JP4332310B2 - Method for producing titanium oxide layer, titanium oxide layer produced by this method, and antireflection film using titanium oxide - Google Patents

Description

[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a method for producing a titanium oxide layer comprising an organic titanium compound, a titanium oxide layer produced by this method, and an antireflection film using the titanium oxide layer.
[0002]
[Prior art]
Various displays used for computers such as liquid crystal displays, plasma displays, CRTs, word processors, televisions, display boards, display bodies such as instruments, rearview mirrors, goggles, window glass, etc. A substrate is used. And since characters, figures, and other information are read through these transparent substrates, there is a drawback that when the light is reflected on the surface of the transparent substrate, the information becomes difficult to read.
[0003]
At present, in order to solve the above drawbacks, an antireflection film is formed by laminating layers having different refractive indexes on a base film, and the antireflection film is applied to the surface of the transparent substrate. It is done to prevent reflection.
[0004]
Here, in order to form an excellent antireflection film, it is known that it is necessary to laminate a plurality of thin layers having various refractive indexes in the laminated structure, and depending on the size of the refractive index, Thin layers called a low refractive index layer, a medium refractive index layer, and a high refractive index layer are used. Further, as a method for producing an antireflection film having a laminate formed by laminating a plurality of such thin layers, a plasma CVD method is suitably used. This is because by using the plasma CVD method, a homogeneous thin layer can be formed on the base material in a short time using the source gas.
[0005]
Furthermore, in such a situation, a titanium oxide layer is often laminated as the high refractive index layer in the laminated structure of the antireflection film. This is because the titanium oxide layer can be formed by a plasma CVD method using an organic titanium compound gas as a raw material, and the refractive index is relatively easy to be 1.80 or more.
[0006]
[Problems to be solved by the invention]
However, the titanium oxide layer as a high refractive index layer produced by a conventionally known plasma CVD method has a drawback that it lacks adhesion and transparency because of its high deposition rate, and lacks stability in terms of refractive index, In some cases, the refractive index changed after production. This is because even after the titanium oxide layer is formed, the titanium oxide layer undergoes some reaction with oxygen and moisture in the air, thereby changing the components of the layer. it is conceivable that.
[0007]
The present invention has been made in view of the above problems, and even when a titanium oxide layer is produced in a short time by a plasma CVD method, the adhesion and transparency are good, and the refractive index changes after the layer is produced. An object of the present invention is to provide a method for producing a stable titanium oxide layer that does not occur, and to provide a titanium oxide layer produced by using this method and an antireflection film using the titanium oxide layer in a laminate.
[0008]
[Means for Solving the Problems]
As a means for solving the above-mentioned problem, the present invention provides an organic titanium compound gas and an oxygen gas into a reaction chamber, discharges these gases into a plasma state, and makes the reaction as described in claim 1. A plasma CVD method in which a titanium oxide layer is laminated on a substrate placed in a chamber, and in the presence of water vapor, water is supplied into the reaction chamber in addition to organic titanium compound gas and oxygen gas. Provided is a method for manufacturing a titanium oxide layer using a plasma CVD method, wherein a titanium layer is laminated.
[0009]
In the conventional plasma CVD method, it is considered that a portion that reacts with oxygen and moisture in the air remains in the layer components, and the portion exists in the layer, which causes problems in adhesion and transparency. At the same time, it is considered that the refractive index was unstable.
[0010]
Here, in the following description, a portion that reacts with oxygen or moisture in the air in the layer component may be referred to as “residue”. The reason for “residue” is that it is considered that there is a group that remains unreacted because the organic titanium compound gas and the oxygen gas are not sufficiently reacted when the layer is formed.
[0011]
However, according to the present invention, an organotitanium compound gas and an oxygen gas are supplied into the reaction chamber, these gases are discharged into a plasma state, and the titanium oxide layer is formed on the substrate placed in the reaction chamber. In the plasma CVD method to be laminated, in addition to the organic titanium compound gas and oxygen gas, the titanium oxide layer is laminated in the presence of water vapor by supplying water vapor in the reaction chamber. Therefore, even in a portion which becomes a residue in the conventional plasma CVD method, it is possible to react with oxygen or water vapor. As a result, no residue is generated in the layer component.
[0012]
Therefore, the titanium oxide layer produced by the method of the present invention does not cause problems in adhesion and transparency, and the layer components may change when the residues in the layer react with oxygen or water vapor. Therefore, the refractive index does not change.
[0013]
Furthermore, in order to solve the above-mentioned problems, the present invention provides a titanium oxide layer manufacturing method according to claim 1, wherein the water vapor is entrained by oxygen gas in the reaction chamber. Provided is a method of manufacturing a titanium oxide layer characterized by being supplied.
[0014]
According to the present invention, in the method for producing a titanium oxide layer according to claim 1, since the water vapor is entrained with oxygen gas and supplied into the reaction chamber, oxygen and water vapor are sufficiently present. A titanium oxide layer can be laminated in step (b).
[0015]
Further, in order to solve the above-mentioned problems, the present invention provides an oxidation characterized by being manufactured by the method for manufacturing a titanium oxide layer according to claim 1 or claim 2 as described in claim 3. Provide a titanium layer.
[0016]
According to the present invention, since the titanium oxide layer is manufactured by the method for manufacturing a titanium oxide layer according to claim 1 or 2, the so-called residue does not exist in the titanium oxide layer. . Therefore, it can be said that the layer is a titanium oxide layer having a stable refractive index without changing the layer components after the layer formation.
[0017]
Furthermore, in order to solve the above-mentioned problems, the present invention provides, as described in claim 4, a reflective body having a base material and a laminated body in which a plurality of thin layers are laminated on the base material. It is a prevention film, Comprising: At least 1 layer of the thin layers in the said laminated body is a titanium oxide layer of the said Claim 3, and a reflectance is 5-25% ((lambda) = 550nm), The transmittance | permeability Is 70-90% (λ = 550 nm).
[0018]
According to the present invention, the antireflection film has a base material and a laminate formed by laminating a plurality of thin layers on the base material, and at least of the thin layers in the laminate Since one layer is the titanium oxide layer according to claim 3, since the refractive index of the titanium oxide layer does not change and the titanium oxide layer has no residue, Since the adhesiveness with the layer is also excellent, the laminate can be prevented from peeling off.
[0019]
Further, according to the present invention, since the antireflection film has a reflectance of 5 to 25% (λ = 550 nm), it can be used for various applications conventionally used.
[0020]
Furthermore, according to the present invention, since the antireflection film has a transmittance of 70 to 90% (λ = 550 nm), it is sufficient in transparency, and can be used for various applications as described above. it can.
[0021]
In order to solve the above problems, the present invention provides the antireflection film according to claim 4, wherein the layer structure of the laminate is refracted from the substrate side. A silica layer as a medium refractive index layer having a refractive index of 1.55 or more and less than 1.80 (λ = 550 nm), a titanium oxide layer as a high refractive index layer according to claim 3, and a refractive index of less than 1.55 Provided is an antireflection film characterized by being a silica layer as a low refractive index layer.
[0022]
Furthermore, in order to solve the above problems, the present invention provides the antireflection film according to claim 4, wherein the layer configuration of the laminate is from the substrate side, as described in claim 6. A titanium oxide layer as a high refractive index layer according to claim 3, a silica layer as a low refractive index layer having a refractive index of less than 1.55, a titanium oxide layer as a high refractive index layer according to claim 3, An antireflection film characterized by being a silica layer as a low refractive index layer having a refractive index of less than 1.55.
[0023]
By making the laminate of the antireflection film as a layer structure as described above, in the titanium oxide layer as the high refractive index layer in the layer structure, the effect described in claim 3 is exhibited, and By adopting the above layer structure, reflection of light can be efficiently prevented.
[0024]
DETAILED DESCRIPTION OF THE INVENTION
[1] Method for producing titanium oxide layer
First, the manufacturing method of the titanium oxide layer of this invention is demonstrated using drawing.
[0025]
In the method for producing a titanium oxide layer of the present invention, an organic titanium compound gas and an oxygen gas are supplied into a reaction chamber, and these gases are discharged into a plasma state and oxidized on a substrate placed in the reaction chamber. A plasma CVD method for laminating a titanium layer, characterized by laminating a titanium oxide layer in the presence of water vapor by supplying water vapor in addition to the organic titanium compound gas and oxygen gas into the reaction chamber. CVD method. In other words, the method of the present invention has a great feature in that the conventional plasma CVD method is improved, and water vapor is supplied into the reaction chamber to form a layer in the presence of water vapor.
[0026]
FIG. 1 is a schematic configuration diagram showing an example of a plasma CVD apparatus for carrying out the method of the present invention.
[0027]
A plasma CVD apparatus 1 shown in FIG. 1 is a parallel plate type plasma CVD apparatus, and includes a reaction chamber 2, an organic titanium compound gas tank 3, an oxygen gas tank 4, a water vapor generator 5, and a vacuum pump 6. And is roughly composed of the following. An upper electrode 10 and a lower electrode 11 are installed in the reaction chamber 2, and a power supply device 12 is connected to the lower electrode 11.
[0028]
When the titanium oxide layer of the present invention is manufactured by the plasma CVD apparatus 1, the base material 20 is placed on the lower electrode 11, and the inside of the reaction chamber 2 is depressurized using the vacuum pump 6. Then, a predetermined power is applied to the lower electrode 11.
[0029]
In this state, the organic titanium compound gas is introduced from the organic titanium compound gas tank 3 to the vicinity of the electrode in the reaction chamber, and the oxygen gas from the oxygen gas tank 4 reacts with the water vapor generated in the water vapor generator 5. It is introduced near the electrode in the chamber 2. At this time, the degree of opening and closing of the valve 13 between the reaction chamber 2 and the vacuum pump 6 is controlled to keep the pressure in the reaction chamber 2 at a predetermined pressure. By doing so, the organic titanium compound gas introduced into the reaction chamber 2 is discharged into a plasma state, and oxygen gas (O) introduced into the reaction chamber 2 together with the organic titanium compound gas. ₂ ), And water vapor (H ₂ O) undergoes a chemical reaction, and as a result, a titanium oxide layer is formed on the substrate 20.
[0030]
Since the titanium oxide layer formed in this manner can sufficiently cause a chemical reaction with a large amount of oxygen gas and water vapor gas, the component of the layer does not change after the layer formation, and the refractive index Is also stable.
[0031]
The reaction chamber 2 in the plasma CVD apparatus 1 for carrying out the method of the present invention, the tanks 3 and 4 for various gases, the vacuum pump 6 and the like are not particularly limited, and a conventionally known plasma CVD apparatus. The same can be used.
[0032]
In addition, the structure and the like of the water vapor generating apparatus which is a specific apparatus for carrying out the method of the present invention are not particularly limited as long as it is an apparatus capable of generating water vapor to be introduced into the reaction chamber 2. Any water vapor generator may be used, but the water used as the raw material for the water vapor is preferably distilled water or ion exchange water. This is because these waters have few impurities, and therefore a uniform titanium oxide layer can be formed.
[0033]
Here, the amount of water vapor introduced into the reaction chamber 2 is not particularly limited, and can be arbitrarily determined depending on the thickness of the titanium oxide layer to be stratified and the stratification speed. However, in order to form a more stable titanium oxide layer, it is preferable to introduce water vapor so that the volume ratio of the organic titanium compound gas and water vapor is in the ratio of 1: 0.5 to 1: 5. This volume ratio is in a standard state (25 ° C., 1 atm). This is because if the volume ratio of the organic titanium compound gas is less than 0.5, the volume ratio of the water vapor introduced is less than 0.5, and the amount of water vapor is insufficient, resulting in an unstable layer like the conventional titanium oxide layer. On the other hand, if the volume ratio of the organic titanium compound gas to the volume ratio of water vapor introduced to 1 is greater than 5, the formation of the organic titanium layer will be adversely affected, and a powder is formed instead of a thin layer. This is because there are cases.
[0034]
As the organic titanium compound gas used in the method of the present invention, Ti (i-OC _Three H ₇ ) _Four (Titanium tetra i-propoxide), Ti (OCH _Three ) _Four (Titanium tetramethoxide), Ti (OC ₂ H _Five ) _Four (Titanium tetraethoxide), Ti (n-OC _Three H ₇ ) _Four (Titanium tetra n-propoxide), Ti (n-OC _Four H ₉ ) _Four (Titanium tetra n-butoxide), Ti (t-OC _Four H ₉ ) _Four (Titanium tetra-t-butoxide), Ti (sec-OC _Four H ₉ ) _Four Titanium alkoxide of (titanium tetra sec-butoxide) and TiCl _Four (Titanium tetrachloride). Among them, Ti (i-OC _Three H ₇ ) _Four (Titanium tetra i-propoxide), Ti (t-OC _Four H ₉ ) _Four (Titanium tetra-t-butoxide) is preferred because of its high vapor pressure.
[0035]
When such an organic titanium compound gas is introduced into the reaction chamber 2, an assist gas for uniformly distributing the gas in the reaction chamber may be used. In this case, the assist gas is not particularly limited.
[0036]
The method and apparatus for introducing water vapor into the reaction chamber 2 are not particularly limited, and any method and apparatus can be used as long as a certain amount of water vapor can be introduced. However, since the organic titanium compound gas easily reacts with water vapor, the introduction into the reaction chamber needs to be performed separately. Therefore, in the method of the present invention, when introducing water vapor into the reaction chamber, it is preferable to introduce it with oxygen gas. For example, in the plasma CVD apparatus 1 shown in FIG. It is preferable to provide the water vapor generating device 5 in the middle of the pipe connecting the reaction chamber 2. By doing so, oxygen gas and water vapor can be simultaneously supplied into the reaction chamber, and the structure of the plasma CVD apparatus can be simplified.
[0037]
When introducing water vapor into the reaction chamber 2, it can be accompanied with a gas other than the oxygen gas. For example, if the gas is poorly soluble in water such as nitrogen gas, helium gas, argon gas, Even if it considers from the viewpoint of control of the amount of introduction, there is no particular limitation.
[0038]
In the method for producing a titanium oxide layer of the present invention, an organic titanium compound gas and an oxygen gas are supplied into a reaction chamber, and these gases are discharged into a plasma state and oxidized on a substrate placed in the reaction chamber. A plasma CVD method for laminating a titanium layer, characterized by laminating a titanium oxide layer in the presence of water vapor by supplying water vapor in addition to the organic titanium compound gas and oxygen gas into the reaction chamber. The CVD method is not particularly limited, and the parallel plate type plasma CVD apparatus 1 shown in FIG. 1 is not necessarily used.
[0039]
FIG. 2 is a schematic configuration diagram of a take-up type plasma CVD apparatus 20. The winding type plasma CVD apparatus 20 is suitably used when the substrate 15 is a long film, and the basic structure thereof is the same as that of the parallel plate type plasma CVD apparatus shown in FIG. It is.
[0040]
In the winding-type plasma CVD apparatus 20 shown in FIG. 2, first, a long base film 21 is unwound from a base unwinding section 22 and introduced into a plasma CVD reaction chamber 23 in a vacuum vessel. . The entire reaction vessel is evacuated by a vacuum pump 24. At the same time, the reaction chamber 23 is supplied with an organic titanium compound gas at a specified flow rate from an organic titanium compound gas tank 25, and oxygen gas and water vapor are respectively piped from an oxygen gas tank 26 and a steam generator 27. Supplied using Each pipe may be heated with a heater or the like to prevent liquefaction (particularly, the organic titanium compound gas may be heated because it is easily liquefied). Next, the base film 21 unwound from the base unwinding section 22 and introduced into the reaction chamber 23 is wound around the stratification drum 28 via the reverse roll R, while being synchronized with the rotation of the stratification drum 28. It is sent in the direction of the reverse roll R ′. At this time, the temperature of the stratification drum 28 can be controlled, and the surface temperature of the base film 21 and the surface temperature of the stratification drum 28 are substantially equal. Therefore, the surface temperature of the base film 1 on which titanium oxide is deposited during plasma CVD, that is, the deposition temperature of plasma CVD can be arbitrarily controlled. In this example, the stratification temperature when the titanium oxide layer is deposited on the base film 1 by the plasma CVD method is displayed by the surface temperature of the stratification drum 28 at that time.
[0041]
An RF voltage is applied by the power source P between the electrode 29 and the stratification drum 28. At this time, the frequency of the power source is not limited to the RF frequency (Radio Frequency), and an appropriate frequency from a low frequency to a high frequency can be used. Then, by applying an RF voltage between the electrode 29 and the stratification drum 28, plasma is generated around these electrodes. The organic titanium compound gas, oxygen gas, and water vapor react in this plasma to generate titanium oxide and deposit it on the base film 21 wound around the stratification drum 28 to form a titanium oxide layer. Thereafter, the base film 21 having the titanium oxide layer formed on the surface thereof is wound up by the base winding part 22 ′ through the reverse roll R ′.
[0042]
By using the winding type plasma CVD apparatus 20 as described above, the base film 21 is exposed to a high temperature, and a titanium oxide layer can be formed without stretching, deformation, curling, or the like. Furthermore, according to the apparatus, the material gas flow rate / pressure, discharge conditions, and the feed rate of the base film 21 can be controlled over a wide range, such as the refractive index and film thickness of the formed titanium oxide layer. A film having desired optical characteristics can be obtained without changing the above.
[0043]
In addition, there are two types of plasma CVD methods, a capacitively coupled plasma CVD method and an inductively coupled plasma CVD method, depending on the power application method used to generate plasma. It is also possible to use the plasma CVD method.
[0044]
[2] Titanium oxide layer
Next, the titanium oxide layer of the present invention will be described.
[0045]
The titanium oxide layer of the present invention is characterized by being manufactured by the above-described method for manufacturing a titanium oxide layer of the present invention. The titanium oxide layer produced by this method has no so-called “residue” in the components of the layer. Therefore, the titanium oxide layer of the present invention can be suitably used as a thin layer constituting the laminate in the antireflection film because the refractive index does not change by reacting with oxygen or water vapor in the air.
[0046]
The component of the titanium oxide layer of the present invention is Ti: O: C = 1: 2.2 to 2.7: 0.1 to 0.5 in terms of relative atoms, and Ti—O—CO— The carbonic acid ester and carbonate which are hardly contained such as Ti bond, that is, the carbonic acid ester and carbonate are below the detection limit when XPS measurement is performed with the XPS measuring apparatus and measurement conditions described below.
[0047]
(XPS measuring device)
VG Scientific: XPS (ESCAVAB 220i-XL)
(XPS measurement conditions)
X-ray source: Monochromated Al Kα,
X-ray output: 10KV, 20mA (200W)
Lens: Large Area XL,
Aperture opening: FOA = open, AA = open
Measurement area: 700μmφ
Charge neutralization: Electron neutralization gun + 4V, neutralization assist mask used
Photoelectron escape depth: 90 degrees
[0048]
[3] About antireflection film
Next, the antireflection film using the above-described titanium oxide layer of the present invention will be described.
[0049]
As shown in FIG. 3, the antireflection film 30 of the present invention includes a base material 31 and a laminate 32 that is provided on the base material 31 and is formed by laminating a plurality of thin layers. The antireflection laminate 32 is characterized in that the above-described titanium oxide layer 33 of the present invention is used in one layer.
[0050]
Hereinafter, (1) substrate 31 and (2) laminate 32 constituting antireflection film 30 of the present invention will be described with reference to FIG.
[0051]
(1) Base material
First, the base material 31 will be described.
[0052]
In the antireflection film 30 of the present invention, the base material 31 is a portion that becomes the foundation of the antireflection film. The base material 31 is not particularly limited as long as it is a polymer film transparent in the visible light region. Examples of the polymer film include triacetyl cellulose film, diacetyl cellulose film, acetate butyrate cellulose film, polyether sulfone film, polyacrylic film, polyurethane film, polyester film, polycarbonate film, polysulfone film, and polyether. Examples thereof include a film, a trimethylpentene film, a polyether ketone film, an acrylonitrile film, and a methacrylonitrile film. Furthermore, a colorless film can be used more preferably. Among them, a uniaxial or biaxially stretched polyester film is preferably used because it is excellent in transparency and heat resistance, and a polyethylene terephthalate (PET) film is particularly preferable. Triacetylcellulose is also preferably used in that it has no optical anisotropy. The thickness of the polymer film is preferably about 6 μm to 188 μm.
[0053]
(2) Laminate
Next, the laminated body 32 will be described.
[0054]
The laminated body 32 is located on a base material and is formed by laminating a plurality of thin layers, and has at least one titanium oxide layer 33 of the present invention described above. In general, an antireflection film exhibits an antireflection effect on the entire laminate 32 by laminating a plurality of layers having different optical characteristics. The laminated body 32 in the antireflection film 30 of the present invention only needs to be provided with at least one titanium oxide layer of the present invention, and the other layers are freely laminated so that the antireflection film as a whole has an antireflection effect. Is possible.
[0055]
The antireflection film 30 of the present invention shown in FIG. 3 is also a diagram showing an example of a preferred laminated structure using the titanium oxide layer 33 of the present invention, and has a refractive index of 1.55 or more and 1.80 from the base material 31 side. A silica layer 35 as a medium refractive index layer of less than (λ = 550 nm), the titanium oxide layer 33 of the present invention as a high refractive index layer, a silica layer 34 as a low refractive index layer having a refractive index of less than 1.55, Has a laminated structure.
[0056]
Thus, it is preferable that the low refractive index layer is provided in the outermost layer of the laminate. The titanium oxide layer 33 of the present invention functions as a high-refractive index layer in the antireflection film. However, the titanium oxide layer 33 is laminated together with the low-refractive index layer to efficiently prevent light reflection due to the difference in refractive index. Because it can.
[0057]
Here, the silica layer 34 can be suitably used as the low refractive index layer, and the refractive index is preferably less than 1.55 (wavelength λ = 550 nm). When forming the antireflection film, the refractive index of the silica layer is preferably determined relatively in relation to the other layers laminated, and exhibits an antireflection effect due to the balance of the entire laminate. However, the refractive index of the silica layer as the low refractive index layer in the case of a general laminate is preferably in the above range.
[0058]
Moreover, it is preferable that the middle refractive index layer is provided in the laminated body. The medium refractive index layer is a layer used for enhancing the antireflection function. Here, when the low refractive index layer and the titanium oxide layer 33 as the high refractive index layer of the present invention are in contact with each other, light reflection can be efficiently prevented. It is preferably provided under the titanium oxide layer 33 of the present invention.
[0059]
Such a medium refractive index layer is particularly limited as long as it is a layer formed of a material that is transparent in the visible light region and has a refractive index of 1.55 or more and less than 1.80 (λ = 550 nm). Although not intended, the silica layer 35 can be suitably used as in the low refractive index layer. Also, other than the silica layer, for example, Al ₂ O _Three , SiN, SiON, ZrO ₂ , SiO ₂ ZnO ₂ A fine particle dispersed in an organosilicon compound or the like may be used.
[0060]
In addition, as a raw material gas used when forming a silica layer used as a low refractive index layer or a medium refractive index layer by a plasma CVD method, organic silicone is preferable, and specifically, hexamethyldisiloxane (HMDSO), tetramethyl Disiloxane (TMDSO), methyltrimethoxysilane (MTMOS), methylsilane, dimethylsilane, trimethylsilane, diethylsilane, propylsilane, phenylsilane, tetramethoxysilane, octamethylcyclotetrasiloxane, octamethylcyclotetrasiloxane, tetraethoxysilane Etc. can be used.
[0061]
The antireflection film 40 of the present invention shown in FIG. 4 is a view showing another example of a preferable laminated structure using the titanium oxide layer 33 of the present invention, and the book as a high refractive index layer from the substrate 31 side. Titanium oxide layer 33 of the invention, silica layer 34 as a low refractive index layer having a refractive index of less than 1.55, titanium oxide layer 33 of the present invention as a high refractive index layer, low refractive index having a refractive index of less than 1.55 It has a laminated structure of a silica layer 34 as an index layer.
[0062]
By adopting such a laminated structure, it is possible to efficiently prevent light reflection due to the difference in refractive index of each thin layer, and the titanium oxide layer 33 of the present invention has good adhesion to other thin layers. Since the titanium oxide layers 33 are alternately laminated, the adhesion of the entire laminate can be improved.
[0063]
In the antireflection film of the present invention, a hard coat layer (not shown) can be provided in addition to the laminate.
[0064]
The hard coat layer used in the present invention is a layer formed for the purpose of imparting strength to the antireflection film of the present invention. Therefore, it is not always necessary depending on the application of the antireflection film.
[0065]
The material for forming the hard coat layer is not particularly limited as long as it is a material transparent in the visible light range and can give strength to the antireflection film. For example, UV curable acrylic hard A coat, a thermosetting silicone coating, or the like can be used. In addition, the thickness of the hard coat layer is usually in the range of 1 to 30 μm, and the manufacturing method of such a hard coat layer can use a normal coating method, and is not particularly limited. Absent.
[0066]
Although the hard coat layer is provided, the purpose of providing the hard coat is to give the antireflection film strength and not to improve the antireflection function. It is preferable to install in the position away from the silica layer 5 to perform, and it is preferable to install in the position immediately above a base film.
[0067]
The present invention is not limited to the above embodiment. The above-described embodiment is an exemplification, and any structure that has substantially the same configuration as the technical scope described in the claims of the present invention and has the same operational effects can be used. It is included in the technical scope of the present invention.
[0068]
【Example】
The present invention will be described in more detail with reference to examples.
[0069]
Example 1
Using the apparatus 20 of FIG. 2, a polyethylene terephthalate (PET) film having a thickness of 100 μm was used as a base material, and a titanium oxide layer was formed on the base material. As the organic titanium compound gas, titanium tetraisopropoxide Ti (i-OC) vaporized at 120 ° C was used. _Three H ₇ ) _Four Was used. Further, water vapor was generated using a conventionally known water vapor generator, and was introduced into the reaction chamber along with oxygen gas. The flow rates of the organic titanium compound gas, oxygen gas, and water vapor are as shown below. The plasma CVD apparatus 20 of FIG. 2 used this time is a capacitive coupling type, and a 13.56 MHz RF power source was used as a high frequency power source. Further, the feeding speed of the polymer film as the base material during continuous film formation is 1 m / min. Other conditions are described below.
[0070]
<Film formation conditions>
Applied power: 1kW
Titanium tetraisopropoxide gas flow rate: 100 sccm
Oxygen gas flow rate: 1000 sccm
Water vapor flow rate: 100sccm
Drum surface temperature (stratification temperature): 30 ° C
[0071]
The above gas flow unit sccm is standard cubic cm par minute.
[0072]
The measurement results of the titanium oxide layer formed on the polyethylene terephthalate film under the above conditions are shown below.
[0073]
<Titanium oxide layer measurement results>
Film thickness: 150nm
Deposition rate: 150 nm · m / min
Refractive index (λ = 550 nm): 2.00
The following apparatus was used for the measurement of the titanium oxide layer.
[0074]
<Apparatus used for titanium oxide film measurement>
Film thickness measurement: Ellipsometer (model number UVISELTM manufacturer JOBIN YVON)
Refractive index measurement: Ellipsometer (model number UVISELTM manufacturer JOBIN YVON)
[0075]
As shown in the above-described titanium oxide film formation results, a uniform titanium oxide film having a refractive index of 2.00 at a film formation temperature of 30 ° C. has a film formation speed of 150 nm · m / min and has a high film formation speed of polyethylene terephthalate. It could be formed on a film. As a result of measuring this titanium oxide film with an ellipsometer, it was found that there was no coloring problem with an extinction coefficient of 0.0001 at λ = 550 nm. In addition, the polyethylene terephthalate film after forming the titanium oxide film was in a good state with little elongation and no deformation.
[0076]
Furthermore, a titanium oxide layer was manufactured, and the refractive index after heating and humidifying (80 ° C., 90% Rh) for 24 hours was measured. As a result, it was found that the refractive index was stable.
[0077]
(Comparative Example 1)
A titanium oxide layer was produced under the same conditions as in Example 1 except that water vapor was not supplied. Moreover, the apparatus used for the measurement of the manufactured titanium oxide layer is the same as that of the above-mentioned Example 1. The results are shown below.
[0078]
<Titanium oxide layer measurement results>
Film thickness: 210nm
Stratification speed: 210 nm · m / min
Refractive index (λ = 550 nm): 2.00
[0079]
As shown in the above-described titanium oxide film formation results, a homogeneous titanium oxide film having a refractive index of 2.00 at a film formation temperature of 30 ° C. has a film formation speed of 210 nm · m / min and a high film formation speed of polyethylene terephthalate. It could be formed on a film. The titanium oxide film was measured with an ellipsometer. As a result, it was a thin layer that lacked adhesion and further had an extinction coefficient of 0.1 at λ = 550 nm, which was remarkably lacking in transparency.
[0080]
In addition, the titanium oxide layer was manufactured, and the refractive index after heating and humidifying (80 ° C., 90% Rh) for 24 hours was 2.15. It was found that the refractive index also changed significantly. .
[0081]
The transmittance at λ = 550 nm was measured for each of the titanium oxide layers of Example 1 and Comparative Example 1. The result is shown in FIG.
[0082]
As is clear from FIG. 5, it was found that the titanium oxide layer shown in Example 1 of the present invention has excellent transmittance.
[0083]
(Example 2)
Using the plasma CVD apparatus 20 shown in FIG. 2, the antireflection film of the present invention having the laminated structure shown in FIG. 3 was produced. The conditions for forming each layer are shown below.
[0084]
A polyethylene terephthalate film (thickness: 100 μm) was used as the base film (30).
[0085]
As the hard coat layer, an ultraviolet curable resin PET-D31 (Daiichi Seika Kogyo Co., Ltd.) was formed by coating. The ultraviolet curing condition was 480 mJ and the thickness was 6 μm.
[0086]
For the medium refractive index layer (35), ZrO ₂ Fine particle coating solution No. 1221 (ZrO ₂ A coating solution consisting of 0.3 part by weight of a binder (ionizing radiation curable type organosilicon compound) with respect to 100 parts by weight of fine particles was formed by wire bar coating. The ultraviolet curing condition was 480 mJ and the thickness was 88 nm.
[0087]
The titanium oxide layer of the present invention as the high refractive index layer (33) was formed under the same conditions as in Example 1.
[0088]
As the low refractive index layer (34), SiO ₂ The layer was formed by plasma CVD.
[0089]
The antireflection film formed under the above conditions was in a good state with no slight elongation or deformation of the polymer film. The reflection spectral characteristics of the antireflection film prepared under the above conditions are shown in FIG. From FIG. 6, the reflectance near 550 nm, which is easy for humans to sense, was low, and the antireflection effect was good. The visibility reflectance at this time was a good value of 0.3%.
[0090]
The spectral reflectance was measured with a spectrophotometer (model number: UV-3100PC, manufacturer: Shimadzu Corporation).
[0091]
【The invention's effect】
According to the method for producing a titanium oxide layer of the present invention, an organic titanium compound gas and an oxygen gas are supplied into a reaction chamber, and these gases are discharged into a plasma state on the substrate placed in the reaction chamber. In the plasma CVD method of laminating a titanium oxide layer, the titanium oxide layer is sufficiently laminated in the presence of water vapor by supplying water vapor in addition to the organic titanium compound gas and oxygen gas into the reaction chamber. Therefore, even in a portion that becomes a residue in the conventional plasma CVD method, it is possible to react with oxygen and water vapor. As a result, no residue is generated in the layer component.
[0092]
Therefore, the titanium oxide layer produced by the method of the present invention does not cause problems in adhesion and transparency, and the layer components may change when the residues in the layer react with oxygen or water vapor. Therefore, the refractive index does not change.
[0093]
Moreover, since the antireflection film of the present invention uses the titanium oxide layer of the present invention as a high refractive index layer of the laminate, both the transmittance and the reflectance are excellent.
[Brief description of the drawings]
FIG. 1 is a schematic configuration diagram of a parallel plate type plasma CVD apparatus.
FIG. 2 is a schematic configuration diagram of a take-up type plasma CVD apparatus.
FIG. 3 is a schematic cross-sectional view showing an example of the antireflection film of the present invention.
FIG. 4 is a schematic sectional view showing another example of the antireflection film of the present invention.
FIG. 5 is a diagram showing the measurement results of transmittance for titanium oxide layers of examples and comparative examples.
FIG. 6 is a diagram showing reflection spectral characteristics of an antireflection film of an example.
[Explanation of symbols]
1. Parallel plate type plasma CVD apparatus
20 ... Winding type plasma CVD apparatus
31 ... Base material
32 ... Laminate
33 ... titanium oxide layer
34 ... Silica layer as a low refractive index layer
35 ... Silica layer as medium refractive index layer

Claims (2)

An antireflection film having a base material and a laminate formed by laminating a plurality of thin layers on the base material, wherein the layer configuration of the laminate is from the base material side,
A silica layer as a medium refractive index layer having a refractive index of 1.55 or more and less than 1.80 (λ = 550 nm);
A plasma CVD method in which an organic titanium compound gas and an oxygen gas are supplied into a reaction chamber, these gases are discharged into a plasma state, and a titanium oxide layer is laminated on a substrate placed in the reaction chamber. In addition to the organic titanium compound gas and the oxygen gas, the reaction chamber is formed by using a plasma CVD method in which a titanium oxide layer is stacked in the presence of water vapor by supplying water vapor, and the component is a relative atomic number. Ti: O: C = 1: 2.2 to 2.7: 0.1 to 0.5 and a titanium oxide layer as a high refractive index layer having a transmittance of 70 to 90% (λ = 550 nm) ,
A silica layer as a low refractive index layer having a refractive index of less than 1.55,
And
An antireflection film characterized in that the reflectance of the antireflection film is 0.3% . An antireflection film having a base material and a laminate formed by laminating a plurality of thin layers on the base material, wherein the layer configuration of the laminate is from the base material side,
A silica layer as a medium refractive index layer having a refractive index of 1.55 or more and less than 1.80 (λ = 550 nm);
A plasma CVD method in which an organic titanium compound gas and an oxygen gas are supplied into a reaction chamber, these gases are discharged into a plasma state, and a titanium oxide layer is laminated on a substrate placed in the reaction chamber. In addition to the organic titanium compound gas and oxygen gas, water vapor is supplied into the reaction chamber so that the volume ratio of the organic titanium compound gas to water vapor is in the ratio of 1: 0.5 to 1: 5 . It is formed using a plasma CVD method in which a titanium oxide layer is laminated in the presence of water vapor, and the components are relative atoms, Ti: O: C = 1: 2.2 to 2.7: 0.1 to 0 And a titanium oxide layer as a high refractive index layer having a transmittance of 70 to 90% (λ = 550 nm) ,
A silica layer as a low refractive index layer having a refractive index of less than 1.55,
An antireflective film characterized by being

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