible to use other than the hydrogenated bisphenol type epoxy resin as the low refractive index epoxy resin. For example, an epoxy resin containing 1,2-epoxy-4- (2-oxiranyl) cyclohexane is used in combination. be able to. This epoxy resin is used in combination to finely adjust the refractive index, and is an optimal resin for facilitating the production of a transparent laminate because it is solid at room temperature.

  Then, the above-described high refractive index cyanate ester resin is mixed with an epoxy resin such as a low refractive index hydrogenated bisphenol type epoxy resin to prepare and use a resin composition that approximates the refractive index of glass fiber. is there. The mixing ratio of the high refractive index cyanate ester resin and the low refractive index epoxy resin is arbitrarily adjusted so as to approximate the refractive index of the glass fiber. Here, it is desirable that the refractive index of the resin composition be as close as possible to the refractive index of the glass fiber. It is preferable to do this.

  The resin composition is preferably prepared such that the cured resin has a glass transition temperature (Tg) of 170 ° C. or higher. When the glass transition temperature is 170 ° C. or higher, the heat resistance of the transparent laminate can be increased. The upper limit of the glass transition temperature is not particularly set, but practically about 280 ° C. is the upper limit of the glass transition temperature. The glass transition temperature can be adjusted by changing the blending ratio of the cyanate ester resin in the resin composition, and depends on the type of low refractive index resin used together. If the cyanate ester resin is about 30% by mass or more in the resin component, the glass transition temperature of the resin composition can be adjusted to 170 ° C. or more.

  Furthermore, a curing initiator (curing agent) can be blended in the resin composition. An organic metal salt can be used as the curing initiator. Examples of the organic metal salt include salts of an organic acid such as octanoic acid, stearic acid, acetylacetonate, naphthenic acid, and salicylic acid with a metal such as Zn, Cu, and Fe. These may be used alone or in combination of two or more. Among them, zinc octoate is preferable. By using zinc octoate as the curing initiator, the glass transition temperature of the cured resin can be increased. The content of the organic metal salt such as zinc octoate in the resin composition is not particularly limited, but is preferably in the range of 0.01 to 0.1 PHR.

  A cationic curing agent can also be used as the curing initiator. Thus, by using a cationic curing agent, the transparency of the resin can be enhanced. The cationic curing agent is not particularly limited, and aromatic sulfonium salts, aromatic iodonium salts, ammonium salts, aluminum chelates, boron trifluoride amine complexes, and the like can be used. The content of the cationic curing agent in the resin composition is not particularly limited, but is preferably in the range of 0.2 to 3.0 PHR.

  Further, a curing catalyst such as a tertiary amine such as triethylamine or triethanolamine, 2-ethyl-4-imidazole, 4-methylimidazole, 2-ethyl-4-methyl-imidazole (2E4MZ) may be used as a curing initiator. it can. The content of the curing catalyst in the resin composition is not particularly limited, but is preferably in the range of 0.5 to 5 PHR.

  As described above, a resin composition can be prepared by blending an epoxy resin such as a high refractive index cyanate ester resin, a low refractive index hydrogenated bisphenol type epoxy resin, and a curing initiator. This resin composition is used as a resin varnish after being dissolved or dispersed in a solvent as required. The solvent is not particularly limited, but benzene, toluene, xylene, methyl ethyl ketone, methyl isobutyl ketone, acetone, methanol, ethanol, isopropyl alcohol, 2-butanol, ethyl acetate, butyl acetate, propylene glycol monomethyl ether, Propylene glycol monomethyl ether acetate, diacetone alcohol, N, N′-dimethylacetamide and the like can be used.

  On the other hand, the glass fiber is preferably E glass or NE glass in view of the effect of increasing the impact resistance of the transparent laminate. E glass is also called non-alkali glass and is a glass that is widely used as a glass fiber for resin reinforcement, and NE glass is NewE glass. Moreover, it is preferable to surface-treat glass fiber with the silane coupling agent normally used as a glass fiber processing agent in order to improve impact resistance. The refractive index of the glass fiber is preferably in the range of 1.55 to 1.57, and more preferably in the range of 1.555 to 1.565. If the refractive index of glass fiber is this range, the transparent laminated board excellent in visibility can be obtained. As the glass fiber base material, a glass fiber woven fabric or non-woven fabric can be used.

  A prepreg can be prepared by impregnating a glass fiber base material with a varnish of a resin composition, heating and drying. The drying conditions are not particularly limited, but a drying temperature of 100 to 160 ° C. and a drying time of 1 to 10 minutes are preferable.

  Next, one or a plurality of the prepregs are stacked and heated and pressed to cure the resin composition, thereby obtaining a transparent laminate. The conditions for the heat and pressure molding are not particularly limited, but a temperature range of 150 to 200 ° C., a pressure of 1 to 4 MPa, and a time of 10 to 120 minutes are preferable.

  In the transparent laminate obtained as described above, a resin matrix formed by polymerizing an epoxy resin such as a high refractive index cyanate ester resin and a low refractive index hydrogenated bisphenol type epoxy resin is a cyanate ester resin. By containing the glass, a glass transition temperature is high, and a transparent laminate having excellent heat resistance can be obtained. In addition, epoxy resins such as cyanate ester resin and hydrogenated bisphenol type epoxy resin are all excellent in transparency, and a transparent laminate having high transparency can be obtained. In this transparent laminated plate, the glass fiber base material content is preferably in the range of 25 to 65% by mass, and within this range, high impact resistance can be obtained due to the reinforcing effect of the glass fiber. Sufficient transparency can be obtained.

  Here, as a glass fiber base material, in order to obtain high transparency, it is preferable to use a plurality of thinly laminated ones. Specifically, it is preferable to use a glass fiber substrate having a thickness of 50 μm or less and to use two or more glass fiber substrates having a thickness of 50 μm or less. Although the minimum of the thickness of a glass fiber base material is not specifically limited, About 10 micrometers is a practical minimum. The number of glass fiber substrates is not particularly limited, but about 20 is the practical upper limit. When producing a transparent laminate using a plurality of glass fiber base materials in this way, each glass fiber base material is impregnated with a resin composition and dried to produce a prepreg, and a plurality of the prepregs are stacked and heated. A transparent laminate can be obtained by pressure molding, but a prepreg is produced by impregnating and drying a resin composition in a state where a plurality of glass fiber base materials are stacked, and this prepreg is heated and pressure-molded. A transparent laminate may be obtained.

  Then, the transparent substrate according to the present invention is formed by laminating the transparent gas barrier layer 2 having gas barrier properties and the transparent gas absorbing layer 3 having gas absorbability on the surface of the transparent laminate 1 produced as described above. A can be obtained.

  The gas barrier layer 2 and the gas absorption layer 3 are laminated on the transparent laminate 1 by forming the gas barrier layer 2 on the surface of the transparent laminate 1 and absorbing the gas on the gas barrier layer 2 as shown in FIG. The layer 3 may be formed, and as shown in FIG. 1B, the gas barrier layer 2 is formed on one surface of the transparent laminate 1, and the gas absorbing layer is formed on the other surface. 3 may be formed. When this transparent substrate A is used as a display substrate as shown in FIG. 3, the display driving element 10 is mounted on the lower side of the figure in FIGS. 1 (a) and 1 (b). In this case, the gas barrier layer 2 is disposed on the side farther from the driving element 10 than the gas absorption layer 3, and the gas barrier layer 2 is disposed outside the gas absorption layer 3 in the display.

  In the transparent substrate A formed by laminating the gas barrier layer 2 and the gas absorption layer 3 on the transparent laminate 1 as described above, the gas such as water vapor or oxygen in the outside air can be blocked by the gas barrier layer 2 first. It is possible to prevent the gas from being transmitted to the driving element 10. Even if these gases permeate the gas barrier layer 2, the permeated gas is absorbed by the gas absorption layer 3. Therefore, when the display driving element 10 is mounted on the transparent substrate A, it is possible to prevent these gases from acting on the driving element 10 and deteriorating the liquid crystal molecules 14 of the driving element 10.

The gas permeability of the transparent substrate A formed by laminating the gas barrier layer 2 and the gas absorption layer 3 on the transparent laminate 1 is desirably a water vapor permeability (WVTR) of 0.1 g / m ² · 24 h or less. . When the water vapor transmission rate (WVTR) of the transparent substrate A is 0.1 g / m ² · 24 h or less, it is possible to effectively prevent a gas such as water vapor from acting on the driving element 10 and deteriorating. . It goes without saying that the water vapor transmission rate (WVTR) is preferably as small as possible. Here, the water vapor transmission rate is a value measured by a method based on JIS Z0208 (1976).

  Further, by providing the gas barrier layer 2 and the gas absorption layer 3 on the surface of the transparent laminate 1, the irregularities on the surface of the transparent laminate 1 can be filled with the gas barrier layer 2 and the gas absorption layer 3 to be flattened. The smoothness of the surface of the transparent substrate A formed by the gas barrier layer 2 and the gas absorption layer 3 can be improved. In this way, by increasing the smoothness of the surface of the transparent substrate A, when the liquid crystal molecules 14 of the driving element 10 are filled with the pair of transparent substrates A arranged in parallel as shown in FIG. The interval between the electrodes can be set to a uniform size, the liquid crystal molecules 14 can be prevented from being disturbed in alignment, and light scattering can be prevented from occurring. Can be produced.

  As for the smoothness of the surface of the transparent substrate A formed by the gas barrier layer 2 and the gas absorption layer 3, the surface roughness Ra is preferably 20 μm or less. When the surface roughness Ra is 20 μm or less, the interval between the transparent substrates A can be set more uniformly, and it is possible to more reliably prevent the occurrence of alignment disorder in the liquid crystal molecules, and light scattering occurs. This can be prevented. Needless to say, the surface roughness Ra is preferably as small as possible. Here, the surface roughness Ra is an arithmetic average roughness defined by JIS B0601 (1994), and the measurement was performed as follows. Using a surface roughness meter "SURFCOM 130A" manufactured by Tokyo Seimitsu Co., Ltd., the surface irregularities of the transparent laminate were measured at 3 points in the vertical, horizontal and 45 ° bias directions, respectively. The average value was taken as the Ra value.

The transparent gas barrier layer 2 having gas barrier properties is not particularly limited, but silicon nitride (SiN ₃ ), silicon oxynitride (SiON), silicon oxide (SiO ₂ ), aluminum oxide (Al ₂ O) ₃ ) and a thin film of an inorganic material such as magnesium oxide (MgO). Formation of a thin film of these inorganic materials can be performed using a vapor deposition method. For example, a chemical vapor deposition method (CVD) such as thermal CVD, plasma CVD, or laser CVD, vacuum deposition, or ion plating is used. Physical vapor deposition (PVD) such as coating, sputtering, and laser ablation can be employed. The thickness of the gas barrier layer 2 is not particularly limited, but is preferably in the range of about 10 to 1000 nm.

  Moreover, the film thickness of the transparent gas absorption layer 3 which has gas absorptivity is although it does not specifically limit, The range of about 1-1000 micrometers is preferable. The gas absorption layer 3 is not particularly limited, but preferably contains an organometallic compound as a gas absorption component.

  Examples of the organometallic oxide include a compound containing a divalent or higher metal and the metal having a chemical bond with oxygen.

  One such organometallic compound containing a metal having a valence of 2 or more and having a chemical bond with oxygen is a compound obtained by a reaction between an alkylaluminum and a polysiloxane having a silanol group.

  Examples of the alkylaluminum include trimethylaluminum, triethylaluminum, tripropylaluminum, tributylaluminum, trihexylaluminum, trioctylaluminum, diisobutylaluminum hydride, diethylaluminum ethoxide and the like.

  For example, by using trioctylaluminum as the alkylaluminum and reacting trioctylaluminum with a polysiloxane having a silanol group, an organometallic compound as shown in [Chemical Formula 1] can be obtained.

  And, as shown in [Chemical Formula 2], this organometallic compound is capable of chemically reacting with water to trap it and absorb water vapor.

  Further, as shown in [Chemical Formula 3], this organometallic compound can also react with oxygen to be captured and absorb oxygen.

   Further, as one of organometallic compounds containing the above divalent or higher metal and the metal having a chemical bond with oxygen, there is trivalent metal-dialkyl oxide-monoethyl acetoacetate. The trivalent metal is selected from aluminum, lanthanum, yttrium, and gallium.

  This organometallic compound is represented by the general formula [Chemical Formula 4] (wherein R1 to R3 and R5 are each independently an alkyl group having 1 or more carbon atoms, an aryl group, a cycloalkyl group, or a heterocyclic group. , Represents an organic group containing an acyl group, and M represents a trivalent metal atom). This metal organic compound reacts and traps chemically with moisture, and can absorb water vapor.

  As specific examples, the following [Chemical 5] to [Chemical 10] can be mentioned.

  One of organometallic compounds containing the above divalent metal and having a chemical bond with oxygen is tetravalent metal-dialkyl oxide-diethyl acetoacetate. The tetravalent metal is selected from germanium and silicon.

  This organometallic compound is represented by the general formula of [Chemical Formula 11] (wherein R1, R3 and R4 are each independently an alkyl group having 1 or more carbon atoms, an aryl group, a cycloalkyl group or a heterocyclic group). , Represents an organic group containing an acyl group, and M represents a tetravalent metal atom). This metal organic compound reacts and traps chemically with moisture, and can absorb water vapor.

  As specific examples, the following [Chemical 12] to [Chemical 13] can be mentioned.

  In addition, as an organometallic compound containing a metal having a divalent or higher valence and having a chemical bond with oxygen, a carboxylate is added to three trivalent metals having a (3-valent metal-oxygen-) 6-membered ring. There are compounds in which a group is coordinated, and compounds in which a phenoxy group is coordinated to three trivalent metals of a (3-valent metal-oxygen-) 6-membered ring. The trivalent metal is preferably aluminum.

  This organometallic compound is represented by the general formula of [Chemical Formula 14] (wherein R1 to R3 are independently an alkyl group having 1 or more carbon atoms, an aryl group, a cycloalkyl group, a heterocyclic group, an acyl group) An organic group containing a group, and M represents a trivalent metal atom). This metal organic compound reacts and traps chemically with moisture, and can absorb water vapor.

  Specific examples include those represented by [Chemical 16] to [Chemical 17] in addition to the aluminum oxide octylate represented by [Chemical 15].

  2 (a) and 2 (b) show another embodiment of the present invention, in which a second gas barrier layer 4 is laminated on the exposed surface of the gas absorption layer 3, and the gas absorption layer 3 is outside air. In this case, the second gas barrier layer 4 is used so as not to touch. When the gas absorption layer 3 is exposed and exposed to the outside air, gas such as water vapor in the atmosphere is constantly absorbed by the gas absorption layer 3, so that the gas absorption capacity of the gas absorption layer 3 is saturated and decreases in a short time. Therefore, there is a possibility that the effect of absorbing and blocking the gas such as water vapor that passes through the transparent substrate A by the gas absorption layer 3 cannot be maintained for a long time. For this reason, the gas absorption layer 3 is covered with the second gas barrier layer 4 so as not to come into contact with the outside air, and the gas absorption layer 3 absorbs and blocks the gas that passes through the transparent substrate A. It can last for a long time. The second gas barrier layer 4 can be formed of the same material as that of the transparent gas barrier layer 2 described above. By forming the second gas barrier layer 4 transparently, the second gas barrier layer 4 is formed. Even if the gas absorbing layer 3 is used while being coated, the transparency of the transparent substrate A can be maintained.

  Here, the problem that the gas absorption layer 3 touches the outside air and absorbs gas such as water vapor in the atmosphere is that the transparent substrate A is manufactured by laminating the gas barrier layer 2 and the gas absorption layer 3 on the transparent laminate 1. This often occurs until the transparent substrate A is incorporated into a product such as a display. After the transparent substrate A is incorporated, the second gas barrier layer 4 is sometimes unnecessary. In this case, it is desirable that the second gas barrier layer 4 be peelable.

  As such a peelable second gas barrier layer 4, for example, a resin film such as polyvinyl alcohol, ethylene vinyl alcohol copolymer, polyamide, cellulose, acrylic resin, or a metal foil such as aluminum foil or copper foil is used. Can do. And, by laminating these resin films or metal foils on the surface of the gas absorption layer 3 by thermocompression bonding, the gas absorption layer 3 can be coated as a second gas barrier layer 4 that can be peeled off. When the second gas barrier layer 4 becomes unnecessary, it can be easily peeled off and removed.

  Further, in the above embodiment, one gas barrier layer 2 and one gas absorption layer 3 are provided. However, a plurality of gas barrier layers 2 and gas absorption layers 3 may be provided. Gas blocking and absorption can be performed in a plurality of layers, and the gas blocking performance of the transparent substrate A can be enhanced.

  Next, the present invention will be specifically described with reference to examples.

Example 1
As a high refractive index resin, solid cyanate ester resin (“BADCy” manufactured by Lonza, 2,2-bis (4-cyanatophenyl) propane: refractive index 1.59) is 52 parts by mass, as a low refractive index resin. 48 parts by mass of an epoxy resin containing solid 1,2-epoxy-4- (2-oxiranyl) cyclohexane (“EHPE3150” manufactured by Daicel Chemical Industries, Ltd .: refractive index 1.51) was added, and further curing started 0.02 parts by mass of zinc octoate was blended as an agent, 50 parts by mass of toluene and 50 parts by mass of methyl ethyl ketone were added thereto, and the mixture was stirred and dissolved at a temperature of 70 ° C. to prepare a varnish of the resin composition. The refractive index of the cured product of this resin composition was 1.56.

  Next, a glass fiber cloth having a thickness of 25 μm (Asahi Kasei Electronics Co., Ltd., product number “1037”, E glass, refractive index 1.562) is impregnated with the varnish of the above resin composition and heated at 150 ° C. for 5 minutes. Thus, the solvent was removed and the resin was semi-cured to prepare a prepreg.

  Then, two sheets of this prepreg are stacked, sandwiched between release-molded glass plates, set in a press machine, and heated and pressed under conditions of 170 ° C., 2 MPa, 15 minutes, whereby the resin content is 63% by mass. A transparent laminate 1 having a thickness of 80 μm was obtained.

The transparent laminate 1 had a surface roughness Ra of 90 nm and a water vapor transmission rate (WVTR) of 2.6 g / m ² 24 h.

Next, a transparent gas barrier layer 2 made of silicon nitride (SiN ₃ ) having a thickness of 100 nm was formed on the surface of the transparent laminate 1 by plasma CVD. The surface roughness Ra of the gas barrier layer formed on the transparent laminate 1 is 20 nm, and the water vapor transmission rate (WVTR) of the transparent laminate 1 on which the gas barrier layer 2 is formed is 0.01 g / m ² 24 h. It was.

  Next, trioctyl aluminum (manufactured by Sigma Aldrich) and polydimethylsiloxane having silanol groups at both ends (YT3807, manufactured by GE-Toshiba Silicone) are formed on the surface of the gas barrier layer 2 formed on the transparent laminate 1. A solution composition obtained by stirring and reacting in mass in a hexane solution was spin-coated and dried to form a transparent gas absorption layer 3 having a thickness of 50 μm, and the gas absorption layer 3 and the gas barrier layer 2 were laminated. A transparent substrate A was obtained (see FIG. 1 (a)).

In this transparent substrate A, the roughness Ra of the surface on which the gas absorption layer 3 and the gas barrier layer 2 are formed is 17 nm, and the water vapor transmission rate (WVTR) of the transparent substrate A on which the gas absorption layer 3 and the gas barrier layer 2 are formed. ) Was 0.007 g / m ² 24 h.

(Example 2)
A transparent gas barrier layer 2 made of silicon oxynitride (SiON) having a thickness of 100 nm was formed on the surface of the transparent laminate 1 obtained in Example 1 by sputtering. The surface roughness Ra of the gas barrier layer 2 formed on the transparent laminate 1 is 20 nm, and the water vapor transmission rate (WVTR) of the transparent laminate 1 on which the gas barrier layer 2 is formed is 0.01 g / m ² 24 h. there were.

  Next, a toluene 50 mass% solution composition of aluminum oxide octylate (trade name: Olipe AOO, manufactured by Hope Pharmaceutical Co., Ltd.) is roll coated on the surface of the gas barrier layer 2 formed on the transparent laminate 1 and dried. Thus, a transparent gas absorption layer 3 having a film thickness of 50 μm was formed, and a transparent substrate A in which the gas absorption layer 3 and the gas barrier layer 2 were laminated was obtained (see FIG. 1A).

In this transparent substrate A, the roughness Ra of the surface on which the gas absorption layer 3 and the gas barrier layer 2 are formed is 17 nm, and the water vapor transmission rate (WVTR) of the transparent substrate A on which the gas absorption layer 3 and the gas barrier layer 2 are formed. ) Was 0.007 g / m ² 24 h.

(Example 3)
The transparent substrate A formed with the gas absorption layer 3 and the gas barrier layer 2 obtained in Example 1 is used, and the surface of the gas absorption layer 3 is made of silicon oxynitride (SiON) having a thickness of 100 nm by sputtering. A transparent second gas barrier layer 4 was formed, and a transparent substrate A in which the second gas barrier layer 4, the gas absorption layer 3, and the gas barrier layer 2 were laminated was obtained (see FIG. 2A).

In this transparent substrate A, the roughness Ra of the surface on which the second gas barrier layer 4, the gas absorption layer 3 and the gas barrier layer 2 are formed is 15 nm. The second gas barrier 4, the gas absorption layer 3 and the gas barrier layer 2 The water vapor transmission rate (WVTR) of this transparent substrate A having formed was 0.008 g / m ² 24 h.

Example 4
The transparent substrate A formed with the gas absorption layer 3 and the gas barrier layer 2 obtained in Example 2 is used, and the surface of the gas absorption layer 3 is made of silicon oxynitride (SiON) having a thickness of 100 nm by sputtering. A transparent second gas barrier layer 4 was formed, and a transparent substrate A in which the second gas barrier layer 4, the gas absorption layer 3, and the gas barrier layer 2 were laminated was obtained (see FIG. 2A).

In this transparent substrate A, the roughness Ra of the surface on which the second gas barrier layer 4, the gas absorption layer 3 and the gas barrier layer 2 are formed is 13 nm. The second gas barrier 4, the gas absorption layer 3 and the gas barrier layer 2 are formed. The water vapor transmission rate (WVTR) of this transparent substrate A having formed was 0.008 g / m ² 24 h.

(Example 5)
The transparent substrate 1 formed with the gas absorption layer 3 and the gas barrier layer 2 obtained in Example 1 was used, and a polyvinyl alcohol film having a thickness of 50 μm was pressure-bonded to the surface of the gas absorption layer 3 with a hot roll. A possible second gas barrier layer 4 was formed, and a transparent substrate A in which the peelable second gas barrier layer 4, the gas absorption layer 3, and the gas barrier layer 2 were laminated was obtained (see FIG. 2A).

In this transparent substrate A, the surface roughness Ra on the side where the peelable second gas barrier layer 4, gas absorption layer 3 and gas barrier layer 2 are formed is 13 nm, and the second gas barrier 4, gas absorption layer 3, The transparent substrate A on which the gas barrier layer 2 was formed had a water vapor transmission rate (WVTR) of 0.008 g / m ² 24 h.

(Example 6)
Using the transparent substrate A on which the gas absorption layer 3 and the gas barrier layer 2 formed in Example 2 were formed, and a polyvinyl alcohol film having a thickness of 50 μm was pressure-bonded to the surface of the gas absorption layer 3 with a hot roll. A possible second gas barrier layer 4 was formed, and a transparent substrate A in which the peelable second gas barrier layer 4, the gas absorption layer 3, and the gas barrier layer 4 were laminated was obtained.

In this transparent substrate A, the surface roughness Ra on the side where the peelable second gas barrier layer 4, gas absorption layer 3 and gas barrier layer 2 are formed is 13 nm, and the second gas barrier 4, gas absorption layer 3, The transparent substrate A on which the gas barrier layer 2 was formed had a water vapor transmission rate (WVTR) of 0.008 g / m ² 24 h.

As seen in Examples 1 to 6 above, the transparent laminate 1 has a surface roughness Ra of 90 nm and a water vapor transmission rate (WVTR) of 2.6 g / m ² 24 h. The transparent substrate A obtained by laminating the layer 2 and the gas absorption layer 3 and additionally the second gas barrier layer 4 has a surface roughness Ra of 13 to 20 nm and a water vapor transmission rate (WVTR). It is 0.007-0.008 g / m < ² > 24h, and it is confirmed that surface smoothness and gas barrier property can be improved greatly.

1 shows an example of an embodiment of the present invention, and (a) and (b) are schematic views. An example of other embodiments of the present invention is shown, and (a) and (b) are schematic views, respectively. It is a figure which shows schematic structure of a liquid crystal display.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Transparent laminated board 2 Gas barrier layer 3 Gas absorption layer 4 2nd gas barrier layer

Claims (16)

  A resin composition prepared by mixing a high refractive index resin having a refractive index higher than that of glass fiber and a low refractive index resin having a refractive index lower than that of glass fiber so that the refractive index approximates the refractive index of glass fiber. A transparent laminated plate produced by impregnating and curing a glass fiber substrate, and a transparent gas barrier layer having a gas barrier property and a transparent gas absorbing layer having a gas absorbing property are laminated on the transparent laminated plate A transparent substrate characterized by.   2. The transparent substrate according to claim 1, wherein the transparent substrate is mounted with a display drive element, and the gas barrier layer is disposed on a side farther from the drive element than the gas absorption layer.   The transparent substrate according to claim 1, wherein the gas absorption layer is formed to contain a gas absorption component, and the gas absorption component is made of an organometallic compound.   The transparent substrate according to claim 3, wherein the organometallic compound contained in the gas absorption layer is a compound containing a metal having a valence of 2 or more, and the metal has a chemical bond with oxygen.   The transparent substrate according to claim 4, wherein the organometallic compound is a compound obtained by a reaction between an alkylaluminum and a polysiloxane having a silanol group.   The transparent substrate according to claim 4, wherein the organometallic compound is a trivalent metal-dialkyl oxide-monoethyl acetoacetate.   The transparent substrate according to claim 6, wherein the trivalent metal is at least one selected from aluminum, lanthanum, yttrium, and gallium.   The transparent substrate according to claim 4, wherein the organometallic compound is tetravalent metal-dialkyl oxide-diethyl acetoacetate.   The transparent substrate according to claim 8, wherein the tetravalent metal is at least one selected from germanium and silicon.   An organometallic compound is a compound in which a carboxylate group is coordinated to three trivalent metals of a (-3valent metal-oxygen-) six-membered ring, and three (3-valent metal-oxygen-) six-membered rings The transparent substrate according to claim 4, wherein the transparent substrate is at least one selected from compounds in which a phenoxy group is coordinated to a trivalent metal.   The transparent substrate according to claim 10, wherein the trivalent metal is aluminum.   The transparent substrate according to any one of claims 1 to 11, wherein the gas absorption layer is covered with a second gas barrier layer that is shielded from outside air.   The transparent substrate according to claim 12, wherein the second gas barrier layer is transparent.   The transparent substrate according to claim 1, wherein at least one of a transparent gas barrier layer and a transparent gas absorption layer is formed in a plurality of layers.   The transparent substrate according to claim 1, wherein the surface roughness (Ra) is 20 nm or less.   The transparent substrate according to any one of claims 1 to 15, wherein the second gas barrier layer disposed in the outermost layer is peelable.

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