JPH112812A - Reflection conductive substrate, reflection liquid crystal display device, and manufacture of reflection conductive substrate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the reflection conductive substrate which is lightweight and has high heat resistance and rigidity by laminating a reflection layer which contains white pigment and resin, a barrier layer formed of silica, and a conductive layer in order on a laminate plate formed of fiber cloth set with resin. SOLUTION: The reflection conductive substrate 11 is constituted by laminating the reflection layer 13 containing the white pigment and resin, the barrier layer 14 formed of silica, and the conductive layer 15 in order on one main surface of the laminate plate 12 formed of the fiber cloth impregnated with thermosetting resin. The silica constituting the barrier layer 14 is produced preferably from polysilazane having a cyclic structure. Further, the reflection layer 13 and barrier layer 14 may be formed on both the surfaces of the laminate plate 12. As the material of the fiber cloth used for the laminate plate 12, there are glass such as E glass, D glass, and S glass and a filament of resin such as aromatic polyamide. The laminate plate 12 is preferably of double stack constitution from the point of view of weight reduction.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a reflective conductive substrate, a reflective liquid crystal display device, and a method of manufacturing a reflective conductive substrate, and more particularly to a liquid crystal display device mounted on a portable information terminal device. The present invention relates to a suitable reflective conductive substrate, a reflective liquid crystal display device, and a method for manufacturing a reflective conductive substrate.

[0002]

2. Description of the Related Art In recent years, with the development of satellite communication and mobile communication technology, the demand for small portable information terminal equipment is increasing.
Display devices mounted on many portable information terminal devices are required to be thin, and liquid crystal display devices are most frequently used.

Further, since a display device for a 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. The device is heavily used.

FIG. 4 is a sectional view of a conventional reflection type liquid crystal display device. In FIG. 4, a reflective liquid crystal display device 41 is disposed to face each other, and has a pair of conductive substrates 42 and 43 made of glass, each having an electrode layer formed on each of the opposing surfaces. , 43, and a light reflecting layer 45 made of a mixture of a white pigment and PET, provided on the surface of the conductive substrate 42 opposite to the liquid crystal layer. I have.

As described above, the reflection type liquid crystal display device is provided with the light reflection layer 45 instead of the backlight generally used in the transmission type liquid crystal display device. The conductive substrate used in the above-mentioned reflection type liquid crystal display device is generally formed on a glass plate having a thickness of 0.7 to 1.1 mm having optical characteristics such as high light transmittance, low haze, and low retardation. To
This is a transmission type conductive substrate on which a conductive layer made of a transparent conductive material is formed.

Since the transmission type conductive substrate uses a glass plate having heat resistance and chemical resistance, for example, photoetching is performed in processes such as formation of an alignment film and electrodes in the manufacture of a liquid crystal display device. It has sufficient strength for processes such as sputtering and sputtering.

[0007] In addition, characteristics required for the conductive substrate, such as oxygen barrier properties, water vapor barrier properties, and scratch resistance, are also good. However, since the above-mentioned transmission type conductive substrate uses glass, it has low impact resistance and is very heavy. When the thickness of the glass plate is reduced in order to reduce the weight of the substrate, the impact resistance is further reduced, so that it is difficult to reduce the weight. Therefore, in a small portable information terminal device that is required to have high impact resistance and light weight,
It has been studied to use a resin film such as a plastic film for the conductive substrate.

FIG. 5 shows a sectional view of a conventional conductive substrate using a resin film. In FIG. 5, the conductive substrate 51 is
An anchor coat layer 53 and a transparent electrode layer 54 are sequentially laminated on one main surface of the heat-resistant transparent resin film 52, and a barrier layer 55 is formed on the other main surface of the heat-resistant transparent resin film 52.
And the hard coat layer 56 are sequentially laminated.

[0009] Unlike a glass plate, a conductive substrate using a resin film is lightweight without breaking. However, in general, all functions such as oxygen barrier properties, water vapor barrier properties, and scratch resistance cannot be borne by a single resin. Therefore, in the conductive substrate 51 using a resin film, a barrier layer 55 having an oxygen barrier property and a water vapor barrier property, and a hard coat layer 56 having a scratch resistance are required.

Further, the transparent electrode layer 54 cannot be formed directly on the heat-resistant resin film 52. Therefore, it is necessary to provide the anchor coat layer 53 between the heat-resistant resin film 52 and the transparent electrode layer 54.

In FIG. 5, the barrier layer 55 is a single layer having an oxygen barrier property and a water vapor barrier property. However, it is very difficult to impart the oxygen barrier property and the water vapor barrier property to a single resin. The barrier layer 5
5 has a two-layer structure in which a layer having an oxygen barrier property and a layer having a water vapor barrier property are laminated. However, in general, a resin having a water vapor barrier property has a high surface energy and has low affinity with other resins. Therefore, it is necessary to perform a surface treatment in order to bond another resin to the resin having the water vapor barrier property.

As described above, in the production of a conductive substrate using a resin film, an enormous number of resin layers need to be laminated, and many steps are required. Will happen.

Further, a conductive substrate using a resin film is formed by laminating a plurality of resin layers having a large coefficient of linear thermal expansion and different coefficients of thermal expansion. And heat resistance such as thermal dimensional stability is low. Further, since the rigidity of the conductive substrate is poor, deformation of the substrate such as the above-described warpage or bending easily occurs.

Therefore, as shown in FIG. 6, when both the pair of conductive substrates 62 and 63 are made of resin, there arises a problem that alignment of the substrates becomes difficult in manufacturing a liquid crystal display device. This problem is particularly remarkable when forming an array electrode because a higher temperature process is required.

As shown in FIG. 7, when one of the pair of conductive substrates 72 and 73 is made of glass and the other conductive substrate 73 is made of resin, There is no problem such as the positioning of the image. However, since glass is used, there arises a problem that impact resistance is low and weight reduction becomes difficult.

[0016]

As described above, the conductive substrate used in the conventional reflection type liquid crystal display device has a light weight and sufficient impact resistance, oxygen barrier properties, water vapor barrier properties, and the like. In order to obtain scratch resistance, the configuration became complicated and many steps were required for manufacturing the substrate. In addition, since heat resistance and rigidity are low, deformation such as warpage or bending is likely to occur, and it is difficult to manufacture a display device.

The present invention is a reflective conductive material which is thin and lightweight, has sufficient impact resistance, oxygen barrier properties, water vapor barrier properties, and scratch resistance, has a simple structure, and has high heat resistance and high rigidity. It is an object to provide a method for manufacturing a substrate, a reflective liquid crystal display device, and a reflective conductive substrate.

[0018]

SUMMARY OF THE INVENTION The present invention comprises a laminate including a fiber cloth impregnated with a resin and cured, a reflective layer including a white pigment and a resin, formed on the laminate, and a silica. A reflective conductive substrate, comprising: a barrier layer formed on the reflective layer; and a conductive layer formed on the barrier layer.

The present invention is characterized in that, in the reflective conductive substrate, the silica constituting the barrier layer is formed from polysilazane having a cyclic structure. The present invention is characterized in that in the reflective conductive substrate, the reflective layer and the barrier layer are formed on both surfaces of the laminate.

The present invention also provides a laminate including a fiber cloth impregnated with a resin and cured, a reflective layer including a white pigment and a resin and formed on the laminate, and a reflective layer including silica and including a silica. Formed on the barrier layer, a reflective conductive substrate including a conductive layer formed on the barrier layer, and provided to face the surface of the reflective conductive substrate on which the conductive layer is formed, and A transparent resin substrate having a transparent electrode formed on the opposite surface,
A reflective liquid crystal display device comprising a liquid crystal layer provided between the reflective conductive substrate and a transparent resin substrate.

Further, the present invention provides a method of applying a mixture of a white pigment and a thermosetting resin to one main surface of a laminated board obtained by impregnating a resin with a fiber cloth as a core material and curing the resin to heat the reflective layer. Forming a barrier layer containing silica by applying and heat-treating a polysilazane having a cyclic structure on the reflective layer, and forming a conductive layer on the barrier layer. A method for manufacturing a reflective conductive substrate is provided.

[0022]

Embodiments of the present invention will be described below in more detail with reference to the drawings. FIG.
1 shows a cross-sectional view of a reflective conductive substrate according to one embodiment of the present invention.

In FIG. 1, a reflective conductive substrate 11 is formed of a reflective layer 13 containing a white pigment and a resin and silica on one main surface of a laminate 12 made of a fiber cloth impregnated with a thermosetting resin. The barrier layer 14 and the conductive layer 15 are sequentially laminated.

The laminate used for the reflective conductive substrate of the present invention is made of a fiber cloth impregnated with a thermosetting resin.
Examples of the material of the fiber cloth used include glass such as E glass, D glass, and S glass, and filaments such as resin such as aromatic polyamide.

The diameter of the filament is preferably 20 μm or less. By using a filament having a diameter of 20 μm or less, the reflective conductive substrate can be made thinner and lighter, and the mechanical strength of the substrate can be increased.

When these filaments are made into a fiber cloth,
It can be used as a non-woven fabric without weaving, but plain weave,
It is preferable to use it as a woven or woven cloth by weaving methods such as satin weave and twill weave. The thickness of the fiber cloth is 30 to 1
The thickness is preferably 00 μm, more preferably 30 to 50 μm. When the thickness of the fiber cloth is within the above range, the reflective conductive substrate can be made thinner and lighter, and the mechanical strength of the substrate can be increased.

The surface roughness of the produced fiber cloth changes depending on the weave of the filament. When fabrics are produced using the same filaments, the surface roughness increases in the order of twill, satin, and plain weave, but by forming the barrier layer with a sufficient thickness, it is necessary to smooth the substrate surface. Can be.

In the case where the fiber cloth is produced by plain weaving, it is easy to impregnate the fiber cloth with a resin described later, and the production cost of the laminate can be reduced. The fiber cloth described above is impregnated with a thermosetting resin. Examples of the resin used for impregnating the fiber cloth include thermosetting resins having high heat resistance, such as a phenol resin-epoxy resin mixture and a bismaleimide-triazine resin mixture. It is particularly preferable to use a phenol novolak resin as the phenol resin and a bisphenol-type epoxy resin as the epoxy resin because high heat resistance can be obtained.

As the bismaleimide, those derived from diaminodiphenylmethane can be used, but those derived from a compound in which the phenyl group of diaminodiphenylmethane is substituted with an alkyl group may also be used. The triazine resin can be obtained by a dehydrochlorination reaction between bisphenol A and cyanogen chloride. In addition,
As these bismaleide-triazine resin mixtures, those commercially available from Mitsubishi Engineering-Plastics Corporation as BT resins to which an epoxy resin or the like has been added can be used.

The laminate used for the reflective conductive substrate of the present invention is manufactured as described below. First, the above-mentioned thermosetting resin composition is dissolved in an organic solvent such as a ketone-based solvent, and impregnated into the above-mentioned fiber cloth. This is primarily dried to produce a prepreg, which is B-staged. This prepreg, for example, two sheets, using a hot press,
20-60kg while heating to about 150-180 ° C
/ Cm ² . In addition, this is 150
A laminate is obtained by heating to about 180 ° C. to cure the thermosetting resin. It is preferable that the ratio of the resin component in the laminate is controlled to 40 to 60% by weight.

The laminated board manufactured as described above has a configuration in which two fiber cloths are stacked. However, the number of layers is not particularly limited as long as it is lightweight and thin, and sufficient mechanical strength can be obtained. . However, in order to suppress the anisotropy of the laminate, it is preferable that the laminate has a structure in which an even number of fiber cloths are stacked, and most preferably, a structure in which two sheets are stacked from the viewpoint of weight reduction.

The thickness of the laminate is preferably 50 to 200 μm, more preferably 50 to 100 μm. If the thickness of the laminate is within the above range,
The reflective conductive substrate can be made thinner and lighter,
The mechanical strength of the substrate can be increased.

As a laminate used for the reflective conductive substrate of the present invention, a laminate manufactured by a laminate manufacturer is commercially available.
A laminate having a surface covered with a metal foil may be used. In addition,
Metal foil stretched on such commercially available laminates is
It can be easily removed by etching.

The white pigment used in the reflective layer of the reflective conductive substrate of the present invention may be, for example, a commonly used white pigment such as titania. This white pigment is dispersed in a thermosetting silicone resin dispersed in a BTX solvent, applied to a laminate and dried,
By further heating, a reflective layer is formed.

At this time, the weight ratio (P / R ratio) of the white pigment to the silicone resin is preferably 2.5 to 6, and more preferably 4 to 6. When the P / R ratio is equal to or more than the above lower limit, the linear thermal expansion coefficient of each layer constituting the reflective conductive substrate can be reduced, and the thermal dimensional stability of the substrate can be improved. However, when the P / R ratio exceeds the above upper limit, dispersion of the white pigment becomes difficult.

The thickness of the reflection layer is preferably 5 to 10 μm. When the thickness of the reflective layer is within this range, the color of the laminate is concealed in white without significantly increasing the thickness or weight of the reflective conductive substrate, and the surface roughness is reduced to some extent. be able to.

The barrier layer of the reflective conductive substrate of the present invention comprises:
It can be composed of silica. The silica constituting this barrier layer is preferably obtained from polysilazane. Polysilazane is a compound of the general formula H ₃ Si (NHSiH ₂ ) _n N
The linear silazane represented by HSiH ₃ or the general formula (SiH ₂
NH) _n is a polymer having a cyclosilazane skeleton represented by _n . These polysilazanes are hydrolyzed and
Upon polycondensation, the Si—N bond of the polysilazane is broken and S
This produces i-O bonds and produces silica and ammonia. Therefore, when the polysilazane has hydrogen atoms bonded to silicon atoms, hydrogen atoms bonded to silicon atoms remain in the produced silica.

As the polysilazane, a low-temperature fired polysilazane having a cyclic structure, such as a cyclic perhydropolysilazane to which a Pd complex is added as a catalyst, such as a Tonen polysilazane low-temperature fired NL110 type commercially available from Tonen Corporation, is used. By heating at a relatively low temperature of about 100 to 150 ° C., polysilazane can be changed to silica, which is preferable.

In particular, when a polysilazane having a condensed ring structure is used as a low-temperature firing type polysilazane having a cyclic structure, the ratio of hydrogen atoms bonded to silicon atoms in silica, which is a reaction product, is reduced. Since the number of oxygen atoms bonded to silicon atoms increases, a strong and dense barrier layer can be formed.

The formation of the barrier layer using the above-mentioned polysilazane can be performed, for example, as follows. First, a xylene solution of polysilazane is applied and dried on a reflective layer formed on a laminate, and is then placed in a hydrogen peroxide solution for 2 to 4 times.
Let it soak for about an hour. Next, the laminate is pulled up from the hydrogen peroxide solution and heated at a temperature of about 100 to 150 ° C. for 1 to 48 hours to form a barrier layer composed of silica.

In general, a layer made of silica can be formed by a vapor deposition method or a sol-gel method. However, it is difficult to form a film having a sufficient thickness by the vapor deposition method, and even if it is formed, cracks and pinholes are generated. Further, in the sol-gel method, heating at a very high temperature is required to convert the alkoxide into an oxide. Therefore, it cannot be applied to a substrate using resin.

On the other hand, when the above-mentioned polysilazane is used, a silica film having a sufficient thickness can be obtained at a relatively low temperature of about 100 to 150 ° C. The thickness of the barrier layer thus formed is preferably from 0.5 to 2 μm, more preferably from 1.5 to 2 μm. When the thickness of the barrier layer is within the above range, sufficient oxygen barrier properties and water vapor barrier properties can be obtained without greatly increasing the thickness and weight of the reflective conductive substrate. Further, in the above-described reflective layer, the surface roughness cannot be sufficiently reduced, but when the thickness of the barrier layer is equal to or more than the lower limit, the surface roughness of the substrate can be sufficiently reduced. Become.

In the reflective conductive substrate of the present invention, the material used for the conductive layer includes In ₂ O ₃ —SnO ₂ mixture (ITO), TiO ₂ / Ag / TiO ₂ , BiO ₃ ,
Transparent conductive materials such as nO ₂ (F), CdSnO ₃ and V ₂ O ₅ .nH ₂ O can be used. Preferably, the conductive layer is formed to a thickness of 500 to 3000 Å.

In the reflective conductive substrate of the present invention, the reflective layer and the barrier layer may be formed on both sides of the laminate. FIG. 2 shows a cross-sectional view of a reflective conductive substrate according to another embodiment of the present invention.

In FIG. 2, a reflective conductive substrate 21 has a reflective layer 23, a barrier layer 24, and a conductive layer 25 sequentially laminated on one main surface of a laminated plate 22, and a reflective layer 23 on the other main surface. Layer 2
6 and the barrier layer 27 are sequentially laminated.

As described above, when the reflective conductive substrate is configured to be symmetrical with respect to the laminate, the two main surfaces of the laminate have the same coefficient of thermal expansion, and even when heated,
Deformation such as warpage hardly occurs.

FIG. 3 is a sectional view of a reflection type liquid crystal display device provided with the above-mentioned reflection type conductive substrate. In FIG. 3, the reflective liquid crystal display device 31 is provided to face a reflective conductive substrate 32 and a surface of the reflective conductive substrate 32 on which a conductive layer (not shown) is formed. A transparent resin substrate 33 on which a transparent electrode (not shown) is formed, and a liquid crystal layer 3 provided between the reflective conductive substrate 32 and the transparent resin substrate 33
4.

As the transparent resin substrate 33 used in the thus configured reflection type liquid crystal display device, a conventional transparent resin substrate used conventionally as shown in FIG. 5 can be used. As described above, the transparent resin substrate has an anchor coat layer and a transparent electrode layer sequentially laminated on one main surface of the heat-resistant transparent resin film, and a barrier layer and a transparent electrode layer on the other main surface of the heat-resistant transparent resin film. The hard coat layers are sequentially laminated.

Examples of the material of the heat-resistant transparent resin film used for the transparent resin substrate include polycarbonate, polyarylate, and polyether sulfone, norbornene-based resin commercially available as ARTON from Nippon Synthetic Rubber Co., and Asahi Kasei Corporation. A-PPE includes commercially available thermosetting allylated polyphenylene ether.

The barrier layer used for the transparent resin substrate is also required to have an oxygen barrier property and a water vapor barrier property. In general, resins having these functions at the same time are known other than resins containing a halogen atom. Absent. However, when a resin containing a halogen atom is used, free halogen ions are mixed into the liquid crystal layer, which adversely affects the characteristics of the device. Therefore, the barrier layer is usually composed of a composite film in which a resin film having an oxygen barrier property and a resin film having a water vapor barrier property are stacked.

Examples of the resin having an oxygen barrier property constituting the transparent resin substrate include nylon and an ethylene-vinyl alcohol copolymer, and examples of the resin having a water vapor barrier property include polyethylene. it can. These resin films preferably have a thickness of 5 to 10 μm. When the thickness exceeds 10 μm, the light transmittance of the transparent resin substrate decreases, and when the thickness is less than 5 μm, the barrier property becomes insufficient.

When the hard coat layer used in the transparent resin substrate is made of a urethane resin, a silicone resin, an acrylic resin, or the like, sufficient scratch resistance can be obtained. The anchor coat layer is usually composed of a primer such as an acrylic resin, a coupling agent, or the like.

As the transparent resin substrate, a heat-resistant transparent resin film having at least one principal surface on which a barrier layer made of silica similar to that described for the reflective conductive substrate is used is used. Is preferred. When the transparent resin substrate is configured in this manner, a high barrier property can be obtained with a simple configuration, and the thickness and weight of the reflective liquid crystal display device can be reduced.

The thickness of this barrier layer is 0.3 to 2.0 μm.
m, more preferably 0.3 to 1.0 μm. In addition, it is preferable to form the barrier layer on both sides of the heat-resistant transparent resin film because the barrier property is further improved.

In the reflection type liquid crystal display device of the present invention, the liquid crystal layer is made of the same liquid crystal material as used in a normal reflection type liquid crystal display device. Although the reflective conductive substrate of the present invention has been described as being used for a reflective liquid crystal display device, the present invention can be applied to, for example, a display device using electroluminescence.

[0056]

Embodiments of the present invention will be described below. (Example 1) A reflective conductive substrate (1) was produced as follows.

First, a glass epoxy copper clad laminate TLC551M having a thickness of 0.1 mm and a width of 1 m, which is commercially available from Toshiba Chemical Company, is subjected to an etching treatment to peel off a copper foil, and a laminate made of E glass is formed. Produced.

One-part heat-resistant white paint No. 1 made by Okitsumo in which titania was dispersed in a silicone resin was used. 4264-2 was impregnated and white paint was applied to both sides of the laminate. This was heated at a temperature of 150 ° C. for 4 hours to cure the paint, and a reflective layer having a thickness of 5 μm was formed on both sides of the laminate at the center of the laminate.

Next, a xylene solution containing 20% by weight of a low-temperature fired cyclic perhydropolysilazane manufactured by Tonen Co., Ltd.
Dipped in L110 type,
Dry for 0 minutes. This laminate was immersed in a hydrogen peroxide solution for 4 hours, and further heated at a temperature of 150 ° C. for 2 hours, so that the central portion of the laminate was placed on the reflective layers formed on both sides of the laminate. Thus, a barrier layer made of silica having a thickness of 1.7 μm was formed.

Since the dip coating method was employed in the above-mentioned coating, unevenness in the thickness of the coating film occurred at the end of the laminate. Therefore, the ends parallel to the liquid surface during immersion were cut and removed with a width of 10 cm, respectively, and the ends perpendicular to the liquid surface were cut and removed with a width of 5 cm each.

Further, a 1000 angstrom thick IT was formed on one main surface of the laminate by sputtering.
By forming the O film as a conductive layer, a reflective conductive substrate (1) was obtained. During the production of the reflective conductive substrate (1), no warping or bending of the substrate occurred.

The linear thermal expansion coefficient of the reflection-type conductive substrate (1) manufactured as described above was measured.
It was found to be an extremely small value of 0 ^-5 / ° C. Further, when the surface roughness was measured, R _max was 11 nm.

Example 2 A reflective conductive substrate (2) was manufactured as follows. First, a thickness of 0.1 mm commercially available from Mitsubishi Engineering-Plastics Corporation
A copper-clad laminate CCL-H860 having a width of 1 m and a width of 1 mm was subjected to an etching treatment to peel off the copper foil, thereby producing a laminate made of E glass.

A reflective conductive substrate (2) was produced in the same manner as in Example 1 except that this laminated plate was used. During the production of the reflective conductive substrate (2), no warping or bending of the substrate occurred.

When the coefficient of linear thermal expansion of the reflective conductive substrate (2) produced as described above was measured, it was 1.3 × 1.
It was found to be an extremely small value of 0 ^-5 / ° C. When the surface roughness was measured, R _max was 9 nm.

Example 3 A reflective conductive substrate (3) was manufactured as follows. First, a poly-p-phenylenephthalamide fiber manufactured by DuPont-Toray-Kevlar Co., Ltd. commercially available from Sakai Sangyo Co., Ltd.
Phenol novolak resin and bisphenol F type epoxy resin were added to 10 mm plain weave fiber cloth T-740.
The mixture was mixed at a weight ratio of 4: 168, and impregnated with a thermosetting resin composition consisting of a ketone-based solvent to which 1.5% by weight of Novacure 3721, a latent enhancement catalyst manufactured by Asahi Kasei Corporation, was added. This fiber cloth was dried at 80 ° C. for 1 hour to produce two prepregs.

These two prepregs were laminated so that the MD or TD directions of the respective fiber cloths crossed each other, and hot-pressed at a pressure of 40 kg / cm ² and a temperature of 150 ° C. to produce a laminated board. . In addition, the ratio of the resin component in the manufactured laminated board was 45% by weight, and the thickness was 0.17 mm.

A reflective conductive substrate (3) was produced in the same manner as in Example 1 except that this laminated plate was used. During the production of the reflective conductive substrate (3), no warping or bending of the substrate occurred.

The linear thermal expansion coefficient of the reflective conductive substrate (3) manufactured as described above was measured to be 1.1 × 1
It was found to be an extremely small value of 0 ^-5 / ° C. Further, when the surface roughness was measured, R _max was 7 nm.

Further, as described below, transparent resin substrates (1) and (2) used as the opposite substrates of the reflection type liquid crystal display device were produced. Transparent resin substrate (1) A xylene solution commercially available from Mitsui Tosho Chemical Co., Ltd. containing a 100 μm-thick optical polyethersulfone film at a concentration of 20% by weight of a low-temperature sinterable cyclic perhydropolysilazane. It was immersed in Tonen polysilazane low-temperature firing type N-L110 type manufactured by Tonen Co.
At 30 ° C. for 30 minutes. After immersing this polyether sulfone film in a hydrogen peroxide solution for 4 hours,
Further, by heating at a temperature of 150 ° C. for 2 hours, the thickness of both sides of the polyethersulfone film is reduced to 0.1 mm.
A barrier layer made of 5 μm silica was formed.

Further, on one main surface of the polyethersulfone film, a thickness of 1000
Angstrom ITO film is formed as a conductive layer,
A transparent resin substrate (1) was produced.

The linear thermal expansion coefficient of the transparent resin substrate (1) manufactured as described above was measured to be 5.5 × 10
It was found to be a slightly large value of ^-5 / ° C. Further, when the surface roughness was measured, R _max was 10 nm.

Transparent resin substrate (2) On both sides of a cured film of thermosetting allylated polyphenylene ether having a thickness of 100 μm, which is commercially available from Asahi Kasei Corporation, A transparent resin substrate (2) was formed by forming a barrier layer having a thickness of 1: 1 and forming an ITO film as a conductive layer on one main surface thereof.

The linear thermal expansion coefficient of the transparent resin substrate (2) manufactured as described above was measured.
It was found to be a slightly large value of ^-5 / ° C. Further, when the surface roughness was measured, R _max was 8 nm.

The above-mentioned reflective conductive substrates (1) to (3), transparent resin substrates (1) and (2), and a 0.7 mm-thick alkali-free glass substrate OA commercially available from NEC Corporation -2, the weight and thickness were compared. Table 1
Shows the results.

[0076]

[Table 1]

In Table 1, the reflective conductive substrates (1) to (3)
The weights of the transparent resin substrates (1) and (2) are shown as relative values to the weight of the OA-2 substrate. As is clear from Table 1, the reflective conductive substrate and the transparent resin substrate of the present invention are lighter and thinner than the glass substrate.

Further, the reflective conductive substrates (1) to (3), transparent resin substrates (1) and (2) of Examples 1 to 3 and polycarbonate commercially available from Fujimori Kogyo Co., Ltd. 100μm thick transparent resin substrate AMOR
Water vapor permeability of EX film and 100 μm thick transparent resin substrate FST-5337 based on polyether sulfone, which is commercially available from Sumitomo Bakelite Co., at a temperature of 40 ° C. and a humidity of 60% RH. And oxygen permeability were measured. Table 2 shows the results.

[0079]

[Table 2]

As shown in Table 2, it can be seen that the reflective conductive substrates (1) to (3) of Examples 1 to 3 exhibited good water vapor barrier properties. Transparent resin substrate (1), (2)
Has a lower water vapor barrier property than the reflective conductive substrates (1) to (3), but has a higher AMOLEX and FST-533.
7 shows a higher water vapor barrier property.

Further, it can be seen that the reflective conductive substrates (1) to (3) and the transparent resin substrates (1) and (2) have sufficient oxygen barrier properties. Example 4 A reflection type liquid crystal display device was manufactured as follows.

First, the conductive layer of the reflective conductive substrate (2) prepared in Example 2 was patterned to prepare an array electrode substrate. A polyimide film was applied to the electrode surface of the array electrode substrate and rubbed to form an alignment film.

Next, a polyimide film was applied to the surface of the transparent resin substrate (2) on which the conductive layer was formed, and a rubbing treatment was performed to form an alignment film, thereby forming a common electrode substrate.

A spacer composed of silica fine particles was sprayed on the electrode surface of the array electrode substrate formed as described above.
An array electrode substrate and a common electrode substrate were bonded to each other with a sealing agent made of an epoxy resin so that the respective electrode surfaces faced each other, thereby producing a liquid crystal cell.

After injecting a liquid crystal material from the opening of the liquid crystal cell, the opening is sealed, and a display layer of polyvinyl butyral-iodine having a thickness of 0.2
A 5-inch reflective liquid crystal display device was manufactured by attaching a polarizing film having a thickness of 5 mm.

Note that, when manufacturing a reflection type liquid crystal display device,
There was no process trouble due to deformation such as warping or bending of the reflective conductive substrate. The reflective liquid crystal display did not break even when subjected to a drop test from a height of 1.5 m.

(Embodiment 5) The array electrode substrate was used in Embodiment 1.
A 5-inch reflective liquid crystal display device was manufactured in the same manner as in Example 4, except that the reflective electrode substrate was formed using the reflective conductive substrate prepared in the above, and the common electrode substrate was formed using the transparent resin substrate. did.

Note that, when manufacturing a reflection type liquid crystal display device,
There was no process trouble due to deformation such as warping or bending of the reflective conductive substrate. The reflective liquid crystal display did not break even when subjected to a drop test from a height of 1.5 m.

(Embodiment 6) The array electrode substrate was used in Embodiment 3.
A 5-inch reflective liquid crystal display device was produced in the same manner as in Example 4, except that the reflective liquid crystal display device was formed using the reflective conductive substrate produced in the above.

Note that, when manufacturing a reflection type liquid crystal display device,
There was no process trouble due to deformation such as warping or bending of the reflective conductive substrate. The reflective liquid crystal display did not break even when subjected to a drop test from a height of 1.5 m.

Example 7 A reflection type liquid crystal display device was manufactured in the same manner as in Example 4 except that the size was changed to 7 inches.

Even when the size was set to 7 inches, no trouble occurred in the process due to deformation such as warping or bending of the reflective conductive substrate when manufacturing the reflective liquid crystal display device.
The reflective liquid crystal display did not break even when dropped from a height of 1.5 m.

Example 8 A reflection type liquid crystal display device was manufactured in the same manner as in Example 5 except that the size was changed to 7 inches.

Even when the size was set to 7 inches, no trouble occurred in the process due to deformation such as warping or bending of the reflective conductive substrate when manufacturing the reflective liquid crystal display device.
The reflective liquid crystal display did not break even when dropped from a height of 1.5 m.

Example 9 A reflection type liquid crystal display device was manufactured in the same manner as in Example 6, except that the size was changed to 7 inches.

Even when the size was set to 7 inches, no trouble occurred in the process due to deformation such as warping or bending of the reflective conductive substrate when manufacturing the reflective liquid crystal display device. The reflective liquid crystal display did not break even when dropped from a height of 1.5 m.

(Comparative Example 1) A commercially available polycarbonate-based film having a thickness of 10
A liquid crystal cell was produced in the same manner as in Example 4, except that an array electrode substrate and a common electrode substrate were produced using a 0 μm transparent resin substrate AMOREX film.

Next, on the back surface of the electrode surface of the array electrode substrate of this liquid crystal cell, a one-pack heat-resistant white paint No. 42
64-2 was applied and heated at a temperature of 150 ° C. for 4 hours to cure the coating, thereby forming a reflective layer having a thickness of 5 μm.

After injecting a liquid crystal material from the opening of the liquid crystal cell, the opening is sealed, and a display layer of polyvinyl butyral-iodine having a thickness of 0.2 is formed on the display surface side of the common electrode substrate.
A 5-inch reflective liquid crystal display device was manufactured by attaching a polarizing film having a thickness of 5 mm.

In the production of the reflection type liquid crystal display device, the transparent resin substrate was bent during the substrate transport process, and the transparent resin substrate was warped during the sealing process, resulting in a positioning trouble. Therefore, the positional accuracy of the manufactured liquid crystal cell became insufficient.

When this reflective liquid crystal display device was dropped from a height of 1.5 m, no damage occurred. (Comparative Example 2) Commercially available from Sumitomo Bakelite,
Polyethersulfone base film thickness 10
A reflective liquid crystal display device was manufactured in the same manner as in Comparative Example 1, except that an array electrode substrate and a common electrode substrate were manufactured using a 0 μm transparent resin substrate FST-5337.

In the production of this reflective liquid crystal display device, the transparent resin substrate was bent during the substrate transfer process, and the transparent resin substrate was warped during the sealing process, causing a positioning trouble. Therefore, the positional accuracy of the manufactured liquid crystal cell became insufficient.

When this reflective liquid crystal display device was dropped from a height of 1.5 m, no damage occurred. (Comparative Example 3) An array electrode substrate was manufactured using a 0.7 mm thick non-alkali glass substrate OA-2 commercially available from Nippon Electric Glass Co., Ltd., and a polyether sulfone commercially available from Sumitomo Bakelite Co., Ltd. A liquid crystal cell was produced in the same manner as in Example 4 except that a common electrode substrate was produced using a transparent resin substrate FST-5337 having a thickness of 100 μm and using as a base film.

After injecting a liquid crystal material from the opening of this liquid crystal cell, the opening was sealed, and a display layer of polyvinyl butyral-iodine having a thickness of 0.2 was formed on the display surface side of the common electrode substrate.
mm polarizing film was attached.

Next, on the back side of the electrode surface of the array electrode substrate of this liquid crystal cell, a 200 μm thick white PET, E22, commercially available from Toray Co., Ltd.
Was arranged as a reflective layer to produce a 5-inch reflective liquid crystal display device.

Note that, when manufacturing a reflection type liquid crystal display device,
There was no process trouble due to deformation such as warping or bending of the reflective conductive substrate. However, when the reflective liquid crystal display device was dropped from a height of 1.5 m,
The array electrode substrate was damaged.

(Comparative Example 4) A non-alkali glass substrate OA- having a thickness of 0.7 mm, commercially available from NEC Corporation
A reflective liquid crystal display device was produced in the same manner as in Comparative Example 3, except that a common electrode substrate was produced using Sample No. 2.

Note that, when manufacturing the reflection type liquid crystal display device,
There was no process trouble due to deformation such as warping or bending of the reflective conductive substrate. However, when the reflective liquid crystal display device was dropped from a height of 1.5 m,
The array electrode substrate and the common electrode substrate were damaged.

The weight and thickness of the reflective liquid crystal display devices of Examples 4 to 9 and Comparative Examples 1 to 4 were compared. Table 3 shows the results.

[0110]

[Table 3]

In Table 3, the weights of the reflective liquid crystal display devices of Examples 4 to 9 and Comparative Examples 1 to 3 are shown as relative values to the weight of the reflective liquid crystal display device of Comparative Example 4. As is clear from Table 3, the reflective liquid crystal display devices of Examples 1 to 9 are sufficiently lighter than the reflective liquid crystal display devices of Comparative Examples 3 and 4. Further, the reflective liquid crystal display devices of Examples 4 to 9 have a thickness equal to or less than that of the reflective liquid crystal display devices of Comparative Examples 1 and 2.
It can be seen that the thickness is significantly reduced as compared with the reflective liquid crystal display device of No. 4.

[0112]

As described above, according to the present invention, a reflective conductive substrate is formed by forming a reflective layer containing a white pigment and a resin and a barrier made of silica on a laminate made of a fiber cloth cured with a resin. Since the layers are formed by sequentially laminating layers and conductive layers, they are lightweight, have sufficient impact resistance, oxygen barrier properties, water vapor barrier properties, and scratch resistance, are simple in configuration, have heat resistance and A highly reflective reflective conductive substrate, a reflective liquid crystal display device, and a method for manufacturing a reflective conductive substrate can be provided.

[Brief description of the drawings]

FIG. 1 is a cross-sectional view of a reflective conductive substrate according to an embodiment of the present invention.

FIG. 2 is a cross-sectional view of a reflective conductive substrate according to another embodiment of the present invention.

FIG. 3 is a cross-sectional view of a reflective liquid crystal display device according to an embodiment of the present invention.

FIG. 4 is a sectional view of a conventional reflection type liquid crystal display device.

FIG. 5 is a cross-sectional view of a conventional transparent resin substrate.

FIG. 6 is a cross-sectional view of a conventional reflection type liquid crystal display device.

FIG. 7 is a sectional view of a conventional reflective liquid crystal display device.

[Explanation of symbols]

 11, 21 ... Reflective conductive substrate 12, 22 ... Laminated plate 13, 23, 26 ... Reflective layer 14, 24, 27 ... Barrier layer 15, 25 ... Conductive layer 31 ... Reflective liquid crystal display device 32 ... Reflective conductive Substrate 33 Transparent resin substrate 34 Liquid crystal layer 41, 61, 71 Reflective liquid crystal display device 42, 43, 62, 63, 72, 73 Conductive substrate 44, 64, 74 Liquid crystal layer 45, 65, 75 Light reflection layer 51: conductive substrate 52: heat-resistant transparent resin film 53: anchor coat layer 54: transparent electrode layer 55: barrier layer 56: hard coat layer

Claims (5)

[Claims] 1. A laminate including a fiber cloth impregnated with a resin and cured, a reflective layer including a white pigment and a resin and formed on the laminate, and a reflective layer including silica and formed on the reflective layer. A reflective conductive substrate, comprising: a barrier layer; and a conductive layer formed on the barrier layer. 2. The reflective conductive substrate according to claim 1, wherein the silica constituting the barrier layer is formed from polysilazane having a cyclic structure. 3. The laminate according to claim 1, wherein the reflective layer and the barrier layer are formed on both sides of the laminate.
4. The reflective conductive substrate according to 1. 4. A laminate including a fiber cloth impregnated with a resin and cured, a reflective layer including a white pigment and a resin and formed on the laminate, and a reflective layer including silica and formed on the reflective layer. A reflective conductive substrate including a barrier layer and a conductive layer formed on the barrier layer; and a transparent conductive substrate provided on a surface of the reflective conductive substrate on which the conductive layer is formed. A reflective liquid crystal display device comprising: a transparent resin substrate on which electrodes are formed; and a liquid crystal layer provided between the reflective conductive substrate and the transparent resin substrate. 5. A step of applying a mixture of a white pigment and a thermosetting resin to one main surface of a laminate obtained by impregnating a resin with a fiber cloth as a core material and curing the resin, and heating the laminate to form a reflective layer. Forming a barrier layer containing silica by applying a polysilazane having a cyclic structure on the reflective layer and heat-treating the same; and forming a conductive layer on the barrier layer. Method for manufacturing a mold conductive substrate.