WO2005051654A1

WO2005051654A1 - Resin sheet, liquid crystal cell substrate, liquid crystal display, substrate for electroluminescent display, electroluminescent display and substrate for solar cell

Info

Publication number: WO2005051654A1
Application number: PCT/JP2004/017413
Authority: WO
Inventors: Tadaaki Harada; Yuuzou Akada; Yoshimasa Sakata
Original assignee: Nitto Denko Corporation
Priority date: 2003-11-25
Filing date: 2004-11-24
Publication date: 2005-06-09
Also published as: US20070042168A1; CN1886259A; JP2005153273A; KR20060101483A

Abstract

Disclosed is a resin sheet which is reduced in weight and thickness, improved in impact resistance, and suppressed in thermal shrinkage/expansion. In addition, the resin sheet is excellent in light transmittance for not lowering the display quality of displays and the like. Also disclosed are a substrate for displays, a display and a substrate for solar cells respectively comprising such a resin sheet. The resin sheet is characterized by comprising a cured resin layer containing a fabric-like body which is made of glass fibers and a overcoat layer so formed on the surface of the cured resin layer as to have a surface roughness (Rt) of not more than 200 nm. The resin sheet is further characterized by having a haze value of not more than 10%.

Description

Specification

Resin sheet, liquid crystal cell substrate, liquid crystal display device, electorifice luminescence display device substrate, electoric luminescence display device, and solar cell substrate

Technical field

The present invention relates to a resin sheet mainly used for a display device, a substrate for a display device provided with the resin sheet, a display device, and a substrate for a solar cell.

Background art

[0002] In a liquid crystal display device, an electorum luminescence display device, and the like, the use of a plastic substrate instead of a conventional glass substrate has been proposed from the viewpoint of reducing the weight, thickness, and impact resistance of the display. I have. However, a low coefficient of thermal expansion is required for this type of substrate. There is a problem such as misalignment at the time of forming a color filter.

[0003] In particular, in recent years, in liquid crystal display devices, the active matrix drive system has been adopted in various ways because of its higher display quality than the passive matrix drive system. In this case, since a lower coefficient of thermal expansion is required as compared with the passive matrix driving method, the above-mentioned problem becomes more remarkable. Further, the plastic substrate also has a problem that the mechanical strength is relatively low.

[0004] Conventionally, to solve these problems, a glass fiber woven body in which glass fibers are woven in a cloth shape is impregnated with a resin before curing, formed into a sheet shape, and cured to form a glass fiber material. A resin sheet for a substrate in which a cloth body is embedded in a resin cured layer has been proposed (Patent Documents 1 and 2 below).

[0005] Patent Document 1: Japanese Patent Application Publication No. 2003-50384

Patent Document 2: Japanese Patent Application Laid-Open No. 11 2812

Disclosure of the invention

Problems to be solved by the invention

[0007] However, a glass fiber cloth is embedded in a cured resin layer to form a resin sheet for a substrate. When manufactured, the cured resin layer is composed of two components, glass and resin, so that transmitted light may be diffused and adversely affect light transmittance.

[0008] In addition, in the resin sheet having such a configuration, there is a case where irregularities are easily generated on the surface of the resin sheet due to the shape of the glass fiber cloth-like material, which adversely affects light transmittance. is there.

[0009] Therefore, the present invention provides a resin that is lightweight, thin, and has improved impact resistance, suppresses contraction and expansion due to heat, and has excellent light transmittance so that the display quality of a display device is not degraded. Another object is to provide a sheet, a display device substrate, a display device, and a solar cell substrate each including the resin sheet.

Means for solving the problem

[0010] In view of the above problems, the present invention relates to a resin cured layer including a glass fiber cloth, and an overcoat laminated on the surface of the resin cured layer such that the surface roughness Rt is 200 nm or less. And a resin sheet characterized by having a haze value of 10% or less.

In the present invention, the haze value can be measured, for example, based on JIS K 7136, and specifically, a commercially available haze meter (for example, trade name HM-150, manufactured by Murakami Color Co., Ltd.) It is measured using

The invention's effect

[0012] According to the resin sheet of the present invention, since the resin sheet includes the resin cured layer including the glass fiber cloth, the weight and thickness can be reduced, and the impact resistance can be improved. Contraction and expansion can be suppressed. Therefore, for example, when the liquid crystal cell substrate is used for forming a liquid crystal panel, it is possible to avoid the displacement of the electrodes and the color filters described above. In addition, the resin sheet according to the present invention is caused by the glass fiber fabric because the overcoat layer is laminated on the surface of the resin hardened layer so that the surface roughness Rt is 200 nm or less. The resin sheet is configured such that unevenness is eliminated and the haze value is 10% or less, so that the diffusion of transmitted light is small and the resin sheet is extremely excellent in light transmittance. Therefore, for example, when used as a liquid crystal cell substrate or a substrate for an electroluminescent display device, the display quality of the display device is excellent. Further, the solar cell substrate provided with the resin sheet can contribute to the improvement of the power generation efficiency of the solar cell. Brief Description of Drawings

FIG. 1 is a cross-sectional view showing a resin sheet according to one embodiment.

FIG. 2 is a cross-sectional view showing a resin sheet according to another embodiment.

Explanation of symbols

[0014] 1 resin cured layer

2 Glass fiber cloth

3 Overcoat layer

4 Gas barrier layer

5 Node coat layer

10 Resin sheet

BEST MODE FOR CARRYING OUT THE INVENTION

As shown in FIG. 1, a resin sheet 10 according to the present invention includes a resin cured layer 1 including a glass fiber cloth 2 and a resin cured layer 1 having a surface roughness Rt of 200 nm or less. It has an overcoat layer 3 laminated on the surface of the hardened fat layer 1 and further has a haze value of 10% or less.

Examples of the glass fiber cloth include a woven fabric, a nonwoven fabric, and a knitted fabric. Specifically, in addition to a general glass cloth in which yarn is woven, a glass nonwoven fabric, a roving cloth, and a chopped cloth are used. Known commercial products such as pud strand mats and Sudare cloth can be used.

[0017] Examples of the glass fiber cloth-like material, rather preferable that the density is in the range of 10- 500g / m ^2, 20- preferably from the range force of 350 g / m ^2, of 30- 250 g / m ² Especially preferred range power! / ,. Further, the thickness of the glass fiber filament is preferably 3 to 15 m, more preferably 5 to 13 m, and particularly preferably 5 to 10 m. As the material of the glass fiber, soda glass, borosilicate glass, alkali-free glass, or the like is used. Alkali-free glass is preferred because alkali components may adversely affect TFTs and the like.

The thickness of the glass fiber cloth is preferably 10 to 500 μm, more preferably 15 to 350 μm, and particularly preferably 30 to 250 m.

[0019] Further, the resin constituting the resin-cured layer may be a thermosetting resin such as a polyether sulfone, a polycarbonate, an epoxy resin, an acrylic resin, or a polyolefin resin for various optics. UV-curable resin can be used. Above all, it is preferable to use an epoxy resin from the viewpoint of excellent surface smoothness and good hue.

[0020] The resin cured layer preferably has a thickness of 20 to 800 m. If the thickness is less than 20 m, the strength and rigidity may be insufficient. If the thickness is more than 800 / z m, the advantages of the thin and lightweight resin sheet may be impaired.

[0021] As the epoxy resin constituting the resin cured layer, conventionally known epoxy resins can be used, and examples thereof include bisphenol A type, bisphenol F type, bisphenol S type and their water additives. Bisphenol type; Novolak type such as phenol novolak type and cresol novolak type; Nitrogen-containing ring type such as triglycidyl isocyanurate type ゃ hydantoin type; Alicyclic type; Aliphatic type; Aromatic type such as naphthalene type Low water absorption type such as glycidyl ether type bibiphenyl type; dicyclo type such as dicyclopentadiene type; ester type; ether ester type; and modified types thereof.

[0022] Among these epoxy resins, bisphenol A type epoxy resin, alicyclic epoxy resin, and triglycidyl isocyanurate type epoxy resin are preferred from the viewpoint of excellent discoloration prevention properties. In addition, these epoxy resins may be used alone or in combination of two or more.

[0023] Examples of the dicyclopentadiene type epoxy resin (epoxy resin having a dicyclopentadiene skeleton) include epoxy resins represented by the following chemical formulas (1) and (2). No. In the following chemical formula (2), n is an integer of 1 to 3.

[Chemical 1]

[Formula 2]

_{_{0-CH 2 -CH-CH 2}} 0-CH 2 -CH-CH 2 0-CH 2 -CH-CH 2 "\ Roh

0 Ό ⁷ (2) By using the epoxy resin represented by chemical formula (1) or (2), the retardation in the thickness direction of the resin sheet can be controlled to a small value, and by reducing the retardation in the thickness direction, the laminated film can be used for a liquid crystal display device. When used, light leakage from oblique directions in black display is suppressed, and the display characteristics are further improved.

[0024] It is preferable that the epoxy resin has, for example, an epoxy equivalent of 100 to 1000 (g / eq) and a softening point of 120 degrees or less in terms of improving flexibility and strength of the resin sheet to be formed. No. Further, it is preferable that the epoxy resin is liquid at normal temperature (for example, 5-35 ° C.). Furthermore, when forming a resin sheet, a two-component epoxy resin showing a liquid state at a temperature lower than the temperature at the time of coating, particularly at room temperature, is preferred because of its excellent spreadability and coatability. New

[0025] In addition to the resin, the resin cured layer may contain various additives as necessary.

Examples of the additives include a curing agent, a curing accelerator, an antioxidant, a denaturant, a surfactant, a dye, a pigment, a discoloration inhibitor, and an ultraviolet absorber.

[0026] The curing agent is not particularly limited !, but examples thereof include organic acid compounds such as tetrahydrophthalic acid, methyltetrahydrophthalic acid, hexahydrophthalic acid, and methylhexahydrophthalic acid, and ethylenediamine. And amine-based compounds such as propylenediamine, diethylenetriamine, triethylenetetramine, amine amines thereof, metaphenylenediamine, diaminediphenylmethane, diaminodiphenylsulfonic acid and the like. These curing agents may be used alone or in combination of two or more.

[0027] In addition to the above-mentioned curing agents, for example, amide compounds such as dicyandiamide and polyamide, hydrazide compounds such as dihydrazide, methylimidazole, 2-ethyl-4-methylimidazole, ethildimidazole , Imidazole compounds such as 2,4-dimethylimidazole, 2,4-dimethylimidazole, phe-imidazole, pendecylimidazole, heptadecylimidazole, 2-phenyl-4-methylimidazole, methylimidazoline, 2-ethyl-4-methyl Imidazoline-based compounds such as imidazoline, etinoleimidazoline, isopropylimidazoline, 2,4-dimethylimidazoline, phe-imidazoline, pendecylimidazoline, heptadecylimidazoline, and 2-phenyl-4-methylimidazoline; Enol compounds, urea compounds, polysulfide compounds, etc.

[0028] Further, acid anhydride compounds and the like can also be used as the curing agent, and such acid anhydride compounds are preferable, for example, in terms of discoloration prevention and the like. Specific examples include phthalic anhydride, maleic anhydride, trimellitic anhydride, pyromellitic anhydride, nadic anhydride, glutaric anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, and hexahydrophthalic anhydride. Acid anhydride, methyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, methylnadic anhydride, dodecyl-succinic anhydride, dichlorosuccinic anhydride, benzophenone Examples thereof include tetracarboxylic anhydride and chlorenedic anhydride. Among these acid anhydride compounds, those which are colorless or pale yellow and have a molecular weight of about 140 to about 200 are preferred. For example, phthalic anhydride, tetrahydrophthalic anhydride, hexahydro Examples include phthalic anhydride, methylhexachlorophthalic anhydride, and methylnadic anhydride.

When an epoxy resin is employed as the resin constituting the resin cured layer, the mixing ratio of the epoxy resin and the curing agent is not particularly limited, but an anhydride-based curing agent is used as the curing agent. When a curing agent is used, it is preferable to mix the acid anhydride equivalent to 0.5 to 1.5 equivalent with respect to 1 equivalent of the epoxy group of the epoxy resin, more preferably 0.5 to 1.5 equivalent. 7 One-1.2 equivalents. When the compounding amount of the acid anhydride is 0.5 or more, the hue after curing is more excellent, and when it is 1.5 equivalents or less, sufficient moisture resistance can be maintained. In the case where another curing agent is used, or in the case where two or more curing agents are used in combination, for example, they can be blended in accordance with the ratio as described above.

[0030] The curing accelerator is not particularly restricted but includes, for example, tertiary amines, imidazoles, quaternary ammonium salts, quaternary phospho-dium salts, organic metal salts, Examples thereof include phosphorus conjugates and urea compounds, among which tertiary amines, imidazoles, and quaternary phosphonium salts are particularly preferred. One of these curing accelerators may be used alone, or two or more thereof may be used in combination.

[0031] The mixing ratio of the curing accelerator in the resin cured layer is not particularly limited, and can be appropriately determined according to the type of the resin used and the like. For example, when using epoxy resin, epoxy It is preferable that the curing accelerator is, for example, 0.05 to 7.0 parts by weight based on 100 parts by weight of the resin, and the range of 0.2 to 3.0 parts by weight is more preferable. When the compounding ratio of the curing accelerator is 0.05 parts by weight or more, a sufficient curing promoting effect can be obtained, and when it is 7.0 parts by weight or less, the hue after curing becomes excellent.

[0032] The antioxidant is not particularly limited, and for example, conventionally known compounds such as a phenolic compound, an amine compound, an organic sulfur compound and a phosphine compound can be used.

The modifying agent is not particularly limited, and for example, conventionally known modifying agents such as glycols, silicones, and alcohols can be used.

As the surfactant, for example, various surfactants such as silicone-based, acrylic-based, and fluorine-based surfactants can be used, and among these, silicone-based surfactants are preferable. These surfactants are added, for example, when the resin is cured while being in contact with air by a casting method or the like to form a resin sheet, so as to smooth the sheet surface.

[0034] The resin sheet of the present invention is preferably a resin whose absolute value of the difference in the refractive index between the resin constituting the resin cured layer and the glass fiber cloth is 0-0.01. Is 0-0.008, particularly preferably 0-0.006. If the absolute value of the difference in the refractive index is 0.01 or less, the interface curing between the glass fiber cloth and the resin constituting the resin cured layer in the resin cured layer is suppressed to reduce the haze and to cure the resin. This is because the inherent transparency of the layer can be sufficiently maintained.

The refractive index can be measured by an Abbe refractometer at 25 ° C. and 589 nm.

On the other hand, the overcoat layer 3 constituting the resin sheet 10 of the present invention is laminated on the surface of the resin cured layer 1 so that the surface roughness Rt is 200 μm or less, Preferably, it is laminated on the surface of the resin cured layer 1 so that the surface roughness Rt is 100 m or less. Further, as shown in FIG. 1, the overcoat layer 3 is preferably laminated on both the front and back surfaces of the resin cured layer 1.

By forming such an overcoat layer, it is possible to eliminate irregularities caused by the shape of the glass fiber cloth and the difference in shrinkage between the glass fiber cloth and the resin, and to provide excellent surface smoothness. A highly transparent resin sheet can be obtained. [0036] In the present invention, "surface roughness Rt" refers to a stylus type surface roughness measuring device (for example, trade name P

—11; manufactured by Tencor Corporation), 800 m long wavelength cutoff, 250 m short wavelength cutoff

It shows the difference between the maximum value and the minimum value measured under the condition of an evaluation length of 10 mm.

[0037] The overcoat layer preferably has a thickness of 5 to 70 m from the viewpoint of excellent surface smoothness, preventing gap unevenness in the display device, and making the image of the display device clearer. And more preferably 10 to 30 m.

When the overcoat layer is laminated on both the front and back surfaces of the resin cured layer, the difference in thickness between the front and back overcoat layers is set to 10 m or less from the viewpoint of preventing warpage of the resin sheet. Is preferred.

[0038] The resin constituting the overcoat layer is not particularly limited, but a resin that cures at room temperature can be suitably used in that there is no shrinkage after curing. As the resin that cures at room temperature, for example, an ultraviolet-curable resin using a light-powered thione initiator can be given. Among them, a mixture of an oxetane resin and an epoxy resin can be preferably used from the viewpoint of excellent chemical resistance.

Further, from the viewpoint of enhancing transparency, the resin constituting the overcoat layer preferably has a refractive index difference of 0.03 or less from the resin constituting the resin hardened layer.

[0039] Further, known additives such as antioxidants, ultraviolet absorbers, dyes, pigments, inorganic fillers, and surfactants can be added to the overcoat layer, if necessary. is there

. When the inorganic filler is added, nanoparticles (particle size: 100 nm or less) are preferred because they do not adversely affect the transparency of the resin sheet.

The resin sheet of the present invention contains a glass fiber cloth as described above,

5 ° in linear expansion coefficient to 160 ° C from C is 3. OO X 10- ⁵ / ° C or less and so as it is preferable constructed.

[0041] coefficient of linear expansion, if 3. 00 X 10- ⁵ Z ° C or less, when using the laminated film of the present invention as a liquid crystal cell Le substrate to form a color filter or electrode on its surface, It is possible to sufficiently suppress positional deviations and the like caused by thermal expansion, and it becomes easier to form color filters and the like. Further, the linear expansion coefficient is more preferably 2. OO X 10- ⁵ Z ° C or less, particularly preferred properly 1. or less ⁵ X 10- 5 Z ° C. The coefficient of linear expansion is calculated by obtaining a TMA measurement value for the measured object by the TMA method specified in JIS K 7197, and substituting this value into the following equation. In the following equation, V, Δ Is (T) and Δ Is (T) are the TMA at the temperature T (° C) and T (° C) at the time of measurement.

1 2 1 2

L indicates the length (mm) of the DUT at room temperature 23 ° C.

0

You.

= Linear expansion coefficient ^{[1 / (LX 10 3)} ] · [(Δ ΐ δ (Τ) - A ls (T)) / (Τ - Τ)]

0 2 1 2 1

[0042] In addition, the resin sheet 10 of the present invention has a haze value of 10% or less. The resin sheet is more excellent in transparency, and the display quality of the display device is further improved. Therefore, the haze value is preferably 8% or less, more preferably 5% or less.

Further, the resin sheet of the present invention has a refractive index difference of 0.01 or less between the cured resin layer and the glass fiber cloth so that the light transmittance becomes 88% or more. It is preferred that it be composed.

When the light transmittance is 88% or more, for example, when the resin sheet of the present invention is used for a liquid crystal cell substrate or a substrate for an electroluminescent display device and various image display devices are assembled, characters and images are more likely to be produced. It becomes clearer and the display quality becomes better.

The light transmittance can be determined by measuring the total light transmittance at a wavelength of 550 nm using a high-speed spectrophotometer.

[0044] The method for producing the resin sheet of the present invention is not particularly limited.

For the resin cured layer, for example, casting method, casting method, impregnation method, coating method and the like

Any method can be used as long as the glass fiber cloth is impregnated with resin and cured.

As for the overcoat layer, for example, after the resin constituting the overcoat layer is cast and applied on the resin cured layer using a die coater or the like, the resin is cured to form the overcoat layer. A forming method can be suitably adopted.

[0045] The resin sheet of the present invention is a laminated body further provided with at least one of a hard coat layer harder than the resin cured layer and a gas nolia layer having better gas nolia property than the resin cured layer. In particular, as shown in FIG. 2, it is preferable that the laminate has both the hard coat layer 5 and the gas noria layer 4 and the hard coat layer 5 is laminated as the outermost layer. Yes. If the hard coat layer is laminated as the outermost layer, for example, the scratch resistance and the like of the sheet can be improved. In addition, in various image display devices of a liquid crystal display device, when moisture or oxygen penetrates the liquid crystal cell substrate and enters the liquid crystal cell, the liquid crystal is degraded or bubbles are generated, which results in poor appearance or conductive film. There is a possibility that disconnection of the pattern or the like may occur. However, if the gas barrier layer is laminated, permeation of gas such as moisture and oxygen is prevented. The hard coat layer and the gas barrier layer may be laminated on one of the surfaces, or may be laminated on both surfaces. However, it is preferable that the hard coat layer is laminated at least on the side surface without the lamination of the polarizing plate.

When both the hard coat layer and the gas noria layer are laminated, the laminating order is not particularly limited. However, the laminating layer is laminated on the resin cured layer in the order of the gas noria layer and the hard coat layer. Preferably they are layered. In particular, the hard coat layer is preferably laminated as the outermost layer because it has excellent impact resistance and chemical resistance!

[0047] The material for forming the hard coat layer is not particularly limited, and examples thereof include urethane-based resin, acrylic-based resin, polyester-based resin, polybutyl alcohol, and ethylene-vinyl alcohol copolymer. Polyvinyl alcohol-based resin, Shii-Dani vinyl-based resin, Shii-Dani-bilidene-based resin and the like. Further, for example, polyarylate resin, sulfone resin, amide resin, imide resin, polyethersulfone resin, polyetherimide resin, polycarbonate resin, silicone resin, fluorine Resins, polyolefin resins, styrene resins, butylpyrrolidone resins, cellulose resins, acrylonitrile resins and the like can also be used. Among these, urethane-based resins are more preferable, and urethane acrylate is more preferable. These resins may be used alone or as a blended resin obtained by mixing two or more types.

[0048] The thickness of the hard coat layer is not particularly limited, but is usually, for example, 0.1 to 50 m from the viewpoint of ease of peeling during production and prevention of generation of cracks at the time of peeling. , Preferably in the range of 0.5 to 8 μm, more preferably in the range of 2 to 5 μm.

[0049] Examples of the type of the gaseous layer include an organic gaseous layer and an inorganic gaseous layer. The material for forming the organic gas barrier layer is not particularly limited. Examples thereof include polybutyl alcohol and a partially saponified product thereof, and an ethylene-butyl alcohol copolymer. And the like, and materials having low oxygen permeation such as polyacrylonitrile and polyvinylidene chloride can be used. Among them, a vinyl alcohol-based polymer having a high gas-nolia point force is particularly preferable.

[0050] The thickness of the organic gas barrier layer is, for example, 10 m or less in terms of transparency, prevention of coloring, functions such as gas barrier properties, thickness reduction, and flexibility of the obtained resin sheet. Is more preferably 2 to 10 m, and still more preferably 3 to 5 m. When the thickness is 10 m or less, a lower yellowness index (YI value) can be maintained in the resin sheet, and when the thickness is 2 m or more, a sufficient gas barrier function is maintained.

On the other hand, as a material for forming the inorganic gas noria layer, for example, a transparent material such as silicon oxide, magnesium oxide, aluminum oxide, zinc oxide and the like can be used. Properties: excellent adhesion to base material layer Silicon oxides and silicon nitrides are preferred.

[0052] As the silicon oxide, for example, the ratio of the number of oxygen atoms to the number of silicon atoms is 1.

5-2. 0 is preferred. With such a ratio, for example, the gas barrier properties, transparency, surface flatness, flexibility, film stress, cost, and the like of the inorganic gas barrier layer are further improved. In addition, in the silicon oxide film, the maximum value of the ratio of the number of oxygen atoms to the number of silicon atoms is 2.0.

As the silicon nitride, for example, those in which the ratio of the number of nitrogen atoms (N) to the number of silicon atoms (Si) (Si: N) is 1: 1 to 3: 4 are preferable! /.

[0053] The thickness of the inorganic gas barrier layer is not particularly limited, but is preferably, for example, in the range of 5-200 nm. When the thickness is 5 nm or more, for example, more excellent gas barrier properties can be obtained, and when the thickness is 200 nm or less, transparency, flexibility, film stress, and cost are excellent. .

[0054] As described above, when the resin sheet of the present invention is a laminate, the thickness of the resin sheet differs depending on the number of layers, and the thickness of the resin sheet may be, for example, 30 to 800 m. preferable. According to the resin sheet having such a thickness, the advantages of the resin sheet such as excellent strength and rigidity, thinness and light weight are exhibited most. [0055] The method of laminating the hard coat layer and the gas barrier layer is not particularly limited, and any method may be used on the resin cured layer or on the overcoat layer formed on the surface of the resin cured layer. It can be laminated by a method.

[0056] The resin sheet of the present invention can be used for various applications, and can be particularly suitably used as a liquid crystal cell substrate, a substrate for an electroluminescent display device, and a substrate for a solar cell.

A liquid crystal display device is generally configured by appropriately assembling components such as a polarizing plate, a liquid crystal cell, a reflector or a backlight, and other optical components as necessary, and incorporating a driving circuit. The liquid crystal display device of the present invention can be configured in the same manner as the conventional one, except that a liquid crystal cell is configured using a liquid crystal cell substrate using the resin sheet.

Therefore, for example, a light diffusing plate, an anti-glare layer, an antireflection film, a protective layer, a protective plate provided on the viewing side polarizing plate, or a compensating retardation plate provided between the liquid crystal cell and the viewing side polarizing plate may be used. Various optical components can be appropriately combined with the resin sheet.

[0058] In addition, an electorescent luminescent display device generally has a luminous body in which a transparent electrode, an organic luminescent layer including a luminous body (organic electroluminescent luminescent body), and a metal electrode are sequentially laminated on a transparent substrate. Is configured. The electorescence luminescent display device of the present invention can be configured in the same manner as the conventional one, except that the transparent substrate provided with the resin sheet is used as the transparent substrate.

Example

Hereinafter, the present invention will be described with reference to examples, but the present invention is not limited to these examples.

(Example 1)

35.9 parts (parts by weight, the same applies hereinafter) of 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate represented by the following chemical formula (3) and dicyclopenta represented by the following chemical formula (4) Gen-type epoxy resin (trade name "EXA-7230" (epoxy equivalent: 259), manufactured by Dainippon Ink and Chemicals, Inc.) 10. 1 part, methylnadic anhydride as a curing agent 52.9 parts, curing accelerator Represented by the following chemical formula (5): , o-Jetylphosphodithioate 1. 1 part was stirred and mixed to prepare an epoxy resin solution.

[0061] [Formula 3]

[Formula 4]

[Formula 5]

(C ₄ H ₉ ) ₄ P + (C ₂ H ₅ 0) ₂ R (5)

S

Next, a glass fiber cloth (trade name “NEA2116F S136”, manufactured by Nitto Boseki Co., Ltd., refractive index: 1.513, thickness: 90 m) is impregnated with the above-mentioned epoxy resin liquid, and then under reduced pressure ( (200 Pa) for 60 minutes.

Next, a toluene solution of the urethane Atari rate 17 weight ^_0/0 represented by the following chemical formula (6), cast coated on a stainless steel endless belt from a die at a speed 0. 3mz fraction, to evaporate the toluene and air dried After that, a 2 m-thick hard coat layer was formed by curing using a UV curing apparatus. Subsequently, a glass fiber cloth impregnated with the epoxy resin solution was attached thereon, and cured using a heating device. Thus, a laminate having a thickness of 100 m in which the hard coat layer and the cured resin layer were laminated was obtained. The refractive index of the portion of the resin cured layer other than the glass fiber cloth was measured to be 1.522, and the difference in refractive index between the glass fiber cloth and the portion other than the glass fiber cloth was 0.009. Met. [0063]

(6)

Next, 91 parts of oxetane resin (trade name “Aronoxetane OXT-221” manufactured by Toagosei Co., Ltd.) was used, and 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexane represented by the chemical formula (3) was used. Carboxylate 4.8 parts, optical thione initiator (trade name “Takaji Adeka Obtomer SP-170J manufactured by Asahi Den-Daisha Co., Ltd.”) 4. Mix uniformly 3 parts to obtain a resin solution for forming an overcoat layer. Prepared.

Subsequently, the laminate of the hard coat layer and the resin cured layer was peeled off from the endless belt, and left on a glass plate at 200 ° C. for 1 hour in an atmosphere having an oxygen concentration of 0.1% by purging with nitrogen. Then, after-curing was performed. Next, the resin solution for forming the overcoat layer was coated by casting coating with a single-plate die coater (manufactured by Chugai Furnace Co., Ltd.) so that the cured resin layer had a thickness of 30 m. The resin sheet was sandwiched between glass plates and irradiated with ultraviolet rays to harden the resin, thereby producing a resin sheet having an overcoat layer formed on the surface layer. Incidentally, the irradiation amount of the ultraviolet light was set to 100 MjZcm ² .

(Example 2)

A resin sheet was prepared in the same manner as in Example 1 except that among the resins for forming the overcoat layer, another oxetane resin (trade name “Aronoxetane OXT-121” manufactured by Toagosei Co., Ltd.) was used as the oxetane resin. Produced.

(Comparative Example 1)

A resin sheet was prepared in the same manner as in Example 1, except that the overcoat layer was removed.

(Comparative Example 2)

Example 1 was repeated except that a glass cloth (manufactured by Nitto Bo) with a refractive index of 1.558 and a thickness of 100 m was used as the glass fiber fabric, and a resin sheet without an overcoat layer was used. A resin sheet was produced in the same manner as described above. In the cured resin layer, the difference in the refractive index between the glass fiber cloth and the other parts was 0.036.

[0069] (Evaluation test)

With respect to the resin sheets of Examples and Comparative Examples, the respective items of linear expansion coefficient, flexibility, light transmittance, and surface roughness were measured. In addition, each measuring method was as follows.

[0070] Linear expansion coefficient (Z ° C) •••• TMA / SS15QC (manufactured by Seiko Instruments Inc.) was used to measure and calculate the TMA value at 25 ° C and 160 ° C.

Flexibility—A resin sheet was wrapped around an iron pillar having a diameter of 35 mm, and whether or not cracking occurred was visually observed.

[0072]… High-speed spectrophotometer (CMS-500, manufactured by Murakami Color Research Laboratory, using a halogen lamp)

) Was used to measure the transmittance at λ = 550 nm.

[0073] Straightness: Using a stylus type surface roughness measuring device (P-11, manufactured by Tencor), surface roughness under the conditions of a long wavelength cutoff of 800 m, a short wavelength cutoff of 250 m, and an evaluation length of 10 mm. (The difference between the maximum and minimum values) was measured.

Haze value— “The haze value of each resin sheet was measured using a haze meter (HM-150, manufactured by Murakami Color Co., Ltd.).

[0075] The results are shown in Table 1.

[Table 1]

[0077] As shown in Table 1, the resin sheet of Example 2 had a low linear expansion coefficient, was excellent in light transmittance, and had good surface smoothness. Also, it was excellent in flexibility. In contrast, the resin sheet of Comparative Example 1 was inferior in the coefficient of linear expansion, the light transmittance, and the flexibility as well as the force surface smoothness as in the example. In the resin sheet of Comparative Example 2, the coefficient of linear expansion, the light transmittance, and the flexibility were as good as those of the example, but the surface smoothness was poor, and the force was cloudy with a haze value of 75%. Furthermore, when a transmissive liquid crystal display device was assembled using the resin sheets of the Examples and Comparative Examples, misalignment and misalignment were found in the formation of the alignment film, the patterning of the color filter layer, and the formation of the liquid crystal cell. It did not cause problems such as breakage.

However, in the transmission type liquid crystal display device using the resin sheet of Comparative Example 1, a decrease in image quality, which is considered to be caused by the surface smoothness of the resin sheet, was observed.

In addition, the transmissive liquid crystal display device using the resin sheet of Comparative Example 2 had a screen that was opaque and could not sufficiently function as a display device.

Claims

The scope of the claims

[I] A resin cured layer containing a glass fiber cloth-like body, and an overcoat layer laminated on the surface of the resin cured layer so that the surface roughness Rt is 200 nm or less. A resin sheet characterized by being configured to be 10% or less.

2. The resin sheet according to claim 1, wherein the difference in refractive index between the resin constituting the resin cured layer and the glass fiber cloth is 0.01 or less.

[3] The resin according to claim 1 or 2, wherein the difference in refractive index between the resin constituting the resin cured layer and the resin constituting the overcoat layer is 0.03 or less.榭 Fat sheet.

4. The resin sheet according to claim 1, wherein the overcoat layer is formed of an ultraviolet curable resin.

5. The resin sheet according to claim 4, wherein the ultraviolet curable resin is a mixture of an oxetane resin and an epoxy resin.

[6] The resin sheet according to any one of [15] to [15], wherein the resin constituting the cured resin layer is an epoxy resin.

[7] 25 160榭脂sheet according to claim 1 one 6 linear expansion coefficient in ° C is equal to or less than 3. OX 10- ⁵ Z ° C.

[8] The resin sheet according to any one of [17] to [17], wherein the light transmittance is 88% or more.

[9] The resin sheet according to any one of [18] to [18], further comprising a gas noria layer laminated thereon.

[10] The resin sheet according to any one of [19] to [19], further comprising a hard coat layer laminated thereon.

[II] A liquid crystal cell substrate comprising the resin sheet according to any one of claims 11 to 10.

[12] A liquid crystal display device comprising the liquid crystal cell substrate according to claim 11.

[13] A substrate for an electroluminescent display device, comprising the resin sheet according to any one of [11] to [10].

[14] A substrate comprising the substrate for an electroluminescent display device according to claim 13 Elect-emission luminescence display device.

[15] A substrate for a solar cell, comprising the resin sheet according to any one of claims 11 to 10.