JP2002347161A - Particle-dispersed resin sheet and liquid crystal display - Google Patents

Abstract

(57) [Problem] To provide a particle-dispersed resin sheet or a base, which has a base material layer in which an inorganic oxide is dispersed, is thin and lightweight, and has excellent mechanical strength, dimensional stability, and gas barrier properties. It is an object of the present invention to provide a resin sheet in which minute regions are dispersed in a material layer, which is thin, lightweight, and has excellent mechanical strength, light diffusivity, and gas barrier properties, and a liquid crystal display device using the particle-dispersed resin sheet. I do. A particle-dispersed resin sheet having at least a base layer in which an inorganic oxide is dispersed in a resin and an inorganic gas barrier layer.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a particle-dispersed resin sheet or a base material layer in which an inorganic oxide is dispersed in a base material layer, which is thin, lightweight, and excellent in mechanical strength, dimensional stability and gas barrier properties. The present invention relates to a resin sheet in which minute regions are dispersed, and which is thin, lightweight, and excellent in mechanical strength, light diffusivity, and gas barrier properties, and a liquid crystal display device using the above-described particle-dispersed resin sheet.

[0002]

2. Description of the Related Art With the increase in size of liquid crystal display devices and electroluminescence display devices, glass-based substrates are heavy and bulky, so a resin sheet made of an epoxy-based resin or the like has been proposed as a substrate for the purpose of thinning and weight reduction. Is being developed. However, since the resin sheet undergoes expansion and contraction due to thermal expansion and the ingress and egress of moisture, there has been a problem that displacement occurs during electrode formation and color filter formation. Especially when forming a color filter, R (red), G
It is necessary to form (green), B (blue), and BM (black matrix) at predetermined positions with high precision, and it has been difficult to increase the precision with a resin sheet. First, color filters are formed by R (red), G (green), B
(Blue) and BM (black matrix) are patterned at room temperature for about 2 hours, baked at 150 ° C. for 20 minutes, and then returned to room temperature.
Perform the next color patterning at room temperature for about 2 hours.
Baking is performed at 50 ° C. for 20 minutes. Thus, the combination of patterning and baking is performed for all four colors. When forming a color filter on a resin sheet, the dimensions of the substrate change during patterning at room temperature after firing,
There is a problem that patterning misalignment occurs. In a display device such as a liquid crystal display device, there is a method in which a light diffusion sheet having transparent particles is attached to a viewing side of a liquid crystal cell to prevent glare caused by illumination light or a backlight built into the liquid crystal display device, thereby improving visibility. Was known. However, instead of attaching a light diffusion sheet to the viewing side of a liquid crystal cell, it has been studied to provide a liquid crystal cell substrate with a light diffusion function from the viewpoint of reducing the thickness and weight of the liquid crystal display device. In addition, since a resin sheet made of an epoxy resin or the like lacks gas barrier properties, when the resin sheet is used as a liquid crystal cell substrate, moisture and oxygen penetrate into the cell through the liquid crystal cell substrate to form a transparent conductive film pattern. The problem of disconnection has occurred. In addition, the moisture and oxygen that have penetrated into the cells grow until they form bubbles, causing problems such as poor appearance and deterioration of the liquid crystal. Therefore, a method of laminating an organic gas barrier layer made of polyvinyl alcohol or the like on a resin-based liquid crystal cell substrate has been used. However, a liquid crystal cell substrate having an organic gas barrier layer laminated thereon has a high impurity content, and when a liquid crystal display device is manufactured using a liquid crystal cell substrate having an organic gas barrier layer laminated, electrophoresis of impurity ions eluted from the substrate causes Since the effective electric field to the liquid crystal is reduced, the duty driving such as STN is not performed normally during the AC driving, and as a result, the display is disturbed or the ON / OFF operation is performed.
There was a problem that the OFF startup did not go smoothly.
Further, the organic gas barrier layer is liable to yellow, and when a liquid crystal display device is prepared using a liquid crystal cell substrate on which the organic gas barrier layer is laminated, there is a problem that the display takes on a yellow tint.

[0003]

DISCLOSURE OF THE INVENTION The present invention relates to a particle-dispersed resin sheet or substrate having an inorganic oxide dispersed in a substrate layer, which is thin, lightweight, and excellent in mechanical strength, dimensional stability and gas barrier properties. It is an object of the present invention to provide a resin sheet in which minute regions are dispersed in a material layer, which is thin, lightweight, and has excellent mechanical strength, light diffusivity, and gas barrier properties, and a liquid crystal display device using the particle-dispersed resin sheet. I do.

[0004]

SUMMARY OF THE INVENTION The present invention provides a particle-dispersed resin sheet having at least a base layer in which an inorganic oxide is dispersed in a resin and an inorganic gas barrier layer. It is preferable to use a thermoplastic resin or a thermosetting resin as the resin. The average particle diameter of the inorganic oxide is 1 to 100
It is preferably nm. The ratio of the inorganic oxide to the weight of the substrate layer is preferably 0.1 to 23% by weight. The particle-dispersed resin sheet according to the present invention has λ = 55.
The light transmittance at 0 nm is preferably 85% or more. Further, the particle-dispersed resin sheet according to the present invention comprises 1
The linear expansion coefficient at 00 to 160 ° C is 1.00E-4 /
It is preferable that the temperature is not higher than ° C. The dimensional change calculated from the dimensions after heating at 150 ° C. for 20 minutes and the dimensions after heating at 150 ° C. for 20 minutes and standing at room temperature for 2 hours is +
Preferably it is less than 0.015%. The inorganic gas barrier layer is made of silicon oxide, and the ratio of the number of oxygen atoms to the number of silicon atoms is preferably 1.5 to 2.0. Further, the inorganic gas barrier layer is made of silicon nitride,
The ratio of the number of nitrogen atoms to the number of silicon atoms is 1.0 to 4/3.
It is preferable that The thickness of the inorganic gas barrier layer is preferably 5 to 200 nm. The particle-dispersed resin sheet of the present invention has a moisture permeability of 10 g / m ² · 24 h · at
m or less. Further, the present invention may disperse a fine region having a different refractive index from the resin forming the base layer in the base layer in which the inorganic oxide is dispersed, and the addition amount of the fine region is based on the weight of the base layer. It is preferably 0.1 to 60% by weight. Average particle size of micro area is 0.2 μm to 10
Preferably, the difference in specific gravity between the minute region and the resin forming the base material layer is 1 or less, and the difference in refractive index between the minute region and the resin forming the base material layer is 0.03.
０．１0.10 is preferred. The present invention also provides a particle-dispersed resin sheet having at least an inorganic gas barrier layer and a base layer in which fine regions having a different refractive index from the resin forming the base layer are dispersed.
It is preferable that the addition amount of the fine region is 200 parts by weight or less per 100 parts by weight of the base layer forming resin. The average particle diameter of the fine region is preferably 0.2 μm to 100 μm, the specific gravity difference between the fine region and the resin forming the base layer is preferably 1 or less, and the fine region and the base layer are formed. The difference in refractive index from the resin is preferably from 0.03 to 0.10. The particle-dispersed resin sheet has a moisture permeability of 10
g / m ² · 24 h · atm is preferred.
In the present invention, in the particle-dispersed resin sheet in which the base layer is the outermost layer, the outermost surface of the base layer is preferably smooth. Further, the present invention can provide a liquid crystal display device using the particle-dispersed resin sheet of the present invention.

[0005]

BEST MODE FOR CARRYING OUT THE INVENTION The resin sheet according to the present invention is characterized by having at least a base material layer in which an inorganic oxide is dispersed in a resin and an inorganic gas barrier layer.

In the present invention, it is preferable to use a thermoplastic resin or a thermosetting resin as the resin. As the thermoplastic resin, polycarbonate, polyarylate,
Polyether sulfone, polysulfone, polyester,
Examples thereof include polymethyl methacrylate, polyetherimide, and polyamide. Examples of the thermosetting resin include an epoxy resin, unsaturated polyester, polydiallyl phthalate, and polyisobonyl methacrylate. One or more of these resins can be used, and they can be used as a copolymer or a mixture with other components.

A thermosetting resin is preferably used in order to obtain surface smoothness, and among the thermosetting resins, an epoxy resin is particularly preferably used from the viewpoint of hue. As the epoxy resin, for example, bisphenol A such as bisphenol A type, bisphenol F type, bisphenol S type and their water addition, novolak type such as phenol novolak type and cresol novolak type, triglycidyl isocyanurate type and hydantoin type Nitrogen-containing ring type,
Examples thereof include aromatic type such as alicyclic type, aliphatic type and naphthalene type, low water absorption type such as glycidyl ether type and biphenyl type, dicyclo type, ester type and ether ester type, and modified forms thereof. These may be used alone or in combination. Among the above various epoxy resins, it is preferable to use a bisphenol A type epoxy resin, an alicyclic epoxy resin, or a triglycidyl isocyanurate type from the viewpoint of anti-discoloration properties.

As such an epoxy resin, those having an epoxy equivalent of 100 to 1000 and a softening point of 120 ° C. or lower are preferably used in view of physical properties such as flexibility and strength of the obtained resin sheet. From the viewpoint of obtaining an epoxy resin-containing liquid having excellent coating properties and spreadability into a sheet, etc., a two-liquid mixed type liquid which shows a liquid state at a temperature lower than the temperature at the time of coating, particularly at room temperature, can be preferably used.

[0009] Epoxy resins include a curing agent, a curing accelerator, and if necessary, an antioxidant, a denaturant, a surfactant, a dye, a pigment, a discoloration inhibitor,
Various conventionally known additives such as an ultraviolet absorber can be appropriately compounded.

The curing agent is not particularly limited, either.
One or more appropriate curing agents depending on the epoxy resin can be used. Incidentally, examples thereof include organic compounds such as tetrahydrophthalic acid and methyltetrahydrophthalic acid, hexahydrophthalic acid and methylhexahydrophthalic acid, ethylenediamine and propylenediamine, diethylenetriamine and triethylenetetramine, and their amine adducts and meta Examples include amine compounds such as phenylenediamine, diaminodiphenylmethane, and diaminodiphenylsulfone.

Amide compounds such as dicyandiamide and polyamide; hydrazide compounds such as dihydrazide; methylimidazole, 2-ethyl-4-methylimidazole, ethylimidazole and isopropylimidazole, 2,4-dimethylimidazole and phenylimidazole; Imidazole compounds such as undecyl imidazole, heptadecyl imidazole, and 2-phenyl-4-methylimidazole are also examples of the curing agent.

Further, methylimidazoline, 2-ethyl-4-methylimidazoline, ethylimidazoline and isopropylimidazoline, 2,4-dimethylimidazoline and phenylimidazoline, undecylimidazoline and heptadecylimidazoline, and 2-phenyl-4-methylimidazoline Examples of the curing agent include imidazoline compounds, phenol compounds, urea compounds, and polysulfide compounds.

In addition, acid anhydride compounds and the like are also mentioned as examples of the curing agent, and from the viewpoint of preventing discoloration, such acid anhydride curing agents can be preferably used. Examples include phthalic anhydride and maleic anhydride, trimellitic anhydride and pyromellitic anhydride, nadic anhydride and glutaric anhydride, tetrahydrophthalic anhydride and methyltetrahydrophthalic anhydride, hexahydrophthalic anhydride and Examples include methylhexahydrophthalic anhydride, methylnadic anhydride, dodecenylsuccinic anhydride, dichlorosuccinic anhydride, benzophenonetetracarboxylic anhydride, and chlorendic anhydride.

In particular, they are colorless or pale yellow, such as phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride and methylhexahydrophthalic anhydride;
An acid anhydride-based curing agent having a molecular weight of about 140 to about 200 can be preferably used.

The mixing ratio of the epoxy resin and the curing agent is such that when an acid anhydride curing agent is used as the curing agent, the acid anhydride equivalent is 0.5 to 1 to 1 equivalent of the epoxy group of the epoxy resin. It is preferable to mix so as to be 5 equivalents, more preferably 0.7 to 1.2 equivalents. If the acid anhydride is less than 0.5 equivalent, the hue after curing becomes worse,
If it exceeds 1.5 equivalents, the moisture resistance tends to decrease. When other curing agents are used alone or in combination of two or more, the amount of use can be in accordance with the above-mentioned equivalent ratio.

Examples of the curing accelerator include tertiary amines, imidazoles, quaternary ammonium salts, organic metal salts, phosphorus compounds, urea compounds, and the like. In particular, tertiary amines, It is preferable to use imidazoles. These can be used alone or in combination.

The amount of the curing accelerator is preferably 0.05 to 7.0 parts by weight, more preferably 0.2 to 3.0 parts by weight, based on 100 parts by weight of the epoxy resin. . If the amount of the curing accelerator is less than 0.05 parts by weight, a sufficient curing promoting effect cannot be obtained, and if it exceeds 7.0 parts by weight, the cured product may be discolored.

Examples of the antioxidant include conventionally known compounds such as phenol compounds, amine compounds, organic sulfur compounds, and phosphine compounds.

Examples of the denaturing agent include conventionally known agents such as glycols, silicones and alcohols.

The above-mentioned surfactant is added for smoothing the surface of the epoxy resin sheet when the epoxy resin sheet is formed by a casting method while exposing the epoxy resin to air. Examples of the surfactant include a silicone type, an acrylic type, and a fluorine type, and a silicone type is particularly preferable.

The inorganic oxide in the present invention includes silica, titanium dioxide, antimony oxide, titania, alumina, zirconia, tungsten oxide and the like. These may be one kind or a mixture of two or more kinds. The average particle size of the inorganic oxide is not particularly limited, but is preferably 1 to 100 nm. If the average particle diameter is less than 1 nm, the dispersibility may be poor, and if it exceeds 100 nm, the optical characteristics of the particle-dispersed resin sheet may be poor.

In the present invention, the amount of the inorganic oxide to be added is preferably 0.1 to 23% by weight, more preferably 5 to 15% by weight, based on the weight of the substrate layer. When the addition amount of the inorganic oxide is less than 0.1% by weight based on the weight of the base material layer, the dimensional change of the particle-dispersed resin sheet is large and it becomes difficult to pattern the color filter layer and to form electrodes. If it exceeds 23%, the light transmittance of the particle-dispersed resin sheet deteriorates.

In the present invention, the material for forming the inorganic gas barrier layer includes silicon oxide, magnesium oxide,
Transparent gas barrier materials such as aluminum oxide and zinc oxide are known, but silicon oxide is preferably used from the viewpoint of gas barrier properties and adhesion to a substrate layer.

In the silicon oxide, the ratio of the number of oxygen atoms to the number of silicon atoms is 1.5 to 2.0. The gas barrier property, transparency, surface flatness, flexibility, film stress, and cost of the inorganic gas barrier layer are required. It is preferable from the point of view. If the ratio of the number of oxygen atoms to the number of silicon atoms is smaller than 1.5, the flexibility and the transparency deteriorate. In silicon oxide, the maximum value of the ratio of the number of oxygen atoms to the number of silicon atoms is 2.0.

As a material for forming the inorganic gas barrier layer, silicon nitride is also preferably used, and a material having a ratio of the number of nitrogen atoms to the number of silicon atoms of from 1.0 to 4/3 is preferred for the gas barrier property of the inorganic gas barrier layer and the transparency. It is preferably used in terms of properties, surface flatness, flexibility, film stress, cost, and the like. In silicon nitride, the maximum value of the ratio of the number of nitrogen atoms to the number of silicon atoms is 4/3.

In the present invention, the thickness of the inorganic gas barrier layer is preferably from 5 to 200 nm. If the thickness of the inorganic gas barrier layer is thinner than 5 nm, good gas barrier properties cannot be obtained, and if the thickness of the inorganic gas barrier layer is thicker than 200 nm, there are problems in terms of transparency, flexibility, film stress, and cost.

The light transmittance of the resin sheet of the present invention is preferably 85% or more, more preferably 88% or more. If the light transmittance is less than 85%, the display at the time of assembling a liquid crystal display device using the particle-dispersed resin sheet becomes dark, and the display quality is reduced.
The light transmittance was measured using a high-speed spectrophotometer at λ = 5.
Measure the transmittance at 50 nm.

The particle-dispersed resin sheet 1 of the present invention
The linear expansion coefficient at 00 ° C to 160 ° C is 1.00E-4.
/ ° C or lower, more preferably 8.
00E-5 / ° C or less is preferable. Linear expansion coefficient is 1.00E-
If the temperature exceeds 4 / ° C., misalignment of patterning is likely to occur when laminating color filters. Also, it becomes difficult to form an electrode on the particle-dispersed resin sheet. The linear expansion coefficient can be measured by the TMA method described in JIS K-7197 and calculated by (Equation 1). In the above formula, ΔIs (T ₁ ) and ΔIs (T ₂ ) are TMA measurement values (μm) at the temperatures T ₁ and T ₂ (° C.) at the time of sample measurement.
L ₀ is the length (mm) of the sample at room temperature.

(Equation 1)

In the particle-dispersed resin sheet of the present invention, the dimensional change rate calculated from the dimensions after heating at 150 ° C. for 20 minutes and the dimensions after heating at 150 ° C. for 20 minutes and standing at room temperature for 2 hours is +0.05. It is preferably less than 015%, more preferably + 0.012% or less. The dimensional change rate is calculated by (B−A) / A × 100, where A is a dimension immediately after heating at 150 ° C. for 20 minutes, and B is a dimension after heating at 150 ° C. for 20 minutes and then left at room temperature for 2 hours. be able to. When the dimensional change rate is + 0.020% or more, misalignment of patterning tends to occur when laminating color filters. Also, it becomes difficult to form an electrode on the particle-dispersed resin sheet.

The resin sheet of the present invention has a moisture permeability of 10 g / m.
Is preferably not more than ² · 24h · atm. If the water vapor transmission rate is greater than 10 g / m ² · 24 h · atm, moisture and oxygen enter the cell, breaking the transparent conductive film pattern and growing until the moisture and oxygen entering the cell form bubbles. This causes problems such as poor appearance and deterioration of liquid crystal.

In the particle-dispersed resin sheet of the present invention, fine regions having a refractive index different from that of the resin forming the base layer may be dispersed in the base layer. The amount is preferably from 0.1 to 60% by weight. That is, in the present invention, the inorganic oxide and the minute region may be simultaneously dispersed in the substrate layer, and the amount of the inorganic oxide added is 0.1 to 23% by weight based on the weight of the substrate layer.
In addition, the minute area is preferably 0.1 to 60% by weight based on the weight of the substrate layer. The expression that the minute regions are dispersed means a state in which the minute regions are present in the entire region of the base material layer without being unevenly distributed in a part of the base material layer.
Since the base material layer has an inorganic oxide, a dimensional change is suppressed, and a light diffusion function is provided by having a minute region.
By providing the light diffusion function, glare caused by illumination light or a backlight built in the liquid crystal display device can be prevented, and visibility can be improved.

As the minute regions, Si-based compounds, alumina, titania, zirconia, tin oxide, indium oxide,
Examples include inorganic particles made of cadmium oxide, antimony oxide, or the like, organic particles made of an acrylic resin, a melamine resin, or the like, and particles obtained by coating the inorganic particles with the organic particles.

Although the particle size of the material for forming the minute region can be determined as appropriate, the average particle size should be 0.2 to 0.2 in order to obtain sufficient light diffusivity.
100 μm, preferably 0.5 to 50 μm, more preferably 1 to 20 μm.

It is preferable that the difference in specific gravity between the minute region and the resin for forming the base layer is 1 g / cm ³ or less. Specific gravity difference is 1
When it is larger than g / cm ³ , it becomes difficult to make the base material layer uniformly contain minute regions.

The difference in refractive index between the minute region and the resin for forming the base layer is preferably 0.03 to 0.10. If the difference in refractive index is smaller than 0.03 or larger than 0.10. A sufficient light diffusion function cannot be provided.

Further, the present invention provides a particle-dispersed resin sheet having at least a base layer in which fine regions having a different refractive index from the resin forming the base layer are dispersed in the resin and an inorganic gas barrier layer. Can be. That is, in the present invention, the base layer may contain only a minute region having a different refractive index from the resin forming the base layer. In the particle-dispersed resin sheet in which the base layer contains only the fine region, the amount of the fine region added is 20 per 100 parts by weight of the base layer forming resin.
0 parts by weight or less, preferably 1 to 150 parts by weight, more preferably 2 to 100 parts by weight.

In the present invention, it is preferable to use a thermoplastic resin or a thermosetting resin as the resin. Thermosetting resins are preferred for obtaining surface smoothness, and epoxy resins are most preferred in terms of hue.

The particle size of the fine region can be appropriately determined, but in order to obtain sufficient light diffusivity, the average particle size should be 0.2 to 1%.
00 μm, preferably 0.5 to 50 μm, more preferably 1 to 20 μm.

It is preferable that the difference in specific gravity between the fine region and the resin for forming the base layer is 1 g / cm ³ or less. Specific gravity difference is 1
When it is larger than g / cm ³ , it becomes difficult to make the base material layer uniformly contain minute regions.

The difference in the refractive index between the minute region and the resin for forming the base layer is preferably 0.03 to 0.10. If the difference in the refractive index is smaller than 0.03 or larger than 0.10. A sufficient light diffusion function cannot be provided.

The particle-dispersed resin sheet having an inorganic gas barrier layer and a base material layer in which fine regions having different refractive indices are dispersed in at least a resin has a moisture permeability of 10 g / m ² · 24.
It is preferably at most h · atm. 10g moisture permeability
If it is larger than / m ² · 24 h · atm, moisture and oxygen enter the cell, and the transparent conductive film pattern breaks, and the moisture and oxygen entering the cell grow until they form bubbles, resulting in poor appearance. This causes problems such as causing the liquid crystal and deteriorating the liquid crystal.

In the particle-dispersed resin sheet of the present invention, it is most preferable that the base material layer has a fine region having a refractive index different from that of the inorganic oxide and the base material layer at the same time. When the base material layer has the inorganic oxide and the minute region at the same time, the dimensional change of the particle-dispersed resin sheet can be suppressed, and a light diffusion function can be provided to improve display quality. The particle dispersion resin sheet obtained by laminating the inorganic gas barrier layer on the particle dispersion resin sheet in which the base material layer has a minute region having a refractive index different from that of the inorganic oxide at the same time has a small dimensional change rate and has a light diffusion function. It has good quality and has a higher gas barrier function. In addition, since the inorganic gas barrier layer has a low impurity ion content, when a liquid crystal display device is manufactured, duty driving such as STN or ON / O
FF startup can be performed smoothly. In addition, the display quality is good because yellowing does not occur as in the case where an organic gas barrier layer is laminated.

In the particle-dispersed resin sheet according to the present invention in which the substrate layer is the outermost layer, the outermost surface of the substrate layer is preferably smooth. JIS B 0601-199
4 means that the surface roughness (Ra) is 1 nm or less. The smoothness facilitates formation of an alignment film, a transparent electrode, and the like.

By providing electrodes on the particle-dispersed resin sheet of the present invention, liquid crystal cells of, for example, TN type, STN type, TFT type, and ferroelectric liquid crystal type can be formed.

The particle-dispersed resin sheet of the present invention can be used for various applications, and is also preferably used as a liquid crystal cell substrate, a substrate for an electroluminescent display, or a substrate for a solar cell.

A liquid crystal display device is generally formed by appropriately assembling components such as a polarizing plate, a liquid crystal cell, a reflector or a backlight, and optical components as necessary, and incorporating a drive circuit. In the present invention, there is no particular limitation except that the above-mentioned particle-dispersed resin sheet is used, and it can be formed according to a conventional method. Therefore,
In forming the liquid crystal display device according to the present invention, for example, a light diffusion plate, an anti-glare layer, an antireflection film, a protective layer, a protective plate provided on the polarizing plate on the viewing side, or compensation provided between the liquid crystal cell and the polarizing plate on the viewing side. An appropriate optical component such as a retardation plate for use can be appropriately combined with the particle-dispersed resin sheet.

[0047]

EXAMPLES The present invention will be described below with reference to examples.
The present invention is not limited to these examples. The particle-dispersed resin sheet in the present invention can be produced by a casting method, a casting method, or the like. In the examples, the production method by the casting method is exemplified.

Example 1: 100 parts by weight of a liquid epoxy resin represented by the chemical formula (Chemical Formula 1) and a solid epoxy resin represented by the chemical formula (Chemical Formula 2) were mixed, and the mixture was stirred at 90 ° C. while heating to completely dissolve the resin. After allowing the mixture to cool to room temperature, a main agent was obtained. Next, 100 parts by weight of methyl hexahydrophthalic anhydride represented by the chemical formula (Chemical Formula 3) and 12 parts by weight of the modifier represented by the chemical formula (Chemical Formula 4) are mixed, and the mixture is heated and stirred at 120 ° C. to perform an esterification reaction. After cooling, the mixture is cooled to 80 ° C. and allowed to cool to room temperature, and tetra-n-butylphosphonium o, o- represented by the chemical formula (5)
2 parts by weight of diethyl phosphorodithioate were stirred and mixed to obtain a curing agent. The average particle diameter is 1 in 460 parts by weight of the curing agent.
2 nm silica particles (AERO manufactured by Nippon Aerosil Co., Ltd.)
(SILR974) 8.4 parts by weight and 380 parts by weight of the main agent were mixed by stirring to prepare a liquid containing an epoxy resin.

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First, a 17% by weight toluene solution of urethane acrylate represented by the chemical formula (Chem. 6) was cast and applied to a stainless steel endless belt at a running speed of 0.3 m / min, and air-dried to evaporate the toluene. Thereafter, the mixture was cured using a UV curing device to form a urethane acrylate layer having a thickness of 2.0 μm. Subsequently, the epoxy resin-containing liquid was applied onto the urethane acrylate layer by casting at a rate of 0.3 m / min, heated at 150 ° C. using a heating device, and then heated and cured at 180 ° C. for 20 minutes. An epoxy resin layer of 400 μm was formed. Next, the laminate composed of the urethane acrylate layer and the epoxy resin layer was peeled off from the endless belt made of stainless steel, and the oxygen concentration was reduced to 0.5 by nitrogen replacement.
% On a glass plate in an atmosphere of 1% for 1 hour. Then, SiOx (x = x) was added to the epoxy resin layer side of the laminate comprising the urethane acrylate layer and the epoxy resin layer.
1.9) was converted to a batch sputtering system SM manufactured by Nippon Vacuum.
Using H-2306RE, 30 cc of argon gas was introduced, and sputtering was performed at a frequency of 500 W and a pressure of 0.4 Pa for 6 minutes and 20 seconds to form a 100 nm inorganic gas barrier layer.

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Example 2 The amount of silica particles added was 16.8.
A particle-dispersed resin sheet was obtained in the same manner as in Example 1 except that the amount was changed to parts by weight.

Example 3 The amount of silica particles added was 25.2.
A particle-dispersed resin sheet was obtained in the same manner as in Example 1 except that the amount was changed to parts by weight.

Example 4 A particle-dispersed resin sheet was obtained in the same manner as in Example 1 except that the amount of silica particles was changed to 84 parts by weight.

Example 5 A particle-dispersed resin sheet was obtained in the same manner as in Example 1, except that the amount of silica particles was changed to 168 parts by weight.

Example 6: In preparing an epoxy resin-containing liquid in Example 1, instead of adding 8.4 parts by weight of silica particles having an average particle diameter of 12 nm, an average particle diameter of 30 n was used.
A particle-dispersed resin sheet was obtained in the same manner as in Example 1, except that 168 parts by weight of the m alumina particles were added.

Example 7 A base material and a curing agent were prepared in the same manner as in Example 1. Next, 84 parts by weight of silica particles having an average particle diameter of 12 nm (Aerosil 974 manufactured by Nippon Aerosil Co., Ltd.) were added to 460 parts by weight of the curing agent, and Tospearl 145 (Toshiba Silicone) (particle size: 3.5 μm) was used as a fine region.
-4.2 μm) and 7.56 parts by weight of the base agent 38
0 parts by weight were stirred and mixed to prepare an epoxy resin-containing liquid. Next, a particle-dispersed resin sheet was obtained in the same manner as in Example 1. That is, a laminate comprising a urethane acrylate layer, an epoxy resin layer containing an inorganic oxide and minute regions, and an inorganic gas barrier layer was obtained from the outermost layer.

Example 8 A base material and a curing agent were prepared in the same manner as in Example 1. Next, 7.56 parts by weight of Tospearl 145 (Toshiba Silicone) (particle size: 3.5 μm to 4.2 μm) and 380 parts by weight of the main agent are mixed with 460 parts by weight of the curing agent as a minute area, and the epoxy resin is contained. A liquid was prepared. Next, a particle-dispersed resin sheet was obtained in the same manner as in Example 1. That is, a laminate comprising a urethane acrylate layer, an epoxy resin layer containing a minute region, and an inorganic gas barrier layer from the outermost layer was obtained.

Example 9: When preparing an epoxy resin-containing liquid in Example 8, instead of adding 7.56 parts by weight of Tospearl 145 (Toshiba Silicone), an average particle size of 4 was used.
A particle-dispersed resin sheet was obtained in the same manner as in Example 8, except that 7.56 parts by weight of Eposta M30 (Nippon Shokubai), which was an acrylic particle having a particle diameter of μm, was added. That is, a laminate comprising a urethane acrylate layer, an epoxy resin layer containing a diffuser, and an inorganic gas barrier layer from the outermost layer was obtained.

Comparative Example 1 An epoxy resin-containing liquid was prepared in the same manner as in Example 1 except that silica particles were not added. Then, a 17% by weight urethane acrylate toluene solution was cast and applied to a stainless steel endless belt at a running speed of 0.3 m / min, air-dried to evaporate the toluene, and then cured using a UV curing device. 2.0 μm thick
Was formed. Subsequently, a 5.5% by weight aqueous solution of a polyvinyl alcohol-based resin was cast and applied on the urethane acrylate layer at a rate of 0.3 m / min.
Drying was performed at 10 ° C. for 10 minutes to form a polyvinyl alcohol layer having a thickness of 3.7 μm. Subsequently, the epoxy-based resin-containing liquid was applied onto the polyvinyl alcohol layer by casting at a rate of 0.3 m / min, and heated at 150 ° C. using a heating device.
The coating was heated and cured at 0 ° C. for 20 minutes to form an epoxy resin layer having a thickness of 400 μm. Next, a urethane acrylate layer,
The laminate composed of the polyvinyl alcohol layer and the epoxy resin layer was peeled off from the endless belt made of stainless steel, and left on a glass plate at 180 ° C. for 1 hour in an atmosphere having an oxygen concentration of 0.5% by replacing with nitrogen to remove the resin sheet. Obtained.

Comparative Example 2 An epoxy resin-containing liquid was prepared in the same manner as in Example 1. Then, a 17% by weight urethane acrylate toluene solution was cast and applied to a stainless steel endless belt at a running speed of 0.3 m / min, air-dried to evaporate the toluene, and then cured using a UV curing device. A urethane acrylate layer having a thickness of 2.0 μm was formed. Subsequently, 5.5% by weight of the polyvinyl alcohol resin
Is applied on the urethane acrylate layer at a rate of 0.3 m / min., And dried at 100 ° C. for 10 minutes.
A polyvinyl alcohol layer having a thickness of μm was formed. Subsequently, the epoxy-based resin-containing liquid was applied onto the polyvinyl alcohol layer by casting at a rate of 0.3 m / min.
After heating at a temperature of 180 ° C., the resin was cured by heating at 180 ° C. for 20 minutes to form an epoxy resin layer having a thickness of 400 μm. Next, the laminate composed of the urethane acrylate layer, the polyvinyl alcohol layer, and the epoxy resin layer was peeled off from the stainless steel endless belt, and the oxygen concentration was reduced to 0.5 by nitrogen replacement.
% On a glass plate in an atmosphere of 1% for 1 hour to obtain a resin sheet.

Comparative Example 3 An epoxy resin-containing liquid was prepared in the same manner as in Example 1 except that silica particles were not added. Next, a 17% by weight toluene solution of urethane acrylate represented by the chemical formula (Chemical formula 6) was cast and applied to a stainless steel endless belt at a running speed of 0.3 m / min, and air-dried to volatilize the toluene. The composition was cured using a UV curing apparatus to form a urethane acrylate layer having a thickness of 2.0 μm. Subsequently, the epoxy resin-containing liquid was applied onto the urethane acrylate layer by casting at a rate of 0.3 m / min, heated at 150 ° C. using a heating device, and then heated and cured at 180 ° C. for 20 minutes. An epoxy resin layer of 400 μm was formed. Next, the laminate composed of the urethane acrylate layer and the epoxy resin layer was peeled off from the endless belt made of stainless steel, and the oxygen concentration was reduced to 0.5 by nitrogen replacement.
% On a glass plate in an atmosphere of 1% for 1 hour. Then, SiOx (x = x) was added to the epoxy resin layer side of the laminate composed of the urethane acrylate layer and the epoxy resin layer.
1.9) was converted to a batch sputtering system SM manufactured by Nippon Vacuum.
Using H-2306RE, 30 cc of argon gas was introduced, and sputtering was performed at a frequency of 500 W and a pressure of 0.4 Pa for 6 minutes and 20 seconds to form a 100 nm inorganic gas barrier layer.

Evaluation test: light transmittance (%), coefficient of linear expansion (/ ° C.), dimensional change (%), oxygen transmittance (cc / m ²⁾
24 h · atm), yellowness index (YI value), moisture permeability (g / m ² · 24 h · atm), display quality Light transmittance is high-speed spectrophotometer (Murakami Color CMS-500)
Using a halogen lamp), the transmittance at λ = 550 nm was measured. Linear expansion coefficient (/ ° C) is TMA / SS150
100 ° C. using C (manufactured by Seiko Instruments Inc.)
And the TMA value (μm) at 160 ° C. was measured and calculated. The dimensional change rate was measured using an STM5 Olympus digital small measuring microscope (manufactured by Olympus Corporation) by measuring the size immediately after heating at 150 ° C. for 20 minutes and the size after heating at 150 ° C. for 20 minutes and then leaving at room temperature for 2 hours. Calculated. Oxygen permeability was measured using OX-TRAN TWIN manufactured by Modern Controls according to the oxirant method. The measurement conditions were 40 ° C. and 43% RH. The yellowness index (YI value) was determined by Murakami Color Co., Ltd. using CMS-500.
It measured according to IS standard K-7103. The sample is 30 ×
A 50 mm flat plate was used. The moisture permeability is JIS-Z0208
The measurement was performed using the moisture-permeable cup and accessories specified in the above.
Further, a liquid crystal display device was assembled using the liquid crystal cells prepared in Examples 1 to 26 and Comparative Examples 1 and 2, and a ring-shaped illumination device was irradiated at an angle of 20 ° in a dark room to apply a voltage to the liquid crystal display device. The display quality of black display was examined in the state, and the display quality of white display was examined in the state where no voltage was applied. The display quality rank is determined as follows. A: Yellowness of display and glare of white display were suppressed. B: Although the yellowish color of the display was suppressed, glare was observed in a white display to such an extent that it could be used. C: The glare of white display was suppressed, but it was yellowish enough to withstand use. D: The display had a yellowish color enough to withstand use, and the white display showed glare enough to withstand use.

The results are shown in Table 1.

[Table 1]

When silica particles were added in Examples 1 to 5, both the coefficient of linear expansion and the rate of dimensional change were small, and the formation of color filters and the formation of electrodes were easy. The light transmittance was high and the weather resistance was good. Further, when a liquid crystal display device was prepared using this resin sheet, the yellow tint of the display was suppressed. However, the white display exhibited some glare that could be used. When alumina particles were added in Example 6, both the coefficient of linear expansion and the rate of dimensional change were small, and the formation of color filters and the formation of electrodes were easy. The light transmittance was high and the weather resistance was good. Further, when a liquid crystal display device was prepared using this resin sheet, the yellow tint of the display was suppressed. However, the white display exhibited some glare that could be used. Example 7
Resin sheet has low linear expansion coefficient and dimensional change rate,
The formation of color filters and the formation of electrodes were easy. The light transmittance was high and the weather resistance was good. Further, when a liquid crystal display device was prepared using this resin sheet, yellowness of display and glare of white display were suppressed. In Examples 8 and 9, the linear expansion coefficient was large, but the dimensional change rate was small, and there was no problem in laminating the color filter layers and forming the electrodes. The light transmittance was high and the weather resistance was good. Further, when a liquid crystal display device was prepared using this resin sheet, yellowness of display and glare of white display were suppressed. When no silica particles were added in Comparative Example 1, the light transmittance was high, but both the linear expansion coefficient and the dimensional change rate were large, and it was difficult to form a color filter layer and form an electrode. When a liquid crystal display device was prepared using this resin sheet, air bubbles were mixed into the liquid crystal.
The display quality was yellowish enough to withstand use, and glaring enough to endure use in white display was observed.
Although the linear expansion coefficient and the dimensional change rate of the resin sheet of Comparative Example 2 were slightly large, there was no significant problem in the formation of the color filter and the formation of the electrodes. Light transmittance was high. When a liquid crystal display device was prepared using this resin sheet, the weather resistance was insufficient as compared with the examples. The display quality was yellowish enough to withstand use, and glaring enough to endure use in white display was observed. Comparative Example 3
Although the dimensional change rate was relatively small, the coefficient of linear expansion was large, and it was difficult to form a color filter and an electrode. Further, when a liquid crystal display device was prepared using this resin sheet, there was no problem in weather resistance reliability. As for the display quality, the yellow color of the display was suppressed, but the white display showed glare that could be used.

[0064]

The particle-dispersed resin sheet of the present invention is thin, light and excellent in mechanical strength because it is resin-based. Also, by dispersing the inorganic oxide in the base material layer, the dimensional change of the resin sheet can be suppressed. Further, a light diffusion function can be imparted by dispersing the fine regions in the base material layer. Further, since the inorganic gas barrier layer is laminated on the particle-dispersed resin sheet of the present invention, the resin sheet has a high gas barrier function, and is characterized by being hardly yellowed.

[Brief description of the drawings]

FIG. 1 is a cross-sectional view of a particle-dispersed resin sheet.

FIG. 2 is a sectional view of a particle-dispersed resin sheet.

FIG. 3 is a cross-sectional view of a particle-dispersed resin sheet.

[Explanation of symbols]

 1: Urethane acrylate layer 2: Base layer in which inorganic oxide is dispersed 3: Inorganic gas barrier layer 4: Base layer in which minute region and inorganic oxide are dispersed 5: Base layer in which minute region is dispersed

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) G02B 5/02 G02B 5/02 B G02F 1/1335 G02F 1/1335 (72) Inventor Yoshimasa Sakata Ibaraki, Osaka 1-2-1, Shimohozumi, Ichito, Nitto Denko Corporation (72) Inventor Katsuhiro Nakano 1-1-2, Shimohozumi, Ibaraki-shi, Osaka Nitto Denko Corporation F-term (reference) 2H042 BA02 BA15 BA20 2H091 FA32X LA16 4F100 AA01A AA01B AA12B AA20B AK01A AT00A BA02 BA07 DE01A EH66 GB41 JA02A JB13A JB16A JD02 JD02B JD04A JK01 JK15A JN01A JN18A JN30 YY00A YY00B 4J002 CFA011CF1A1001 CF1A1001

Claims (25)

[Claims] 1. A particle-dispersed resin sheet having at least a substrate layer in which an inorganic oxide is dispersed in a resin and an inorganic gas barrier layer. 2. The particle-dispersed resin sheet according to claim 1, wherein the resin is a thermoplastic resin. 3. The particle-dispersed resin sheet according to claim 1, wherein the resin is a thermosetting resin. 4. An inorganic oxide having an average particle size of 1 to 100.
4. The particle-dispersed resin sheet according to claim 1, wherein 5. The method according to claim 1, wherein the amount of the inorganic oxide is 0.1 to 23% by weight based on the weight of the substrate layer.
5. The particle-dispersed resin sheet according to item 4. 6. The light transmittance at λ = 550 nm is 85%.
The particle-dispersed resin sheet according to claim 1, which is the above. 7. The particle-dispersed resin sheet according to claim 1, wherein the linear expansion coefficient at 100 ° C. to 160 ° C. is 1.00E−4 / ° C. or less. 8. Dimensions after heating at 150 ° C. for 20 minutes and 1
The particle-dispersed resin sheet according to any one of claims 1 to 7, wherein a dimensional change rate calculated from dimensions after heating at 50 ° C for 20 minutes and standing at room temperature for 2 hours is less than + 0.015%. 9. The inorganic gas barrier layer is made of silicon oxide, and the ratio of the number of oxygen atoms to the number of silicon atoms is 1.5 to 10.
The particle-dispersed resin sheet according to claim 1, wherein the ratio is 2.0. 10. The inorganic gas barrier layer is made of silicon nitride, and the ratio of the number of nitrogen atoms to the number of silicon atoms is 1.0 to 1.0.
The particle-dispersed resin sheet according to any one of claims 1 to 9, wherein the ratio is 4/3. 11. The inorganic gas barrier layer has a thickness of 5 to 20.
The particle-dispersed resin sheet according to claim 1, wherein the thickness is 0 nm. 12. A moisture permeability of 10 g / m ² · 24 h · atm
The particle-dispersed resin sheet according to any one of claims 1 to 11, wherein: 13. The particle-dispersed resin sheet according to claim 1, wherein minute regions having a different refractive index from the resin forming the substrate layer are dispersed in the substrate layer. Resin sheet. 14. The method according to claim 13, wherein the amount of the fine region added is 0.1 to 60% by weight based on the weight of the substrate layer.
3. The particle-dispersed resin sheet according to item 1. 15. An average particle diameter of said minute area is 0.2 μm.
The particle-dispersed resin sheet according to claim 13 or 14, wherein the particle-dispersed resin sheet has a thickness of from 100 to 100 µm. 16. The method according to claim 13, wherein the difference in specific gravity between the minute region and the resin forming the base material layer is 1 or less.
16. The particle-dispersed resin sheet according to 15. 17. The particle-dispersed resin sheet according to claim 13, wherein a difference in refractive index between the minute region and the resin forming the base layer is 0.03 to 0.10. 18. A particle-dispersed resin sheet having at least an inorganic gas barrier layer and a base layer in which fine regions having a different refractive index from the resin forming the base layer are dispersed. 19. The particle-dispersed resin sheet according to claim 18, wherein the amount of the fine region added is 200 parts by weight or less per 100 parts by weight of the base layer forming resin. 20. An average particle size of the microscopic region is 0.2 μm.
The particle-dispersed resin sheet according to claim 18 or 19, wherein the particle-dispersed resin sheet has a thickness of from 100 µm to 100 µm. 21. The method according to claim 18, wherein a difference in specific gravity between the minute region and the resin forming the base material layer is 1 or less.
21. The particle-dispersed resin sheet according to 20. 22. The particle-dispersed resin sheet according to claim 18, wherein a difference in refractive index between the minute region and the resin forming the base material layer is 0.03 to 0.10. 23. A moisture permeability of 10 g / m ² · 24 h · atm
The particle-dispersed resin sheet according to any one of claims 18 to 22, wherein: 24. The particle-dispersed resin sheet according to claim 1, wherein the outermost surface of the particle-dispersed resin sheet in which the substrate layer is the outermost layer is smooth. 25. A liquid crystal display device using the particle-dispersed resin sheet according to claim 1.