JPH1076596A - Laminated film and production thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To remarkably improve the interlayer adhesion and gas barrier properties by providing a film layer of silicone magnesium composite oxide on at least one side of a plastic film and keeping a relationship of the specific gravity of the film layer and the content of magnesium oxide in the film layer within a specific range. SOLUTION: The relationship of the specific gravity of a film layer of silicone magnesium composite oxide and the content of magnesium oxide in the film layer is 2.1<=D-0.029 W<=2.65 (where, D is the specific gravity and W the content). A polyarylate film is used as a plastic film 11, and MgO2 and SiO2 particles are used as metallizing material. These materials are each heated in a time-sharing fashion by a single electron beam gun using a electron beam metallizing method without being mixed and a film layer 12 of silicone magnesium composite oxide is preapared. Ultraviolet rays are applied to this film so prepared to cure a holding layer to thereby obtain a 20μm thick curable resin cured layer 13.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a laminated film for forming a transparent electrode on the surface thereof and a method for producing the same, and more particularly to a laminated film used for producing a liquid crystal cell and a liquid crystal display panel and a method for producing the same.

[0002]

2. Description of the Related Art A glass substrate is currently used as a substrate for a liquid crystal display panel, and is suitable for use as a display portion of a portable information terminal, a palmtop computer or the like. However, glass substrates have drawbacks such as being heavy, easily broken, unable to be made thin, and not bent. Therefore, it is often inconvenient to use a glass substrate for a liquid crystal display panel for use in which it is required to be lightweight, thin, and not easily damaged when inputting with a pen. Therefore, recently, a liquid crystal display panel using a plastic film substrate instead of the glass substrate is being put to practical use.

When a plastic film substrate is used as a liquid crystal display panel substrate, the following characteristics are required. 1. Be transparent in the visible light range. 2. The surface is smooth and hard. 3. Have optical isotropy. 4. It must have a heat resistance of 100°C or higher that can withstand the manufacturing process of a liquid crystal display panel. 5. Withstand chemicals used in the manufacturing process of liquid crystal display panels. 6. Do not delaminate against stress applied during the manufacturing process of liquid crystal display panels. 7. Sufficient gas barrier property. 8. It has excellent moisture resistance. 9. Must have liquid crystal resistance.

In order to satisfy such required characteristics, an anchor coat layer is formed on at least one side of a plastic film, and a layer composed of an ethylene-vinyl alcohol copolymer or polyvinyl alcohol is formed on the anchor coat layer, and the curability is further improved. Laminated film in which a cured resin layer is laminated (JP-A-61-86252); A laminated film in which a layer made of vinylidene chloride resin is formed on at least one surface of a plastic film, and a curable resin cured layer is further laminated (special JP-A-60-134215); SiO _{x formed} by vapor deposition on at least one side of a plastic film.
(However, 1<x<2) A laminated film in which a thin film layer and a curable resin cured product layer are laminated (JP-A-6-175143) and the like are known.

[0005]

However, the above-mentioned JP-A-61-86252 and JP-A-60-1342 have been proposed.
The laminated film described in Japanese Patent No. 15 is obtained by coating a plastic film with an ethylene-vinyl alcohol copolymer (having few functional groups involved in adhesiveness), a curable resin cured product, or the like, and adhering each layer to each other. The power is insufficient. Therefore, due to the stress applied during the manufacturing process of the liquid crystal display panel, delamination of these laminated films may occur, resulting in a low yield of manufacturing the liquid crystal display panel.

Further, those using a layer comprising an ethylene-vinyl alcohol copolymer or polyvinyl alcohol are not sufficiently satisfactory in gas barrier properties and moisture resistance. A liquid crystal display panel using such a laminated sheet cannot be used because the liquid crystal is deteriorated and driving power is increased, or black bubbles are generated in the liquid crystal display portion after long-term use.

The vinylidene chloride resin as described in JP-A-60-134215 is not only insufficient in gas barrier property and moistureproof property, but is also deteriorated by ultraviolet rays and colored yellow, so that it is applied to a liquid crystal display panel. Not suitable for use.

The one using a SiO _x (1<x<2) thin film as described in JP-A-6-175143 is not suitable for a liquid crystal display panel because of its coloring.
Furthermore, SiO _x (where 1<
The x<2) thin film does not have sufficient adhesion to the underlying plastic film, and this laminated film may cause delamination, resulting in a low yield of liquid crystal display panel production.

Under such circumstances, the present invention provides a laminated film having a significantly improved interlayer adhesion and gas barrier property (especially a laminated film for forming a transparent electrode, a laminated film for producing a liquid crystal cell or a liquid crystal display panel). Film) and a method for producing the same.

[0010]

[In the formula, D represents the specific gravity of the silicon zirconium composite oxide thin film layer, and W represents the zirconium oxide content (% by weight) in the silicon zirconium composite oxide thin film layer. ]

Further, according to the present invention, the content of zirconium oxide in the silicon zirconium composite oxide thin film layer is 25-9.
0% by weight of the above laminated film; the thickness of the silicon zirconium composite oxide thin film layer is 30 to 8
The above-mentioned laminated film having a thickness of 000Å; the above-mentioned laminated film having a retardation value of the plastic film of 30 nm or less or 5000 nm or more.

Furthermore, the present invention is characterized in that the curable resin cured product layer is laminated on the silicon-zirconium composite oxide thin film layer, and the interlayer adhesion of each layer is 300 g/inch or more. The above-mentioned laminated film characterized in that the oxygen permeability is 3 cc/m ² ·atm ·day
The following relates to the above-mentioned laminated film, which is characterized in that:

The present invention also provides a step of forming a silicon zirconium composite oxide thin film layer by an electron beam evaporation method in a water vapor partial pressure of 5×10 ^-5 Torr or less, or an electron beam irradiation with an electron beam. The present invention relates to the method for producing a laminated film described above, which comprises a step of forming a film by a vapor deposition method.

Further, the present invention is an electrode substrate comprising a transparent electrode on the surface of the above-mentioned laminated film;
A liquid crystal cell comprising the above laminated film; a liquid crystal display panel comprising the above laminated film.

The present invention will be described in detail below.

As the plastic film, for example,
Polycarbonate film, polystyrene film, polyester film, poly-4-methylpentene film, polyphenylene oxide film, polyamideimide film, polyethersulfone film, polyarylate film, amorphous polyolefin, norbornene-based polymer film, polyvinyl alcohol film, ethylene-vinyl alcohol Copolymer film, cellulose film (cellulose triacetate,
Cellulose diacetate, cellulose acetate butylate, etc.) and the like. Preferred are a polycarbonate film, a polyamide-imide film, a polyether sulfone film, a polyarylate film, and a norbornene-based polymer film. Further, a uniaxially stretched film such as a polyethylene terephthalate film or a polyethylene naphthalate film can also be used. Further, the plastic film may be a single layer or multiple layers.

The retardation value of the plastic film is preferably 30 nm or less or 5000 nm.
Or more, more preferably 0.2 to 20 nm or 8000
~40,000 nm. Retardation value is 30n
When the thickness is m or less, when used in a liquid crystal display panel, interference fringes of visible light do not occur and the display quality is good. Further, when it is 5000 nm or more, the interval of the interference fringes is sufficiently widened in the visible light region, so that the interference fringes do not appear in the liquid crystal display panel and the display quality is good.

The retardation value means the anisotropy (ΔN=Nx-Ny) [N of biaxial refractive index on the film at right angles to each other.
x: refractive index in the axial direction having the maximum refractive index, Ny: refractive index perpendicular to the Nx axis] and the film thickness d (ΔN×d).

The retardation value is measured using an ellipsometer (AEP-100B, manufactured by Shimadzu Corporation). The retardation value can be adjusted by the rate at which the plastic film is formed, the temperature, and the like. In the case of a stretched film, it can also be adjusted by the stretch ratio.

The visible light transmittance of the plastic film is preferably 75% or more, more preferably 80% or more from the viewpoint of visibility of the liquid crystal display panel. The visible light transmittance is measured using an integrating sphere type light transmittance measuring device (NDH-1001DP, manufactured by Nippon Denshoku Industries Co., Ltd.) based on JIS K 7105. The visible light transmittance can be adjusted by changing the heat treatment temperature when forming the plastic film.

From the viewpoint of mechanical strength, the plastic film has a tensile strength of 200 kgf/cm ² or more and a tensile elongation of 5%.
The above is preferable.

The plastic film has a sufficient mechanical strength and is preferably thin, so that the thickness thereof is 50.
˜500 μm is preferred. The thickness is Millitron 1254D
(Manufactured by Mahr). The thickness can be adjusted by changing the discharge rate from the extruder or the film feed rate during the plastic film formation.

The plastic film is generally obtained by forming a film by a casting method (coating method), but other molding methods such as an extrusion method can also be used. In addition, it is preferable to set the film forming conditions so that the retardation value, the visible light transmittance, and the like satisfy the above ranges.

The silicon zirconium composite oxide thin film layer used in the present invention is required to satisfy the following expression (a). 2.1≦D−0.029W≦2.65 (a) [wherein, D is the specific gravity of the silicon zirconium composite oxide thin film layer, and W is the zirconium oxide content rate (weight) in the silicon zirconium composite oxide thin film layer. %) is shown. ] 2.15≦D−0.029W≦2.65 is preferable.

If D-0.029W<2.1, gas barrier properties and interlayer adhesion will be insufficient. Further, as will be described later, D-0.029W>2.65 does not occur.

By the way, bulk silicon-zirconium composite oxide glass (calcia-silica glass; hereinafter also referred to as bulk glass) prepared by a usual melt-quenching method has an ideal three-dimensional network structure and high specific gravity. Have. This is because the melt-quenching method forms complex oxides at a much slower rate than thin-film forming methods such as vacuum deposition method and sputtering method (however, complex oxides formed by melt-quenching method). The object becomes a bulk and does not become a thin film). Such bulk glass has a high gas barrier property because of its ideal three-dimensional network structure. In addition, a large number of reactive groups such as silanol groups are present on the surface of the bulk glass, which also affects the adhesion. Therefore,
It is preferable that the physical properties of the silicon zirconium composite oxide thin film layer be close to those of bulk glass.

In the bulk silicon zirconium composite oxide glass prepared by the melt quenching method,
The relationship between D and W is D-0.029W=2.65.
It is represented by "Glass Handbook; 1987.
Year; Sakuhana, Sakaino, Takahashi, Asakura Shoten”. Further, in the silicon-zirconium composite oxide, the maximum value of D-0.029W is 2.65 regardless of how the composite oxide is produced and in what state. Has been done.

That is, the silicon zirconium composite oxide thin film layer satisfying the formula (a) imparts gas barrier properties to the laminated film of the present invention, and has an adhesion force between layers (as described later,
The adhesion between the plastic film and the thin film layer and the adhesion between the thin film layer and the cured product layer) can be improved. Further, moisture resistance, chemical resistance, heat resistance, liquid crystal resistance and the like can be imparted.

Here, the specific gravity as used in the present invention means the ratio of the mass of a substance occupying a certain volume at a certain temperature to the mass of a standard substance (water at 4° C.) having the same volume.

To measure the specific gravity, the mass and volume of an object are usually measured and the ratio to the mass of water of the same volume at 4° C. is obtained.
It is difficult to measure the volume of the thin film of the present invention. Therefore, in the present invention, the specific gravity (D) of the silicon zirconium composite oxide thin film layer is determined from the thin film alone by dissolving only the plastic film from the laminated film of the plastic film/silicon zirconium composite oxide thin film layer with the solvent. JI
It is measured by the float-sink method of SK 7112.
That is, the sample is immersed in a solution of known specific gravity (mixed solution of carbon tetrachloride and methylene iodide), and the specific gravity of the thin film is measured from the floating state.

The specific gravity can be adjusted by the film forming conditions and the like as described later. For example, when a silicon zirconium composite oxide thin film layer is formed by an electron beam evaporation method, the partial pressure of water vapor is adjusted to 5×10 ⁻⁵ Torr or less, or by adjusting the film formation while irradiating an ion beam. be able to.

The content (W) of zirconium oxide in the silicon zirconium composite oxide thin film layer (100% by weight) is preferably 25 to 90% by weight, more preferably 30 to 80% by weight. When the content of zirconium oxide is less than 25% by weight, the gas barrier property of the laminated film of the present invention tends to be insufficient,
If it exceeds 90% by weight, flexibility tends to be insufficient.

The content of the zirconium oxide is obtained by determining the atomic ratio of silicon (Si) and zirconium (Zr) in the thin film with an ICP emission spectrometer (ICPS-2000; manufactured by Shimadzu Corporation). Is a value obtained by calculating the content ratio of complete zirconium oxide, assuming that and are complete oxides (SiO ₂ , ZrO ₂ ). The zirconium oxide content can be adjusted, for example, by changing the heating time ratio of the electron beam when forming a film in the electron beam evaporation method.

The method for forming the above-mentioned silicon zirconium composite oxide thin film layer is, for example, a PVD method (physical vapor deposition method) such as a vacuum vapor deposition method, a sputtering method, an ion plating method, or a CVD method (chemical vapor deposition method). ) And the like. From the viewpoint of productivity, the vacuum deposition method is preferable,
The electron beam evaporation method is preferable for improving the adhesion with the underlying plastic film.

Zr, ZrO, and ZrO are vapor deposition materials for forming the silicon zirconium composite oxide thin film layer.
₂ , Si, SiO, SiO _{2 and the} like.

The case of forming a film by the electron beam evaporation method will be described below. As a vapor deposition material for forming a film by an electron beam vapor deposition method, ZrO ₂ and SiO ₂ or Zr is preferable.
And SiO _{2 and the} like are used.

When the film is formed by the electron beam evaporation method, the pressure is preferably 3×10 ^-4 Torr or less. The water vapor partial pressure in this pressure is preferably 5×10 ⁻⁵ Torr or less, more preferably 4×10 ⁻⁵ Tor.
It is rr or less. When the water vapor partial pressure exceeds 5×10 ⁻⁵ Torr, the specific gravity of the composite oxide thin film is low, the gas barrier property is not sufficient, and the adhesive force with the plastic film tends to be insufficient. Also, the pressure is 3×1
The same can be said when exceeding 0 ⁻⁴ Torr.

When the partial pressure of water vapor increases, the vapor deposition particles collide with water molecules, and the thin film contains water.
As a result, the three-dimensional network structure of the thin film becomes non-uniform and the specific gravity decreases. Due to this non-uniform structure, the gas barrier property is not good. Further, the collision between the vapor deposition particles and water molecules causes the energy of the vapor deposition particles to be lost, and the bond (adhesion) with the surface of the plastic film is weakened.

The pressure is measured by using an ionization vacuum gauge (MIG-821, manufactured by Nichiden Anelva Co., Ltd.). The water vapor partial pressure is measured by using a residual gas analyzer (AQA-100R, manufactured by Nichiden Anelva Co., Ltd.). The pressure,
The water vapor partial pressure can be adjusted by changing the vacuum evacuation time, using a cryopanel that can preferentially evacuate the water vapor, or the like.

The specific gravity of the silicon zirconium composite oxide thin film layer can also be increased by forming a film by the electron beam evaporation method while irradiating with an ion beam, and the plastic film and the silicon zirconium composite oxide thin film layer can be adhered closely. You can improve your strength.

Preferable examples of the ion species of the ion beam include noble gases such as argon, helium and krypton, and reactive gases such as oxygen.

The ion beam current density is 0.02 to 5.0.
mA/cm ² , ion beam energy is 30 to 300
A range of 0V is preferred. Ion beam current density is 0.0
If it is less than ² mA/cm ² , the effect of ion beam irradiation (the effect of increasing the energy of vapor-deposited particles) tends to be difficult to be exhibited, and if it exceeds 5.0 mA/cm ² , the irradiation amount is too large and the underlying plastic film is not heated. It tends to deform. Further, if the ion beam energy is less than 30V, the effect of ion beam irradiation tends to be difficult to be exhibited, and if it exceeds 3000V, the energy is too high and the plastic film tends to be thermally deformed.

A film is formed under the above conditions (when forming a film by an electron beam evaporation method, the partial pressure of water vapor is 5×10 ⁻⁵ To).
If it is less than or equal to rr, or if a film is formed while irradiating with an ion beam), the energy of vapor deposition particles is very high and a mixed layer is formed at the interface between the plastic film and the silicon zirconium complex oxide thin film layer (plastic film). And a thin film layer causes a physical bond). For this reason, the adhesion between the plastic film and the silicon-zirconium composite oxide thin film layer becomes very strong, showing a value of 300 g/inch or more.

The temperature of the plastic film may be raised (heated) or lowered (cooled).

The thickness of the silicon zirconium composite oxide thin film layer is not particularly limited, but is preferably 3
It is 0-8000Å, more preferably 70-5000Å. If the thickness is less than 30Å, the gas barrier property of the laminated film of the present invention tends to be insufficient, and 8000
If it exceeds Å, flexibility tends to be insufficient.

The thickness of the thin film layer is determined by measuring the atomic ratio of silicon and zirconium in the thin film using an ICP emission spectrometer (ICPS-200
0; manufactured by Shimadzu Corporation, and assumed that silicon and zirconium are perfect oxides (SiO ₂ , ZrO ₂ ), and calculated using the bulk specific gravity of these (SiO ₂ and ZrO ₂ ). Is. The thickness can be adjusted, for example, by changing the input power of the electron beam or the feeding speed of the plastic film when the film is formed by the electron beam evaporation method.

The silicon zirconium composite oxide thin film layer may contain a small amount (up to about 5% by weight based on all components) of other components as long as the characteristics are not impaired. Further, the crystallinity of the silicon zirconium composite oxide thin film is preferably in an amorphous state from the viewpoint of optical isotropy as long as its characteristics are not impaired.

In the laminated film of the present invention, a curable resin cured product layer can be further laminated on the silicon zirconium composite oxide thin film layer. By providing the curable resin cured product layer, when the laminated film of the present invention is used in a liquid crystal panel, the silicon zirconium composite oxide thin film layer is further less likely to be deteriorated by the liquid crystal.

The curable resin cured product layer is, for example, a thermosetting resin (phenoxy ether type crosslinkable resin, epoxy resin, acrylic resin, acrylic silicone resin, silicone resin, polyamideimide resin, melamine resin, phenol). Cured resin layers made of resin, urethane resin, rubber resin, etc., UV curable resin (UV curable acrylic resin, polyamideimide resin, phosphazene resin, etc.), electron beam curable resin, etc. ..

The curable resin cured product layer preferably has a thickness of 0.5 to 50 μm because it is easy to form a film by a wet process as described below and is preferably thin. The thickness of the cured product layer is measured using Millitron 1254D (manufactured by Mahr). The thickness can be adjusted by changing the discharge amount of the curable resin composition from the die or the film feeding speed.

It is preferable that this curable resin cured product layer also has optical isotropy.

When the curable resin cured product layer is formed, the surface roughness of the formed curable resin cured product layer (surface roughness on the surface not in contact with the silicon zirconium composite oxide thin film layer) is preferably Rmax is 0.5 μm or less, Ra is 0.01 μm or less, more preferably Rmax is 0.2 μm or less, Ra is 0.007 μm or less, and further preferably Rmax is 0.1 μm or less and Ra is 0.005 μm.
It is desirable to be less than or equal to m. When the surface roughness is within the above range, the display quality is good when the laminated film of the present invention is used in a liquid crystal display panel.

The outermost layer in the laminated film of the present invention preferably satisfies the above surface roughness, and when the cured product layer is not formed, the thin film layer preferably satisfies the above value.

Rmax represents the maximum height described in JIS B 0601, and Ra represents the center line average roughness described in JIS B 0601. The surface roughness is based on a stylus type surface roughness measuring device (Surfcom 304B, Co., Ltd.) according to JIS B 0651.
It is measured by using (Tokyo Seimitsu Co., Ltd.).

As a method of reducing the surface roughness of the curable resin cured product layer in this way, for example, the following first method is used.
Alternatively, the second method can be mentioned.

As a first method, first, a plastic film/silicon zirconium composite oxide thin film layer,
A heat-curable resin composition, a UV-curable resin composition or an electron beam-curable resin composition is supplied to the gap between the two using a smoothing template material (F) by a die so that the resin composition is To be sandwiched in layers. In this case, the plastic film/silicon zirconium composite oxide thin film layer is supplied to one film-forming roll, and the smoothing template material (F) is supplied to the other film-forming roll. The gap between the rolls is adjusted to a predetermined value.
Then, the sandwiching layer (curable resin composition layer) is cured by heating, UV irradiation or electron beam irradiation to obtain a plastic film/silicon zirconium composite oxide thin film layer/curable resin cured product layer/smoothing template material. A laminated film composed of (F) is obtained. Furthermore, at an appropriate stage after that,
The smoothing template material (F) is peeled off from the laminated film.

The smoothing template material (F) described above is used to reduce the surface roughness of the cured product layer.
A biaxially oriented polyester film such as a biaxially oriented polyethylene terephthalate film or a biaxially oriented polyethylene naphthalate film, or a biaxially oriented polypropylene film is used.

The surface roughness of the smoothing template material (F) is preferably 0.15 μm or less in Rmax and 0.008 in Ra.
μm or less, more preferably 0.05 μm or less in Rmax,
A material having Ra of 0.005 μm or less, more preferably Rmax of 0.01 μm or less and Ra of 0.002 μm or less is used. The surface roughness is also measured in the same manner as above.

In the second method, one of the plastic film/silicon zirconium composite oxide thin film layer or the smoothing template material (F) is applied to either a heat-curable resin composition, an ultraviolet-curable resin composition or an electron beam-curable resin composition. The resin composition is cast (coated), and the smoothing template material (F) or the plastic film/silicon zirconium composite oxide thin film layer is coated on the cast layer, while sandwiching the sandwiching layer ( A curable resin composition layer) is formed by curing the sandwiching layer by heating, UV irradiation or electron beam irradiation while controlling the thickness of the curable resin composition layer). Further, the smoothing template material (F) is peeled off from the laminated film at an appropriate stage thereafter.

When the silicon zirconium composite oxide thin film layer satisfies the formula (a), the adhesion between the silicon zirconium composite oxide thin film layer and the curable resin cured product layer is 3
It is more than 00g/inch and strong enough. Especially D-0.
When 029W=2.65, the specific gravity of the silicon zirconium composite oxide thin film layer is the same as that of bulk glass, and the interlayer adhesion between the thin film layer and the cured product layer is 10 at this time.
It will be extremely strong at over 00 g/inch.

When the thin film layer satisfies the formula (a), a large number of reactive groups such as silanol groups are present on the surface of the silicon zirconium composite oxide thin film layer, like the bulk glass prepared by the usual melt quenching method. Since the surface-reactive group and the curable resin cured product are strongly chemically bonded, the adhesive force between the curable resin cured product layer and the silicon zirconium composite oxide thin film layer becomes extremely strong.

However, even in thin films having the same zirconium oxide content in the composite oxide thin film, the number of surface-reactive groups decreases as the specific gravity of the silicon zirconium composite oxide thin film decreases. The physical implication of reducing the specific gravity of the thin film is that the number of silicon, zirconium and oxygen atoms present in a unit volume is small, and the number of silicon, zirconium and oxygen atoms is also small on the thin film surface. Therefore, the number of reactive groups (Si-O-H, Zr-O-H) terminating the three-dimensional network structure of silicon, zirconium and oxygen is reduced on the surface. That is, even if the content of zirconium oxide in the composite oxide thin film is the same, as the specific gravity decreases, the adhesion between the thin film layer and the curable resin cured product layer decreases.

In the whole laminated film of the present invention obtained as described above, its retardation value is preferably 30 nm or less or 5000 nm or more, more preferably 20 nm or less or 8000 nm or more, and the visible light transmittance is preferably. 70% or more, more preferably 7
It is 5% or more. The retardation value and visible light transmittance can be measured in the same manner as above using the entire laminated film.

Retardation value of the whole laminated film,
The visible light transmittance can be adjusted within the above range by using each layer (plastic film, thin film layer, cured product layer) having a value within the above range.

The oxygen permeability of the laminated film is preferably 3 cc/m ² ·atm ·day or less, more preferably 1 cc/m.
It is less than ²・atm・day. Oxygen permeability is 3cc/m ² ·at
If it exceeds m·day, the gas barrier property of the laminated film tends to be insufficient.

The oxygen permeability was measured using an oxygen permeability measuring device (OX-TRAN100, manufactured by Modern Controls Co., Ltd.), and
It is measured at 5° C. and 80% RH. The oxygen permeability can be adjusted by satisfying the above formula (a).

The interlayer adhesion of each layer of the laminated film is
Preferably 300 g/inch or more, more preferably 5
It is more than 00 g/inch. If the interlayer adhesion is less than 300 g/inch, delamination tends to occur during the manufacturing process of the liquid crystal display panel.

Among the interlayer adhesive forces of each layer of the laminated film of the present invention, the method of measuring the adhesive force between the layers having the weakest adhesive force will be described below. First, on the outermost layer of the laminated film (silicon zirconium composite oxide thin film layer, or the layer having a smoothing template material, the exposed curable resin cured material layer after peeling and removing this) A thermosetting adhesive obtained by adding 10 parts of an isocyanate curing agent (A-3, manufactured by Takeda Pharmaceutical Co., Ltd.) to 100 parts of an adhesive (A-310, manufactured by Takeda Pharmaceutical Co., Ltd.) was applied to a thickness of 3 μm. To do. A 100 μm-thick biaxially stretched polyethylene terephthalate film (E5100 manufactured by Toyobo Co., Ltd.) subjected to corona treatment is laminated on the adhesive layer, and the adhesive is cured at 45° C. for 4 days. In the laminated body composed of the biaxially stretched polyethylene terephthalate film/thermosetting adhesive layer/laminated film thus produced,
The biaxially stretched polyethylene terephthalate film and the portion of the laminated film are grabbed, and the peel strength is measured by the 90° T-type peeling method based on JIS K6854. According to the above measuring method, peeling occurs from the layer having the weakest adhesion.

The interlayer adhesion can be adjusted by satisfying the above expression (a).

The structure of the laminated film of the present invention includes, for example, a plastic film (11)/silicon zirconium composite oxide thin film layer (12); (11)/(12).
/Curable resin cured product layer (13); (12)/(11)/
(12); (13)/(12)/(11)/(12)/
(13); (12)/(13)/(12)/(11)/
Examples include (12)/(13)/(12). Preferably (13)/(12)/(11)/(12)/(1
3).

Using the laminated film of the present invention thus obtained, the outermost layer (silicon zirconium composite oxide thin film layer or curable resin cured product layer) is vacuum-deposited, sputtered, or ion-plated. A transparent electrode can be formed by a method such as a method to obtain an electrode substrate.

Suitable examples of the transparent electrode include indium tin composite oxide, indium zinc composite oxide, indium cadmium composite oxide, and the like, but other conductive metal oxides can also be used.

The thickness of the transparent electrode is preferably 100-3.
It is 000Å. If the thickness is less than 100Å, the conductivity tends to be insufficient, and if it exceeds 3000Å, the transparency tends to be impaired.

For the alignment of liquid crystal molecules, if necessary,
An alignment film can be formed on the formed transparent electrode. Examples of the alignment film include polyimide resin and polyamide-imide resin.

Further, the two electrode substrates manufactured in this way are arranged with a predetermined gap in a state where their transparent electrode sides face each other, liquid crystal is sealed in the gap, and the periphery thereof is sealed with a sealing material. When sealed, a liquid crystal cell is obtained. Examples of the sealing material include epoxy resin and the like.

A liquid crystal display panel is manufactured by laminating a polarizing plate on one surface of the liquid crystal cell and a polarizing plate on the other surface of the liquid crystal cell via a retardation plate. The retardation plate may be omitted, or a compensating liquid crystal cell may be used instead of the retardation plate. Further, the electrode substrate may be an integrated type substrate integrated with a polarizing plate or a retardation plate.

FIG. 1 is a sectional view schematically showing an example of the laminated film of the present invention. FIG. 2 is a sectional view schematically showing an example of an electrode substrate in which a transparent electrode is attached to a laminated film. FIG. 3 is a sectional view schematically showing an example of a liquid crystal cell manufactured using an electrode substrate. FIG. 4 is a cross-sectional view schematically showing an example of a liquid crystal display panel manufactured using a liquid crystal cell.

[0078]

The present invention will be described in more detail with reference to examples, but the present invention is not limited thereto. Hereinafter, “part” means part by weight.

Example 1 (1-1 to 1-3) A polyarylate film was used as the plastic film (11). This plastic film was formed by a casting method from a 20% by weight polyarylate solution using methylene chloride as a solvent. The thickness was 75 μm, the retardation value was 5 nm, and the visible light transmittance was 91%.

On this plastic film (11),
The silicon zirconium composite oxide thin film layer (12) was formed by an electron beam evaporation method. At this time, as a vapor deposition material, 3
˜5 mm size particulate ZrO ₂ (purity 99.5
%) and SiO ₂ (purity 99.9%) were used. Without mixing these vapor deposition materials, the water-cooled copper hearth was partitioned into two water-cooled copper plates, and one electron gun was used as a heating source to heat each of ZrO ₂ and SiO _{2 in} a time-division manner. .. The emission current of the electron gun at that time was 2.5 A, and the heating time ratio was changed as shown in Table 1 in order to change the content of zirconium oxide in the thin film. Also, oxygen gas was supplied at 20 sccm, the center roll temperature was -15°C,
The film feed speed was 120 m/min. Furthermore, an oil diffusion pump and a cryopanel were used as the vacuum exhaust device. As a result, the pressure during vapor deposition is 2.5×10 ⁻⁴ Tor.
The water vapor partial pressure was 3×10 ⁻⁵ Torr. Under the above film forming conditions, a silicon zirconium composite oxide thin film layer (12) having a film thickness of 200 Å was formed. Further, the specific gravity of the thin film was measured, and the results are shown in Table 1.

On one of the pair of film forming rolls arranged in parallel at a slight interval, the laminated film (the silicon zirconium composite oxide thin film layer (12) was laminated on the laminated film (plastic film (11) obtained above). The film-forming roll is fed while the other film-forming roll is made to have a smoothing template (F) with a thickness of 50 μm and a surface roughness Ra=
A biaxially stretched polyethylene terephthalate film (A4100, manufactured by Toyobo Co., Ltd.) having 0.004 μm and Rmax=0.05 μm and not subjected to corona treatment was fed while the smooth surface of the film was supplied. A UV-curable resin composition obtained by adding 4 parts of benzophenone to 100 parts of an epoxy acrylic resin was discharged from a die toward the gap between both film-forming rolls. The discharged ultraviolet curable resin composition was sandwiched between the surface of the plastic film (11) on which the silicon zirconium composite oxide thin film layer (12) was formed and the smooth surface of the smoothing template material (F). So, while running in this state, high pressure mercury lamp, 200w/cm,
Ultraviolet irradiation was performed under the conditions of one lamp, irradiation time of 10 seconds, and a distance of 200 mm between the mercury lamp and the smoothing template material (F). As a result, the sandwiching layer was cured to form a curable resin cured product layer (13) having a thickness of 20 μm.

The same operation as above is carried out on the other surface of the plastic film (11) to form a silicon zirconium composite oxide thin film layer (12) having a thickness of 200 Å and a curable resin cured product layer (13) having a thickness of 20 μm. Was formed. Thereby, the smoothing template material (F)/curable resin cured material layer (13)
/ Silicon zirconium compound oxide thin film layer (12) / Plastic film (11) / Silicon zirconium compound oxide thin film layer (12) / Curable resin cured product layer (13)
/A laminated film having a layer structure of the smoothing template material (F) was obtained. Next, the smoothing template material (F) is peeled and removed,
A laminated film (1) having a layer structure of (13)/(12)/(11)/(12)/(13) was obtained [see FIG. 1].

The surface roughness of the curable resin cured product layer (13) was Ra=0.005 μm or less and Rmax=0.
It was 1 μm or less. Any laminated film (1)
The retardation value is 5 nm and the visible light transmittance is 8
4% and the thickness was 115 μm. Laminated film (1)
The interlayer adhesion (peel strength) of was measured, and the results are shown in Table 1. All exhibited sufficiently strong peel strength, and the peel interface was the interface between the curable resin cured product layer (13) and the silicon zirconium composite oxide thin film layer (12). From these results, the laminated film (1) of the present invention had sufficiently strong interlayer adhesion. The oxygen permeability was measured in order to evaluate the gas barrier properties of the laminated film (1). The results, as shown in Table 1, showed extremely high gas barrier properties.

Then, one curable resin cured product layer (1
A transparent electrode (2) made of indium tin composite oxide having a thickness of 500Å is formed on 3) by a sputtering method, and an electrode substrate (5) [a laminated film (1) with a transparent electrode (2)] is formed. Obtained [see FIG. 2]. This transparent electrode (2)
Had a surface resistivity of 100Ω/□.

In the liquid crystal cell (6), after the alignment film is formed on the transparent electrode (2) surface of the electrode substrate (5), the two electrode substrates (5) are opposed to each other by the transparent electrodes (2). It was prepared by arranging the liquid crystal (3) in a predetermined state with a predetermined gap therebetween, sealing the liquid crystal (3) in the gap, and sealing the periphery with a sealing material (4) [see FIG. 3].

The liquid crystal display panel (7) has a polarizing plate (8) on one side and a polarizing plate (8) on the other side via a retardation plate (9).
It was produced by stacking (see FIG. 4). In the liquid crystal display panel manufactured in this manner, the interlayer adhesion of the laminated film (1) was sufficiently strong so that the laminated film (1) did not undergo delamination during the manufacturing process.

Comparative Example 1 (1-1 to 1-3) The same polyarylate film as in Example 1 was used as a plastic film (11), and a silicon zirconium composite oxide thin film layer (12) was formed thereon. At that time, a silicon zirconium composite oxide thin film layer (12) having a thickness of 200 Å was formed in the same manner as in Example 1 except that only an oil diffusion pump was used as a vacuum exhaust device without using a cryopanel. At this time, the pressure is 5×10 ⁻⁴ To
The rr and water vapor partial pressure were 1.0×10 ⁻⁴ Torr.
The specific gravity of the thin film was measured, and the results are shown in Table 1.

On the thin film layer (12) of the laminated film of the plastic film (11)/silicon zirconium composite oxide thin film layer (12), a curable resin cured product layer (13) was formed in the same manner as in Example 1. did. Further, the silicon zirconium composite oxide thin film layer (12) and the curable resin cured product layer (13) are laminated on the other surface of the plastic film (11) in the same manner as described above to obtain a laminated film (1). It was

The surface roughness of the cured resin layer (13) was Ra=0.005 μm or less and Rmax=0.
It was 1 μm or less. Any laminated film (1)
The retardation value is 5 nm and the visible light transmittance is 8
4% and the thickness was 115 μm. The interlayer adhesion (peel strength) of the laminated film (1) was measured, and the results are shown in Table 1.
It was shown to. The peel strength was low in all cases. The peeling interface is
Both were at the interface between the curable resin cured product layer (13) and the silicon zirconium composite oxide thin film layer (12). Table 1 shows the measurement results of oxygen permeability of the laminated film (1), but it was insufficient for use in a liquid crystal display panel.

A transparent electrode (2) similar to that of Example 1 was formed on the laminated film (1), and then a liquid crystal display panel (7) was prepared in the same manner as in Example 1. However, since the interlayer adhesion of the laminated film (1) is insufficient, the laminated film (1) may be delaminated during the manufacturing process.

Example 2 (2-1 to 2-4) A polyamideimide film was used as the plastic film (11). The thickness was 100 μm, the retardation value was 5 nm, and the visible light transmittance was 90%.

On one side of this plastic film (11), a silicon zirconium composite oxide thin film layer (12) is formed.
Was irradiated with an ion beam to form a film by the electron beam evaporation method. At this time, ZrO ₂ (purity 99.5%) and SiO ₂ (purity 99.9%) in the form of particles having a size of 3 to 5 mm were used as vapor deposition materials. Without mixing these vapor deposition materials, the water-cooled copper hearth was partitioned into two by a water-cooled copper plate, and one electron gun was used as a heating source, and ZrO ₂ and Si were used.
Each O ₂ was heated in time division. The emission current of the electron gun at that time was set to 2.6 A, and the heating time ratio was changed to Table 2 in order to change the content ratio of zirconium oxide in the thin film.
It changed like. Also, oxygen gas was supplied at 5 sccm, the center roll temperature was -15°C, and the film feed rate was 180.
m/min. An oil diffusion pump was used as a vacuum exhaust device. At this time, the pressure was 4.5×10 ⁻⁴ Torr and the water vapor partial pressure was 8×10 ⁻⁵ Torr. Oxygen ions were used as the ion species of the ion beam, the ion beam current density was 1.0 mA/cm ² , and the ion beam energy was 200V. The angle of incidence of the ion beam on the plastic film (11) was 45 degrees. Under the film forming conditions as described above, a silicon zirconium composite oxide thin film layer (12) having a thickness of 300 Å was laminated. Further, the specific gravity of the thin film was measured, and the results are shown in Table 2.

Composition of 35 parts of phenoxyether resin, 35 parts of methyl ethyl ketone, 30 parts of cellosolve acetate, and 50 parts of 75% solution of an adduct of tolylene diisocyanate and trimethylolpropane (Coronate L manufactured by Nippon Polyurethane Industry Co., Ltd.) The curable resin composition of was prepared. Then, the plastic film (1 with the silicon zirconium composite oxide thin film layer (12) is attached.
While running 1), the above curable resin composition was applied onto the thin film layer (12) with a die, and the thin film layer (12) was heated at 100° C. for 3 hours.
Allow to dry for minutes. The same smoothing template material (F) as that used in Example 1 was coated thereon and heated at 150° C. for 5 minutes while being pressed through the roll groups. As a result, the coating layer was cured to form a curable resin cured product layer (13) having a thickness of 20 μm.

On the other side of the plastic film (11), a silicon zirconium composite oxide thin film layer (12) having a thickness of 300 Å and a curable resin cured product layer (13) having a thickness of 20 μm were formed in the same manner as above. It was By this, (F)
/(13)/(12)/(11)/(12)/(13)
A laminated film having a layer structure of /(F) was obtained. Then, the smoothing template material (F) was peeled and removed in the same manner as in Example 1 to obtain a laminated film (1).

The surface roughness of the cured resin layer (13) was Ra=0.004 μm or less and Rmax=0.
It was 1 μm or less. Any laminated film (1)
The retardation value is 5 nm and the visible light transmittance is 8
2% and the thickness was 140 μm. Laminated film (1)
The interlayer adhesion (peel strength) of was measured, and the results are shown in Table 2. All exhibited sufficiently strong peel strength, and the peel interface was the interface between the curable resin cured product layer (13) and the silicon zirconium composite oxide thin film layer (12). From these results, the laminated film (1) of the present invention had sufficiently strong interlayer adhesion. The oxygen permeability was measured in order to evaluate the gas barrier properties of the laminated film (1). As shown in Table 2, the results showed extremely high gas barrier properties.

Then, one curable resin cured product layer (1
A transparent electrode (2) made of indium tin composite oxide having a thickness of 500 Å was formed on 3) by a sputtering method to obtain an electrode substrate (5). The surface resistivity of this transparent electrode (2) was 80Ω/□.

A liquid crystal display panel was produced by using the electrode substrate (5) in the same manner as in Example 1, but neither laminated film (1) was delaminated during the process.

Comparative Example 2 (2-1 to 2-4) The same polyamide-imide film as in Example 2 was used as a plastic film (11), and a silicon zirconium composite oxide thin film layer (12) was formed thereon. At this time, a silicon zirconium composite oxide thin film layer (12) having a thickness of 300Å was laminated in the same manner as in Example 2 except that the ion beam was not used. An oil diffusion pump was used as a vacuum exhaust device. At this time, the pressure during vapor deposition is 4.3×1.
The pressure was 0 ^-4 Torr, and the water vapor partial pressure was 8×10 ^-5 Torr. Further, the specific gravity of the thin film was measured, and the results are shown in Table 2.

On the thin film layer (12) of the laminated film composed of the plastic film (11)/silicon zirconium composite oxide thin film layer (12), a curable resin cured product layer (13) similar to that of Example 2 was formed. did. Further, the silicon zirconium composite oxide thin film layer (12) and the curable resin cured product layer (13) are laminated on the other surface of the plastic film (11) in the same manner as described above to obtain a laminated film (1). It was

The surface roughness of the cured resin layer (13) was Ra=0.004 μm or less and Rmax=0.
It was 1 μm or less. Any laminated film (1)
The retardation value is 5 nm and the visible light transmittance is 8
2% and the thickness was 140 μm. The interlayer adhesion (peel strength) of the laminated film (1) was measured, and the results are shown in Table 2.
It was shown to. The peel strength was low in all cases. The peeling interface is
Both were at the interface between the curable resin cured product layer (13) and the silicon zirconium composite oxide thin film layer (12). The measurement results of oxygen permeability of this laminated film (1) are shown in Table 2, but all were insufficient for use in a liquid crystal display panel.

A transparent electrode (2) similar to that of Example 1 was formed on the laminated film (1), and then a liquid crystal display panel (7) was prepared in the same manner as in Example 1. However, since the interlayer adhesion of the laminated film (1) is insufficient, the laminated film (1) may be delaminated during the manufacturing process.

Example 3 (3-1 to 3-3) A uniaxially stretched polyethylene terephthalate film was used as the plastic film (11). Thickness is 100μ
m, the retardation value was 10200 nm, and the visible light transmittance was 91%.

On this plastic film (11),
The silicon zirconium composite oxide thin film layer (12) was formed by an electron beam evaporation method. At this time, as a vapor deposition material, 3
˜5 mm size particulate ZrO ₂ (purity 99.5
%) and SiO ₂ (purity 99.9%) were used. Without mixing these vapor deposition materials, the water-cooled copper hearth was partitioned into two water-cooled copper plates, and one electron gun was used as a heating source to heat each of ZrO ₂ and SiO _{2 in} a time-division manner. .. The emission current of the electron gun at that time was 2.3 A, and the heating time ratio was changed as shown in Table 3 in order to change the content ratio of zirconium oxide in the thin film. Also, oxygen gas was supplied at 15 sccm, the center roll temperature was -10°C,
The film feed speed was 100 m/min. Furthermore, an oil diffusion pump and a cryopanel were used as the vacuum exhaust device. As a result, the pressure during vapor deposition was 2.8×10 ⁻⁴ Tor.
r, the water vapor partial pressure was 2.5×10 ⁻⁵ Torr. Under the above film forming conditions, a silicon zirconium composite oxide thin film (12) having a film thickness of 200Å was formed. The specific gravity of the thin film was measured, and the results are shown in Table 3.

On one of the pair of film-forming rolls arranged in parallel at a slight interval, the laminated film (plastic film (11) obtained above was laminated with the silicon-zirconium composite oxide thin film layer (12). The film-making roll is run while the other film-forming roll has a thickness of 75 μm and a surface roughness Ra of the smoothing template (F).
A biaxially stretched polyethylene terephthalate film (A4100 manufactured by Toyobo Co., Ltd.) having 0.005 μm and Rmax=0.05 μm and not subjected to corona treatment was fed while the smooth surface of the film was supplied. An ultraviolet curable resin composition obtained by adding 1 part of benzophenone to 100 parts of an epoxy acrylic resin was discharged from a die toward the gap between the film forming rolls. The discharged ultraviolet curable resin composition was sandwiched between the surface of the plastic film (11) on which the silicon zirconium composite oxide thin film layer (12) was formed and the smooth surface of the smoothing template material (F). So, while running in this state, high pressure mercury lamp, 200w/cm,
Ultraviolet irradiation was performed under the conditions of one lamp, irradiation time of 10 seconds, and a distance of 200 mm between the mercury lamp and the smoothing template material (F). As a result, the sandwiching layer was cured to form a curable resin cured product layer (13) having a thickness of 25 μm.

The same operation as above is carried out on the other surface of the plastic film (11) to form a silicon zirconium composite oxide thin film layer (12) having a thickness of 200 Å and a curable resin cured product layer (13) having a thickness of 25 μm. Was formed. As a result, (F)/(13)/(12)/(11)/(12)
A laminated film having a layer structure of /(13)/(F) was obtained. Next, the smoothing template material (F) is peeled and removed,
A laminated film (1) having a layer structure of (13)/(12)/(11)/(12)/(13) was obtained.

The surface roughness of the cured resin layer (13) was Ra=0.005 μm or less and Rmax=0.
It was 1 μm or less. Any laminated film (1)
The retardation value was 10200 nm, the visible light transmittance was 82%, and the thickness was 150 μm. The interlayer adhesion (peeling strength) of the laminated film (1) was measured, and the results are shown in Table 3. All exhibited sufficiently strong peel strength, and the peel interface was the interface between the curable resin cured product layer (13) and the silicon zirconium composite oxide thin film layer (12). From these results, the laminated film (1) of the present invention had sufficiently strong interlayer adhesion. The oxygen permeability was measured in order to evaluate the gas barrier properties of the laminated film (1). As shown in Table 3, the results showed extremely high gas barrier properties.

Then, one curable resin cured product layer (1
A transparent electrode (2) made of indium tin composite oxide having a thickness of 200 Å was formed on 3) by a sputtering method to obtain an electrode substrate (5). The surface resistivity of this transparent electrode (2) was 80Ω/□.

In the liquid crystal cell (6), after the alignment film is formed on the surface of the transparent electrode (2) of the electrode substrate (5), the two electrode substrates (5) are opposed to each other by the transparent electrodes (2). It was produced by arranging the liquid crystal in a state with a predetermined gap, enclosing the liquid crystal (3) in the gap, and sealing the periphery with a sealing material (4).

The liquid crystal display panel (7) has a polarizing plate (8) on one side and a polarizing plate (8) on the other side with a retardation plate (9) interposed therebetween.
Was manufactured by stacking. In the liquid crystal display panel manufactured in this manner, the interlayer adhesion of the laminated film (1) was sufficiently strong so that the laminated film (1) did not undergo delamination during the manufacturing process.

Comparative Example 3 (3-1 to 3-3) The same uniaxially stretched polyethylene terephthalate film as in Example 3 was used as the plastic film (11),
A silicon zirconium composite oxide thin film layer (1
2) was formed. At that time, a silicon zirconium composite oxide thin film layer (12) having a thickness of 200 Å was formed in the same manner as in Example 3 except that a cryopanel was not used as a vacuum exhaust device and only an oil diffusion pump was used. At this time, the pressure is 5.5×10 ⁻⁴ Torr and the water vapor partial pressure is 1.5×1.
It was 0 ⁻⁴ Torr. Further, the specific gravity of the thin film was measured, and the results are shown in Table 3.

On the thin film layer (12) of the laminated film of the plastic film (11)/silicon zirconium composite oxide thin film layer (12), a curable resin cured product layer (13) was formed in the same manner as in Example 3. did. Further, the silicon zirconium composite oxide thin film layer (12) and the curable resin cured product layer (13) are laminated on the other surface of the plastic film (11) in the same manner as described above to obtain a laminated film (1). It was

The surface roughness of the cured resin layer (13) was Ra=0.005 μm or less and Rmax=0.
It was 1 μm or less. Any laminated film (1)
The retardation value was 10200 nm, the visible light transmittance was 82%, and the thickness was 150 μm. The interlayer adhesion (peel strength) of the laminated film (1) was measured, and the results are shown in Table 3. The peel strength was low in all cases. The peeling interface was the interface between the curable resin cured product layer (13) and the silicon zirconium composite oxide thin film layer (12). Table 3 shows the measurement results of oxygen permeability of the laminated film (1), but it was insufficient for use in a liquid crystal display panel.

A transparent electrode (2) similar to that of Example 3 was formed on the laminated film (1), and then a liquid crystal display panel (7) was prepared in the same manner as in Example 3. However, since the interlayer adhesion of the laminated film (1) is insufficient, the laminated film (1) may be delaminated during the manufacturing process.

Example 4 (4-1 to 4-4) A uniaxially stretched polyethylene terephthalate film was used as the plastic film (11). The thickness is 125μ
m, the retardation value was 11,500 nm, and the visible light transmittance was 90%.

On one side of this plastic film (11), a silicon zirconium composite oxide thin film layer (12) is formed.
Was irradiated with an ion beam to form a film by the electron beam evaporation method. At this time, ZrO ₂ (purity 99.5%) and SiO ₂ (purity 99.9%) in the form of particles having a size of 3 to 5 mm were used as vapor deposition materials. Without mixing these vapor deposition materials, the water-cooled copper hearth was partitioned into two by a water-cooled copper plate, and one electron gun was used as a heating source, and ZrO ₂ and Si were used.
Each O ₂ was heated in time division. The emission current of the electron gun at that time was set to 2.6 A, and the heating time ratio was changed to Table 4 in order to change the content of zirconium oxide in the thin film.
It changed like. Also, oxygen gas was supplied at 5 sccm, the center roll temperature was -15°C, and the film feed rate was 180.
m/min. An oil diffusion pump was used as a vacuum exhaust device. At this time, the pressure was 5.3×10 ⁻⁴ Torr and the water vapor partial pressure was 9×10 ⁻⁵ Torr. Oxygen ions were used as the ion species of the ion beam, the ion beam current density was 1.0 mA/cm ² , and the ion beam energy was 200V. The angle of incidence of the ion beam on the plastic film (11) was 45 degrees. Under the film forming conditions as described above, a silicon zirconium composite oxide thin film layer (12) having a thickness of 300 Å was laminated. The specific gravity of the thin film was measured, and the results are shown in Table 4.

Composition consisting of 45 parts of phenoxyether resin, 45 parts of methyl ethyl ketone, 10 parts of cellosolve acetate and 50 parts of 75% solution of an adduct of tolylene diisocyanate and trimethylolpropane (Coronate L manufactured by Nippon Polyurethane Industry Co., Ltd.) The curable resin composition of was prepared. Then, the plastic film (1 with the silicon zirconium composite oxide thin film layer (12) is attached.
While running 1), the above curable resin composition was applied onto the thin film layer (12) with a die, and the film was heated at 100° C. for 5 hours.
Allow to dry for minutes. The same smoothing template material (F) as that used in Example 3 was coated thereon, and heated at 150° C. for 7 minutes while being pressed through the roll groups. As a result, the coating layer was cured to form a curable resin cured product layer (13) having a thickness of 25 μm.

On the other surface of the plastic film (11), a silicon zirconium composite oxide thin film layer (12) having a thickness of 300 Å and a curable resin cured product layer (13) having a thickness of 25 μm were formed in the same manner as above. It was By this, (F)
/(13)/(12)/(11)/(12)/(13)
A laminated film having a layer structure of /(F) was obtained. Then, the smoothing template material (F) was peeled and removed in the same manner as in Example 3 to obtain a laminated film (1).

The surface roughness of the cured resin layer (13) is Ra=0.004 μm or less and Rmax=0.
It was 1 μm or less. Any laminated film (1)
The retardation value was 11,500 nm, the visible light transmittance was 81%, and the thickness was 175 μm. The interlayer adhesion (peeling strength) of the laminated film (1) was measured, and the results are shown in Table 4. All exhibited sufficiently strong peel strength, and the peel interface was the interface between the curable resin cured product layer (13) and the silicon zirconium composite oxide thin film layer (12). From these results, the laminated film (1) of the present invention had sufficiently strong interlayer adhesion. The oxygen permeability was measured in order to evaluate the gas barrier properties of the laminated film (1). As shown in Table 4, the results showed extremely high gas barrier properties.

Then, one curable resin cured product layer (1
A transparent electrode (2) made of indium tin composite oxide having a thickness of 250 Å was formed on 3) by a sputtering method to obtain an electrode substrate (5). The surface resistivity of this transparent electrode (2) was 150Ω/□.

A liquid crystal display panel (7) was produced by using the electrode substrate (5) in the same manner as in Example 3, but neither of the laminated films (1) was delaminated during the process.

Comparative Example 4 (4-1 to 4-4) The same uniaxially stretched polyethylene terephthalate film as in Example 4 was used as the plastic film (11),
A silicon zirconium composite oxide thin film layer (1
2) was formed. At this time, a silicon zirconium composite oxide thin film layer (12) having a thickness of 300Å was laminated in the same manner as in Example 4 except that the ion beam was not used. An oil diffusion pump was used as a vacuum exhaust device. At this time, the pressure during vapor deposition was 5.1×10 ⁻⁴ Torr, and the partial pressure of water vapor was 9×.
It was 10 ⁻⁵ Torr. The specific gravity of the thin film was measured, and the results are shown in Table 4.

On the thin film layer (12) of the laminated film composed of the plastic film (11)/silicon zirconium composite oxide thin film layer (12), a curable resin cured product layer (13) similar to that of Example 4 was formed. did. Further, the silicon zirconium composite oxide thin film layer (12) and the curable resin cured product layer (13) are laminated on the other surface of the plastic film (11) in the same manner as described above to obtain a laminated film (1). It was

The surface roughness of the curable resin cured product layer (13) was Ra=0.004 μm or less and Rmax=0.
It was 1 μm or less. Any laminated film (1)
The retardation value was 11,500 nm, the visible light transmittance was 81%, and the thickness was 175 μm. The interlayer adhesion (peel strength) of the laminated film (1) was measured, and the results are shown in Table 4. The peel strength was low in all cases. All of the peeling interfaces were the curable resin cured product layer (13)/silicon zirconium composite oxide thin film layer (12). The measurement results of oxygen permeability of this laminated film (1) are shown in Table 4, but all were insufficient for use in a liquid crystal display panel.

A transparent electrode (2) similar to that in Example 3 was formed on the laminated film (1), and then a liquid crystal display panel (7) was produced in the same manner as in Example 3. However, since the interlayer adhesion of the laminated film (1) is insufficient, the laminated film (1) may be delaminated during the manufacturing process.

Example 5 (5-1 to 5-4) A norbornene-based polymer film was used as the plastic film (11). The thickness was 100 μm, the retardation value was 2 nm, and the visible light transmittance was 91%.

On one surface of the plastic film (11), a silicon zirconium composite oxide thin film layer (12) is formed.
Was irradiated with an ion beam to form a film by the electron beam evaporation method. At this time, ZrO ₂ (purity 99.9%) and SiO ₂ (purity 99.9%) having a particle size of 2 to 4 mm were used as vapor deposition materials. Without mixing these vapor deposition materials, the water-cooled copper hearth was partitioned into two by a water-cooled copper plate, and one electron gun was used as a heating source, and ZrO ₂ and Si were used.
Each O ₂ was heated in time division. The emission current of the electron gun at that time was set to 2.8 A, and the heating time ratio was changed to Table 5 in order to change the content of zirconium oxide in the thin film.
It changed like. Also, oxygen gas was supplied at 5 sccm, the center roll temperature was -10°C, and the film feed rate was 20 m.
/Min. A turbo molecular pump was used as an evacuation device. At this time, the pressure was 4.0×10 ⁻⁴ Torr and the water vapor partial pressure was 7×10 ⁻⁵ Torr. Oxygen ions were used as the ion species of the ion beam, the ion beam current density was ^2.5 mA/cm ² , and the ion beam energy was 50V. The angle of incidence of the ion beam on the plastic film (11) was 30 degrees. Under the above film forming conditions, a silicon zirconium composite oxide thin film layer (12) having a thickness of 400 Å was laminated. Further, the specific gravity of the thin film was measured, and the results are shown in Table 5.

A silicon zirconium composite oxide thin film layer (12) having a thickness of 400 Å was formed on the other surface of the plastic film (11) in the same manner as above. As a result, a laminated film (1) having a layer structure of (12)/(11)/(12) was obtained.

The surface roughness of this laminated film (1) was Ra=0.004 μm or less and Rmax=0.1 μm.
It was below. Each of the laminated films (1) had a retardation value of 2 nm, a visible light transmittance of 90%,
The thickness was 100 μm. The interlayer adhesion (peeling strength) of the laminated film (1) was measured, and the results are shown in Table 5. All exhibited sufficiently strong peel strength, and the peel interface was the interface between the thermosetting adhesive layer and the silicon-zirconium composite oxide thin film layer (12). From this result, the silicon zirconium composite oxide thin film layer (12) and the plastic film (11) have an adhesive force equal to or higher than the peel strength between them and are sufficiently strong interlayer adhesive force. The oxygen permeability was measured in order to evaluate the gas barrier properties of the laminated film (1). As shown in Table 5, the results showed extremely high gas barrier properties.

Then, on one of the silicon zirconium composite oxide thin film layers (12), a transparent electrode (2) made of indium tin composite oxide having a thickness of 1000 Å is formed by a sputtering method, and an electrode substrate (5) is formed. Got The surface resistivity of this transparent electrode (2) was 30Ω/□.

A liquid crystal display panel was produced in the same manner as in Example 1 using the electrode substrate (5), but no laminated film was peeled off.

Physical properties in the above-mentioned Examples and Comparative Examples were measured as follows.

A. Film Thickness It was measured using Millitron 1254D (manufactured by Mahr). b. Thin film layer thickness ICP emission of the atomic ratio of silicon and zirconium in the thin film
Obtained with an analyzer (ICPS-2000; manufactured by Shimadzu Corporation)
Recon and zirconium are complete oxides (SiO ₂, Zr
O₂), and these (SiO₂And ZrO₂)
It was calculated using the bulk specific gravity of

C. Retardation value It was measured using an ellipsometer (AEP-100B, manufactured by Shimadzu Corporation). d. Visible light transmittance It was measured using an integrating sphere type light transmittance measuring device (NDH-1001DP, manufactured by Nippon Denshoku Industries Co., Ltd.) based on JIS K 7105.

E. Specific gravity (D) A part of the laminated film of the plastic film (11)/thin film layer (12) obtained in the above Examples and Comparative Examples was cut out and the plastic film (11) was dissolved in a solvent, A single film of only the thin film (12) was obtained. The specific gravity of this single film is determined by the float-sink method described in JIS K7112 (the sample is immersed in a solution of known specific gravity (a mixture of carbon tetrachloride and methylene iodide), and the specific gravity of the thin film is measured from the floating condition). It was measured.

F. Zirconium Oxide Content (W) The zirconium oxide content is the ICP emission spectrometer (ICPS-2000;
The content ratio of complete zirconium oxide was calculated on the assumption that silicon and zirconium are perfect oxides (SiO ₂ , ZrO ₂ ) obtained by Shimadzu Corporation.

G. Surface roughness Measured using a stylus type surface roughness measuring device (Surfcom 304B, manufactured by Tokyo Seimitsu Co., Ltd.) according to JIS B 0651.

H. Peel strength (interlayer adhesion) On one surface of the outermost layer (silicon zirconium composite oxide thin film layer (12) or curable resin cured product layer (13)) of the laminated film (1) obtained above. And a polyester polyurethane adhesive (A-310 manufactured by Takeda Pharmaceutical Co., Ltd.) 10
Isocyanate-based curing agent (made by Takeda Pharmaceutical Co., Ltd.: A)
-3) A thermosetting adhesive containing 10 parts was applied to a thickness of 3 μm. A 100 μm-thick biaxially stretched polyethylene terephthalate film (E5100 manufactured by Toyobo Co., Ltd.) having a corona treatment was laminated on the adhesive layer, and the adhesive was cured under the conditions of 45° C. and 4 days. .. In the laminate composed of the biaxially stretched polyethylene terephthalate film/thermosetting adhesive layer/laminated film (1) thus produced, the biaxially stretched polyethylene terephthalate film and the laminated film portion were grabbed and
The peel strength was measured by the 90-degree T-type peeling method based on SK 6854.

I. Oxygen permeability (gas barrier property) Using an oxygen permeability measuring device (OX-TRAN100, manufactured by Modern Controls), oxygen permeability of the laminated film (1) under conditions of 25° C. and 80% RH. The degree was measured.

J. Surface resistivity The resistivity was measured using a resistivity meter (Loresta AP MCP-1400, manufactured by Mitsubishi Petrochemical Co., Ltd.) according to the 4-probe method described in JIS K 7194.

[0140]

[Table 1]

[0141]

[Table 2]

[0142]

[Table 3]

[0143]

[Table 4]

[0144]

[Table 5]

[0145]

INDUSTRIAL APPLICABILITY The laminated film of the present invention has the advantages of a plastic film (flexibility, thinness, light weight, etc.), and also has a very strong interlayer adhesion of the laminated film. Does not peel off. Also,
Since the silicon zirconium composite oxide thin film layer which is a metal oxide is used, the gas barrier property is also extremely excellent.

[Brief description of drawings]

FIG. 1 is a cross-sectional view schematically showing an example of a laminated film of the present invention.

FIG. 2 is a sectional view schematically showing an example of the electrode substrate of the present invention.

FIG. 3 is a sectional view schematically showing an example of a liquid crystal cell of the present invention.

FIG. 4 is a cross-sectional view schematically showing an example of the liquid crystal display panel of the present invention.

[Explanation of symbols]

DESCRIPTION OF SYMBOLS 1 Laminated film 11 Plastic film 12 Silicon zirconium compound oxide thin film layer 13 Curable resin cured material layer 2 Transparent electrode 3 Liquid crystal 4 Sealing material 5 Electrode substrate 6 Liquid crystal cell 7 Liquid crystal display panel 8 Polarizing plate 9 Phase difference plate

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[Procedure amendment]

[Submission date] November 21, 1996

[Procedure Amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0026

[Correction method] Change

[Correction content]

By the way, bulk silicon-zirconium composite oxide glass ( zirconia -silica glass; hereinafter also referred to as bulk glass) prepared by a usual melt-quenching method has an ideal three-dimensional network structure and high specific gravity. Have. This is because the melt-quenching method forms complex oxides at a much slower rate than thin-film forming methods such as vacuum deposition method and sputtering method (however, complex oxides formed by melt-quenching method). The object becomes a bulk and does not become a thin film). Such bulk glass has a high gas barrier property because of its ideal three-dimensional network structure.
In addition, a large number of reactive groups such as silanol groups are present on the surface of the bulk glass, which also affects the adhesion. Therefore, it is preferable that the physical properties of the silicon-zirconium composite oxide thin film layer be close to those of bulk glass.

Claims (11)

[Claims] 1. A laminated film comprising a plastic film, and a silicon zirconium composite oxide thin film layer satisfying the following formula (a) on at least one surface of the plastic film. 2.1≦D−0.029W≦2.65 (a) [wherein, D is the specific gravity of the silicon zirconium composite oxide thin film layer, and W is the zirconium oxide content rate (weight) in the silicon zirconium composite oxide thin film layer. %) is shown. ] 2. The laminated film according to claim 1, wherein the zirconium oxide content in the silicon zirconium composite oxide thin film layer is 25 to 90% by weight. 3. The laminated film according to claim 1, wherein the silicon zirconium complex oxide thin film layer has a thickness of 30 to 8000 Å. 4. The laminated film according to claim 1, wherein the retardation value of the plastic film is 30 nm or less or 5000 nm or more. 5. The laminated film according to any one of claims 1 to 4, wherein a curable resin cured product layer is laminated on the silicon zirconium composite oxide thin film layer. 6. The interlayer adhesion of each layer is 300 g/inch.
It is above, The laminated|multilayer film in any one of Claims 1-5 characterized by the above-mentioned. 7. The laminated film according to claim 1, which has an oxygen permeability of 3 cc/m ² ·atm ·day or less. 8. A step of forming a silicon zirconium composite oxide thin film layer by an electron beam evaporation method in a water vapor partial pressure of 5×10 ⁻⁵ Torr or less, or an electron beam evaporation method while irradiating an ion beam. The method for producing a laminated film according to claim 1, further comprising a film forming step. 9. An electrode substrate comprising a transparent electrode on the surface of the laminated film according to any one of claims 1 to 7. 10. A liquid crystal cell comprising the laminated film according to claim 1. 11. A liquid crystal display panel comprising the laminated film according to claim 1.