JP2002268059A - Reflective liquid crystal cell substrate and liquid crystal display device - Google Patents

Abstract

(57) Abstract: The present invention is thin, lightweight, excellent in mechanical strength and gas barrier properties, hardly yellowed, has a low rate of change in yellowness, has excellent heat resistance, and has excellent light diffusion properties. It is an object to provide a reflective liquid crystal cell substrate and a liquid crystal display device using the reflective liquid crystal cell substrate. A hard coat layer, an epoxy resin layer containing a minute region having a different refractive index from the epoxy resin, and a reflective layer made of a thin metal layer, and
A reflection type liquid crystal cell substrate, wherein the minute regions are unevenly distributed with a concentration distribution in a thickness direction of the epoxy resin layer.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a reflective liquid crystal cell substrate which is thin, lightweight, excellent in mechanical strength and gas barrier properties, low in yellowness change rate, excellent in heat resistance, and excellent in light diffusion. The present invention relates to a liquid crystal display device using a reflective liquid crystal cell substrate.

[0002]

2. Description of the Related Art In recent years, with the development of satellite communication and mobile communication technology, demand for small portable information terminal equipment has been increasing.
Display devices mounted on many small portable information terminal devices are required to be thin, and liquid crystal display devices are most frequently used. In addition, since a display device for a small portable information terminal device is required to have low power consumption and high visibility under external light, a reflection type liquid crystal display device is more preferable than a transmission type liquid crystal display device. It is heavily used. Glass-based reflective liquid crystal cell substrates have a low impact resistance and are very heavy. Therefore, plastic-based reflective liquid crystal cell substrates are being studied. However, plastic-based liquid crystal cell substrates have poor gas barrier properties, and moisture and oxygen pass through the liquid crystal cell substrate and enter the cell, causing breakage of the transparent electrode film pattern and moisture and oxygen entering the cell forming bubbles. Grow up to
Problems such as poor appearance and deterioration of the liquid crystal have been problems. Therefore, inorganic gas barrier layers such as metal oxides and organic gas barrier layers such as polyvinyl alcohol have been studied as gas barrier layers. However, the formation of the inorganic gas barrier layer has a problem that productivity is poor because a film forming method such as a sputtering method or a vacuum evaporation method is used. Further, the organic gas barrier layer has a problem that the organic gas barrier layer is liable to yellow and causes poor appearance. 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.

[0003]

DISCLOSURE OF THE INVENTION The present invention is thin, lightweight, excellent in mechanical strength and gas barrier properties, hardly yellowed, has a low rate of change in yellowness, excellent heat resistance, and excellent light diffusion. It is an object to provide a reflective liquid crystal cell substrate and a liquid crystal display device using the reflective liquid crystal cell substrate.

[0004]

SUMMARY OF THE INVENTION The present invention comprises at least a hard coat layer, an epoxy resin layer containing a minute region having a refractive index different from that of an epoxy resin, and a reflective layer comprising a thin metal layer; It is another object of the present invention to provide a reflective liquid crystal cell substrate, wherein the minute regions are unevenly distributed with a concentration distribution in a thickness direction of the epoxy resin layer. It is preferable that the epoxy resin layer is a single layer or a close-contact superimposed layer of a layer containing a fine region and a layer not containing a fine region. In a reflection type liquid crystal cell substrate in which the epoxy resin layer is the outermost layer and the minute regions are unevenly distributed on the outermost side of the epoxy resin layer, the outermost surface of the epoxy resin layer is smooth. Is preferred. It is preferable that the difference in the refractive index between the fine region and the epoxy resin is 0.03 to 0.10. The reflective liquid crystal cell substrate of the present invention preferably has an oxygen transmittance of 0.3 cc / m ² · 24 h · atm or less. The reflection type liquid crystal cell substrate of the present invention has 20
The yellowness change rate calculated from the yellowness after heating at 0 ° C. for 30 minutes and the yellowness at room temperature is preferably 0.75 or less. The present invention also provides a liquid crystal display using the reflective liquid crystal cell substrate of the present invention.

[0005]

BEST MODE FOR CARRYING OUT THE INVENTION The reflection type liquid crystal cell substrate of the present invention comprises at least a hard coat layer, an epoxy resin layer containing a fine region having a refractive index different from that of the epoxy resin,
And a reflection layer composed of a thin metal layer, and the minute regions are unevenly distributed with a concentration distribution in a thickness direction of the epoxy resin layer.

In the present invention, the reflective layer does not need to be on the outermost layer. That is, the present invention provides a laminate of the outermost layer from the hard coat layer, the epoxy resin layer, and the reflective layer, or a laminate of the outermost layer from the hard coat layer, the reflective layer, and the epoxy resin layer.

In the present invention, the material for forming the hard coat layer includes urethane resin, acrylic resin, polyester resin, polyvinyl alcohol and ethylene.
Examples thereof include a polyvinyl alcohol-based resin such as a vinyl alcohol copolymer, a vinyl chloride-based resin, and a vinylidene chloride-based resin.

Further, polyarylate resins, sulfone resins, amide resins, imide resins, polyethersulfone resins, polyetherimide resins, polycarbonate resins, silicone resins, fluorine resins, polyolefin resins, Styrene-based resins, vinylpyrrolidone-based resins, cellulose-based resins, acrylonitrile-based resins, and the like can also be used for forming the resin layer. Among these resins, urethane resins are preferable, and urethane acrylate is particularly preferably used. In addition, in forming the resin layer,
A blend of two or more kinds of appropriate resins can also be used.

The epoxy resin in the present invention includes:
For example, bisphenol A type such as bisphenol A type, bisphenol F type, bisphenol S type and bisphenol type such as water addition, novolak type such as phenol novolak type and cresol novolac type, nitrogen-containing ring type such as triglycidyl isocyanurate type and hydantoin type, Examples thereof include an alicyclic type, an aliphatic type, an aromatic type such as a naphthalene type, a low water absorption type such as a glycidyl ether type and a biphenyl type, a dicyclo type, an ester type, an ether ester type, and a modified form 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.

The epoxy resin includes 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.
One or more appropriate curing agents depending on the epoxy resin can be used. Incidentally, examples thereof include tetrahydrophthalic acid, methyltetrahydrophthalic acid, organic acid compounds such as hexahydrophthalic acid and methylhexahydrophthalic acid, ethylenediamine, propylenediamine, diethylenetriamine, triethylenetetramine and their amine adducts, 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, isopropylimidazole, 2,4-dimethylimidazole, 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, isopropylimidazoline, 2,4-dimethylimidazoline, phenylimidazoline, undecylimidazoline,
Imidazoline compounds such as heptadecylimidazoline and 2-phenyl-4-methylimidazoline, phenol compounds, urea compounds, and polysulfide compounds are also examples of the curing agent.

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 thereof are phthalic anhydride, maleic anhydride, trimellitic anhydride, pyromellitic anhydride, nadic anhydride, glutaric anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, 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 curing agent having a molecular weight of about 140 to about 200 is 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 used is in accordance with the equivalent ratio described above.

Examples of the curing accelerator include tertiary amines, imidazoles, quaternary ammonium salts, organic metal salts, phosphorus compounds and urea compounds, and particularly, tertiary amines, It is preferable to use imidazoles and phosphorus compounds. 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 modifying agent include known ones such as glycols, silicones and alcohols.

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

In the present invention, in order to impart light diffusivity, it is necessary that the epoxy resin layer contains a minute region having a different refractive index from that of the epoxy resin. It is preferable that the difference in the refractive index between the minute region and the epoxy resin is 0.03 to 0.10. When the difference in the refractive index is smaller than 0.03 or larger than 0.10. Cannot be given.

Examples of the fine region include inorganic particles made of silica, alumina, titania, zirconia, tin oxide, indium oxide, cadmium oxide, antimony oxide, and the like, and organic particles made of a crosslinked or uncrosslinked polymer. In addition, air bubbles mixed into the epoxy resin coating liquid by an appropriate method such as a stirring method can also be used as a material for forming a minute region.

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

The amount of the forming material for the minute area can be appropriately determined according to the degree of light diffusibility. In general, in the case of transparent particles, 200 parts per 100 parts by weight of the epoxy resin is used.
The amount is not more than 0.05 parts by weight, preferably 0.05 to 150 parts by weight, and more preferably 0.1 to 50 parts by weight. When air bubbles and the like are also included, 8
0 vol% or less, preferably 2 to 60 vol%, more preferably 5 to 50 vol%.

In the present invention, in order to impart sufficient light diffusivity, it is necessary that the minute regions are unevenly distributed with a concentration distribution in the thickness direction of the epoxy resin layer. By unevenly distributing the minute regions, the minute regions can be distributed only in a portion close to the liquid crystal layer, and the visibility can be improved by providing a light diffusion function. In the present invention, the minute regions are unevenly distributed. When the epoxy resin layer is divided into two equal parts in the thickness direction, the volume ratio of the minute regions contained in one epoxy resin layer is equal to that of the other epoxy resin layer. More than twice the volume ratio of the micro-regions contained in the resin layer,
It is preferably at least 3 times, more preferably at least 5 times. The volume ratio is (volume of minute region / volume of epoxy resin layer including minute region). As a method of unevenly distributing the minute regions with a concentration distribution in the thickness direction of the epoxy resin, there is a method of causing the minute regions to settle or float based on the difference in specific gravity in a sheet-like spread layer of the epoxy resin coating liquid. No. In this case, the epoxy-based resin layer is composed of a single layer and is separated into a side containing a minute region and a side not containing a minute region.

Further, after applying an epoxy resin coating liquid containing no minute area to make it semi-cured, an epoxy resin coating liquid containing a minute area is applied, and both coating liquids are completely cured. Thus, the minute regions may be unevenly distributed. In this case, the epoxy-based resin layer is composed of a close-contact superimposed layer of a fine region containing layer and a fine region non-containing layer. In this case, the order of application of the epoxy resin coating liquid containing no micro-region and the epoxy resin coating liquid containing micro-region may be reversed. In this manner, by adopting a method in which the first spreading layer is semi-cured and then the other spreading layer is superimposed, it is possible to suppress or prevent the minute region from entering the other spreading layer. When the epoxy-based resin layer is applied in two separate steps as described above, if the epoxy resin layer is within the range of uneven distribution described above, 2 times.
An epoxy resin coating solution containing a minute region may be applied each time.

In the present invention, when the epoxy resin layer is located on the outermost layer and the minute region is located on the outermost side of the epoxy resin layer, the outermost surface of the epoxy resin layer may be smooth. preferable. In the present invention, smooth means that the surface roughness (Ra) is 1 nm or less. This is because the smoothing facilitates formation of the alignment film, the transparent electrode, and the like.

The reflective layer of the present invention needs to be composed of a thin metal layer such as silver or aluminum. The reflective layer has a gas barrier function and prevents moisture and oxygen from penetrating the liquid crystal cell substrate and entering the cell. Therefore, in the present invention, there is no need to laminate an organic gas barrier layer made of polyvinyl alcohol or the like or an inorganic gas barrier layer made of silicon oxide or the like.

The thickness of the reflection layer is preferably 50 to 1000 nm, more preferably 100 to 500 nm.
Is good. When the thickness of the reflective layer is less than 50 nm, reliability such as heat resistance and moisture resistance is reduced. The thickness of the reflective layer is 1
If it exceeds 000 nm, cracks are likely to occur and the cost increases. Further, it cannot be used as a transmission type liquid crystal cell substrate.

The oxygen transmission rate of the reflective liquid crystal cell substrate of the present invention is preferably 0.3 cc / m ² · 24 h · atm or less. More preferably, the oxygen permeability of the liquid crystal cell substrate is 0.15 cc / m ² · 24 h · atm or less. If the oxygen transmission rate exceeds 0.3 cc / m ² · 24 h · atm, moisture and oxygen enter the cell, causing disconnection of the transparent conductive film pattern and moisture and oxygen entering the cell to form bubbles. By that time, problems such as poor appearance and deterioration of the liquid crystal arise.

In the step of assembling the liquid crystal cell from the liquid crystal cell substrate, the step of firing the alignment film and the step of firing the sealing agent are performed at about 150 ° C., and the sputtering of a transparent electrode such as ITO is performed at about 180 ° C. In these steps, in order to maintain the quality reliability of the liquid crystal cell substrate, the liquid crystal cell substrate preferably has heat resistance of 200 ° C. or higher.

In the present invention, the liquid crystal cell substrate is 200
The yellowness change rate calculated from the yellowness after heating at 30 ° C. for 30 minutes and the yellowness at room temperature is preferably 0.75 or less. The yellowness change rate is the yellowness at room temperature as YI,
Assuming that the yellowness after heating at 200 ° C. for 30 minutes is YI ₂₀₀ , it can be calculated by (Equation 1). When the rate of change in yellowness exceeds 0.75, when a liquid crystal display device is formed using the liquid crystal cell substrate, the display quality deteriorates, such as a white display having a yellow tint.

(Equation 1)

An electrode is formed on the reflective liquid crystal cell substrate according to the present invention to provide a reflective liquid crystal cell substrate with electrodes.

As the electrode, a transparent electrode film is preferably used. The transparent electrode film is provided by using a suitable forming material such as indium oxide, tin oxide, indium / tin mixed oxide, gold, platinum, palladium, or a transparent conductive paint, for example, by a vacuum evaporation method, a sputtering method, or a coating method. Alternatively, the transparent conductive film can be formed by a method according to the related art such as a coating method, and the transparent conductive film can be directly formed in a predetermined electrode pattern. An alignment film for liquid crystal alignment provided on the transparent conductive film as needed can also be added by a method according to the related art.

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 reflection type liquid crystal cell substrate is used, and it can be formed according to a conventional method. Therefore, when forming the liquid crystal display device of the present invention, for example, a light diffusion plate provided on the polarizing plate on the viewing side, an anti-glare layer,
Appropriate optical components such as an antireflection film, a protective layer, a protective plate, or a compensating retardation plate provided between the liquid crystal cell and the polarizing plate on the viewing side can be appropriately combined with the reflective liquid crystal cell substrate. It is more preferable to use the minute region containing side or the minute region containing layer as the inside of the cell from the viewpoint of preventing or suppressing the occurrence of parallax and shadow.

EXAMPLES The present invention will be described below with reference to examples.
The present invention is not limited to these examples.

Example 1: 3,4-epoxycyclohexylmethyl having a specific gravity of about 1.2 represented by the chemical formula (1)
3,4-epoxycyclohexanecarboxylate 10
0 parts (parts by weight, hereinafter the same), 125 parts of methylhexahydrophthalic anhydride represented by the chemical formula (Chemical Formula 2), and tetra-n-butylphosphonium o, o-diethylphosphonate represented by the chemical formula (Chemical Formula 3) 3.75 parts of logithioate,
2.25 parts of glycerin and silicone surfactant 0.
07 parts were stirred and mixed, and as a fine area, specific gravity was about 3.9.
Was mixed with 4 parts of alumina to prepare a fine region-containing epoxy resin liquid.

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According to the manufacturing process illustrated in FIG. 2, first, a 17% by weight toluene solution of urethane acrylate represented by the chemical formula (Chem. 4) is cast onto the endless belt 1 made of stainless steel at a running speed of 0.3 m / min. Then, the resultant was air-dried to volatilize the toluene, and then cured using a UV curing device to form a hard coat layer 10 having a thickness of 2 μm. Subsequently, the epoxy resin liquid containing the micro-regions was applied by casting at a rate of 0.3 m / min onto the hard coat layer from the die 5 and cured by using a heating device to form an epoxy resin layer 15 having a thickness of 400 μm.
Was formed. Alumina in the epoxy resin liquid starts sedimentation immediately after coating, and the thickness of the hard coat layer 10 side
The distribution was almost unevenly distributed in the layer of 0 μm, and was separated into the side 11 containing the minute region and the side 12 not containing the minute region.

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Next, the laminate of the hard coat layer and the epoxy resin layer was peeled off from the endless belt, and was replaced on a glass plate at 180 ° C. in an atmosphere having an oxygen concentration of 0.5% by nitrogen replacement.
× After leaving for 1 hour, after-curing was performed. Next, an aluminum reflective layer having a thickness of 1000 nm was formed on the epoxy resin layer side of the laminate including the hard coat layer and the epoxy resin layer by a vacuum evaporation method.

Example 2 A microregion-containing epoxy resin solution was prepared in the same manner as in Example 1. In the step of preparing the epoxy-based resin liquid, an epoxy-based resin liquid containing no fine regions was prepared without mixing alumina. According to the manufacturing process illustrated in FIG. 3, first, a hard coat layer 10 is formed in the same manner as in Example 1, and then an epoxy-based resin liquid containing no fine region is cast and applied at 0.3 m / min from a die 5 and dried. After a semi-cured state is formed in the machine 8 to form a layer containing no micro-region, a micro-region-containing epoxy resin liquid is cast and applied from the die 6 at a rate of 0.3 m / min to form a micro-region-containing layer. By this, the layer containing no fine region and the layer containing fine region were completely cured. In this case, the thickness of the microregion-free layer is 350 μm,
The thickness of the fine region containing layer was 50 μm.

Next, a hard coat layer, a layer containing no fine regions,
The laminated body composed of the micro-region-containing layer was peeled off from the endless belt and left on a glass plate at 180 ° C. for 1 hour in an atmosphere having an oxygen concentration of 0.5% by purging with nitrogen to perform after-curing. Next, an aluminum reflective layer having a thickness of 1000 nm was formed on the side of the layered body containing the microregions by a vacuum evaporation method.

[0043]

Comparative Example 1 First, 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 a UV curing device was used. Cured to a film thickness of 2 μm
Was formed. Subsequently, a 5.5% by weight aqueous solution of a polyvinyl alcohol resin is applied on the hard coat layer by casting at a rate of 0.3 m / min, and dried at 100 ° C. for 10 minutes to form an organic gas barrier layer having a thickness of 3.7 μm. did.
Subsequently, the epoxy resin liquid containing no micro-region prepared in Example 1 was applied onto the organic gas barrier layer by casting at a rate of 0.3 m / min, and was cured using a heating device. A resin layer was formed. Next, the laminate of the hard coat layer, the organic gas barrier layer, and the epoxy resin layer was peeled off from the endless belt, and the oxygen concentration was reduced to 0.5 by nitrogen replacement.
%, And left on a glass plate at 180 ° C. for 1 hour to perform after-curing. Next, an aluminum reflective layer having a thickness of 1000 nm was formed on the epoxy resin layer side of the laminate including the hard coat layer, the organic gas barrier layer, and the epoxy resin layer by a vacuum evaporation method.

Evaluation test: oxygen permeability (cc / m ² · 24)
h · atm), yellowness index (YI value), and display quality The oxygen permeability was measured using OX-TRAN TWIN manufactured by Modern Controls in accordance with the oxirant method. The measurement conditions were 40 ° C. and 43% RH. The yellowness index (YI value) is JI using Murakami Color Co., Ltd., using CMS-500.
It measured according to S specification K-7103. Sample is 30 × 5
A 0 mm flat plate was used. Examples 1 and 2 and Comparative Example 1
Assemble the liquid crystal display device using the liquid crystal cell created in
Irradiating the ring-shaped lighting device at an angle of 20 ° in a dark room,
The display quality of black display was examined under a voltage application state of the liquid crystal display device, and the display quality of white display was examined under no voltage application state.

The results are shown in Table 1.

[Table 1]

When a liquid crystal display device was prepared using the liquid crystal cell substrates of Examples 1 and 2, the weather resistance was good and both black display and white display were excellent. When a liquid crystal display device was prepared using the liquid crystal cell substrate of Comparative Example 1, there was no problem with the weather resistance, but the white display was yellowish. In addition, in white display, glare was observed, which was considered to be caused by the reflection of illumination on the liquid crystal surface.

[0047]

As described above, the reflection type liquid crystal cell substrate of the present invention is thin, light, and excellent in mechanical strength because it is made of resin.
Since the reflection layer has a gas barrier function, there is no need to stack an organic gas barrier layer. Therefore, the reflective liquid crystal cell substrate of the present invention has a feature that the rate of change in yellowness is small and the heat resistance is excellent. Further, the reflection type liquid crystal cell substrate of the present invention has a good light diffusing property by containing a minute region in the epoxy resin layer. Therefore, it is not necessary to newly provide a light diffusion sheet via an adhesive or the like in order to improve visibility. Further, since the reflection type liquid crystal cell substrate of the present invention can form a liquid crystal cell having a light diffusion layer in a portion close to the liquid crystal layer, blurring of an image due to parallax and shadows can be prevented, and visibility can be greatly improved.

[Brief description of the drawings]

FIG. 1 shows an example of a liquid crystal cell substrate of the present invention.

FIG. 2 shows an example of a manufacturing process of the liquid crystal cell substrate of the present invention.

FIG. 3 shows an example of a manufacturing process of the liquid crystal cell substrate of the present invention.

[Explanation of symbols]

 1: Endless belt 2: Drum 3: Drive drum 4: Die for coating hard coat layer 5: Die for coating epoxy resin layer 6: Die for coating epoxy resin layer 7: UV curing device 8: Dryer 9: Drying Machine 10: Hard coat layer 11: Micro-region containing side 12: Micro-region non-containing side 13: Micro-region containing layer 14: Micro-region non-containing layer 15: Epoxy resin layer 16: Reflective layer

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Yoshihiro Kitamura 1-1-2 Shimohozumi, Ibaraki-shi, Osaka Nitto Denko Corporation (72) Inventor Katsuhiro Nakano 1-2-1, Shimohozumi, Ibaraki-shi, Osaka F-term (reference) in Nitto Denko Corporation 2H090 HB08X JB03 JD11 JD17 2H091 FA08X FA08Z FA11X FA11Z FA14Z FA41Z FC02 LA16 4J002 CD001 CD011 CD021 CD031 CD051 CD061 CD131 CD141 DE096 DE126 DE136 DE146 DJ016 FD016A03A03 EA06 EA07 EB04 JA08 JA13

Claims (7)

[Claims] 1. A reflective layer comprising at least a hard coat layer, an epoxy resin layer containing a minute region having a refractive index different from that of an epoxy resin, and a thin metal layer, and
A reflection type liquid crystal cell substrate, wherein the minute regions are unevenly distributed with a concentration distribution in a thickness direction of the epoxy resin layer. 2. The reflection type liquid crystal cell substrate according to claim 1, wherein said epoxy resin layer comprises a single layer or a close-contact superposed layer of a layer containing a fine region and a layer not containing a fine region. 3. An outermost surface of an epoxy-based resin layer in a reflective liquid crystal cell substrate in which the epoxy-based resin layer is an outermost layer and the minute regions are unevenly distributed on the outermost side of the epoxy-based resin layer. Is smooth.
Or the reflective liquid crystal cell substrate according to 2. 4. The reflection type liquid crystal cell substrate according to claim 1, wherein a difference in refractive index between said fine region and said epoxy resin is 0.03 to 0.10. 5. An oxygen permeability of 0.3 cc / m ² · 24 h ·
5. The reflective liquid crystal cell substrate according to claim 1, wherein said substrate is atm or less. 6. The yellowness change rate calculated from the yellowness after heating at 200 ° C. for 30 minutes and the yellowness at room temperature is 0.
The reflective liquid crystal cell substrate according to claim 1, wherein the thickness is 75 or less. 7. A liquid crystal display device using the reflection type liquid crystal cell substrate according to claim 1.