JP2012032551A - Reflective lamination film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a reflective lamination film that achieves both of high reflectance and excellent durability simultaneously.SOLUTION: The reflective lamination film is deposited on a substrate, and includes a base layer on the substrate, a reflective layer containing Ag as a main component on the base layer, a protection layer on the reflective layer, and a transparent reflection increasing layer on the protection layer. The reflective layer contains N, the transparent reflection increasing layer is a laminate containing an Si oxynitride layer, and the laminate contains a low refractive index layer containing an Si oxynitride layer and a high refractive index layer.

Description

  The present invention relates to a reflective laminated film applicable as a visible light reflecting member and a solar reflective member.

  Conventionally, a reflective film made of a metal film as a light reflecting layer in various applications, such as a backlight unit of a liquid crystal display, a reflecting mirror of a projection television, a reflecting member for LED illumination, a reflecting layer of an optical recording medium, and a back electrode film of a thin film solar cell. A member is used.

  A light reflecting member using a metal film has various film configurations suitable for the purpose based on reflectivity, durability, cost, etc., but has a higher reflectivity like a reflector for projection TV. In a required application, a reflective laminated film including a metal layer having a high reflectivity and an inorganic film formed on the metal layer for the purpose of protecting and enhancing the reflection of the metal layer is often used (Non- Patent Document 1).

  For the production of the reflective laminated film, a vacuum deposition method such as a sputtering method is widely used, and Al or Ag is used as the metal layer (Patent Documents 1 and 2). Since Ag has a higher reflectance than Al, it is desirable to use Ag from the viewpoint of improving the reflectance. On the other hand, Ag is likely to cause defects, film peeling, and the like. (Patent Document 3).

  As a method for improving the above problems, a method of alloying an Ag film by adding a noble metal such as Au or Pd or a metal such as Cu or Al to the Ag film (Patent Document 4, Patent Document 5), silicon nitride, or the like A method of laminating the above film as a protective layer on the Ag layer is proposed (Patent Document 6).

JP 2002-267823 A JP 2007-310335 A JP 2006-010930 A JP 2000-109943 A JP 2001-221908 A International Publication WO2007 / 007570 Pamphlet JP 2006-010929 A

Industrial Research Committee Tatsuo Uchida, Hioki Uchiike (supervised), Encyclopedia of Flat Panel Display (2001), page 197

  As described above, the Ag film is liable to generate defects, peel off the film, and the like, and one of the causes is poor durability to moisture, halogen and the like. In the conventional method, durability is improved by adding a noble metal such as Au or Pd to the Ag film and alloying the Ag film, but the durability is improved. There was a problem that the rate would decrease.

  Thus, an object of the present invention is to provide a reflective laminated film capable of simultaneously realizing high reflectivity and good durability.

  As a result of intensive studies on the above-mentioned problems, the present inventor has found that the durability of the Ag film containing N is greatly improved while maintaining an excellent reflectance. Moreover, it discovered that durability could be improved more by using Si oxynitride for the low refractive index layer of the laminated body which comprises the transparent increase reflection layer of Ag upper layer on the other hand. In general, in a laminated body using an Ag film, the durability of the Ag film is improved by reducing the internal stress of the film used in the laminated body, but the Si oxynitride of the present invention is In spite of the fact that the internal stress tends to be higher than that of the Si oxide, it has been found that the durability is improved as compared with the Si oxide film when used in the above laminate.

  That is, the reflective laminated film of the present invention is a reflective laminated film formed on a base material, and the reflective laminated film is a base layer on the base material, a reflective layer mainly composed of Ag on the base layer, A protective layer on the reflective layer; a transparent reflective layer on the protective layer; wherein the reflective layer includes N; and the transparent reflective layer is a laminate including an Si oxynitride layer. It is characterized by that.

  Further, in the reflective laminated film of the present invention, the transparent increased reflection layer includes a low refractive index layer made of Si oxynitride and a high refractive index layer made of a metal oxide, and the refractive index of the high refractive index layer Is characterized by being 0.4 or more higher than the refractive index of the low refractive index layer.

  Further, in the reflective laminated film of the present invention, the protective layer is a metal whose main component is at least one selected from the group consisting of Zn, Sn, Ti, Al, NiCr, Cr, Zn alloy, and Sn alloy, or It is a Zn oxide or In oxide containing 1 to 10% by mass of at least one selected from the group consisting of Al, Ga, and Sn with respect to the metal element. When Al, Ga, or Sn is less than 1% by mass or more than 10% by mass, the stress of the oxide layer becomes high, and the adhesion with the Ag film may be lowered.

  In the reflective laminated film of the present invention, the underlayer is mainly composed of at least one selected from the group consisting of oxides of Al, Ti, Zn, In, Sn, oxynitrides, and nitrides. Features.

In addition, the reflective laminated film of the present invention includes a step of forming a base layer on a substrate using a sputtering method in the manufacturing method thereof, and a mixed gas atmosphere of a rare gas and N ₂ on the base layer. A step of forming a reflective layer mainly composed of Ag, a step of forming a protective layer on the reflective layer, and a Si gas in a mixed gas atmosphere containing a rare gas, N ₂ and O ₂ on the protective layer. Including a step of forming a transparent reflective layer including a step of forming a low refractive index layer made of oxynitride and a step of forming a high refractive index layer on the low refractive index layer. The manufacturing method of the reflective laminated film.

In the method of manufacturing the reflective multilayer film of the present invention, the gas mixture used in the step of depositing the reflective layer, characterized in that it comprises a N ₂ 5 to 40 vol%.

The amount of N ₂ gas is 5% by volume or more and 40% by volume or less, preferably 10% by volume or more and 30% by volume or less. When the amount of the N ₂ gas is less than 5% by volume, no improvement in durability against salt water is observed, and when it exceeds 40% by volume, the deposition rate of the reflective layer is increased despite the fact that the salt water durability does not change greatly. Since it continues to decrease, productivity may decrease.

  In the method for manufacturing a reflective laminated film of the present invention, the mixed gas used in the step of forming the low refractive index layer contains 40 to 70% by volume of a rare gas.

When the amount of the rare gas is less than 40% by volume, the durability may be slightly lowered due to the internal stress of the film. When the amount is more than 70% by volume, the supply amount of N ₂ and O ₂ is insufficient. Thus, an oxynitride deficient in nitrogen or oxygen may be formed, and the transparency of the film may be lost. Furthermore, it was found that when the amount of the rare gas is 40 to 70% by volume and the gas flow rates of nitrogen and oxygen are adjusted so that a low refractive index film is formed, the film formation rate is improved. .

  The reflective laminated film of the present invention is a reflective laminated film having both high reflectivity and durability. Further, in one of the preferred embodiments of the present invention, the sputter target used for the production of the reflective laminated film does not require the addition of metal, so there is no fear that the composition deviation of the film will occur depending on the usage state of the target. It is possible to stably obtain products of the same quality.

The cross-sectional schematic diagram showing one Embodiment of the reflective laminated film of this invention. The cross-sectional schematic diagram showing one Embodiment of the reflective laminated film of this invention. The top view which showed the principal part when seeing a sputtering device from upper direction.

  One preferred embodiment of the present invention is shown in FIG. The reflective laminated film uses a plate glass 3 as a substrate, a base layer 13 on the plate glass 3, a reflective layer 14 mainly composed of Ag on the base layer 13, a protective layer 15 on the reflective layer 14, The transparent increasing reflection layer 19 is provided on the protective layer 15, the reflection layer 14 contains N, and the transparent reflection increasing layer 19 is made of Si oxynitride and the low refractive index layer 16. It is a laminate comprising the high refractive index layer 17 on the layer.

  The underlayer 13 is a layer mainly composed of at least one selected from the group consisting of oxides of Al, Ti, Zn, In, Sn, oxynitrides, and nitrides, and includes the plate glass 3 and the reflective layer. 14 is used to improve the adhesion to the material.

  The reflective layer 14 uses Ag containing N. The thickness of the reflective layer 14 is not particularly limited, but is preferably 50 to 500 nm, more preferably 120 nm or more and 200 nm or less. When the thickness is less than 50 nm, visible to infrared light is transmitted through the reflective layer 14, so that sufficient reflectance cannot be obtained. The upper limit is not particularly limited, but it may be 500 nm or less in consideration of cost.

  The protective layer 15 is a layer provided to prevent the reflective layer 14 from being oxidized during film formation, and to improve the adhesion between the reflective layer 14 and the transparent enhanced reflective layer 19, and Zn , Sn, Ti, Al, NiCr, Cr, Zn alloy, and a metal mainly comprising at least one selected from the group consisting of Sn alloys, or a metal element selected from the group consisting of Al, Ga, and Sn Zn oxide or In oxide containing 1 to 10% by mass of at least one selected from the above is preferable. In particular, the Zn oxide and the In oxide are preferable because they have high adhesion to the Ag film and can easily maintain a high reflectance as compared with the case of using a metal. Further, the thickness of the protective layer 15 is not particularly limited. However, if the thickness is too thin, the reflective layer 14 may be oxidized during the formation of the transparent reflective layer 19. Therefore, the thickness may be preferably 2 to 10 nm.

  The transparent increased reflection layer 19 is a layer including two or more layers having different refractive indexes. The transparent enhanced reflection layer 19 is preferably laminated in the order of the low refractive index layer 16 and the high refractive index layer 17 from the substrate side, and the low refractive index layer 16 and the high refractive index layer 17 are laminated a plurality of times. It may be a thing. In addition to the low-refractive index layer 16 and the high-refractive index layer 17, the transparent increased reflection layer 19 may include other layers as long as the reflectance and durability are not impaired.

The refractive index difference between the low refractive index layer 16 and the high refractive index layer 17 is preferably 0.40 or more, and more preferably 0.50 to 1.10. Note that the optimum thickness of the low refractive index layer 16 and the high refractive index layer 17 varies depending on the wavelength range in which the enhanced reflection effect is desired, so that the thickness of each layer increases the reflectance in the target wavelength range. What is necessary is just to be decided suitably.

The low refractive index layer 16 is made of Si oxynitride, and the high refractive index layer 17 is preferably a metal oxide having a refractive index of 2.00 or more and 2.70 or less. Examples thereof include oxides such as Ti, Zr, Nb, and Ta.

The refractive index of the low refractive index layer 16 may be determined in consideration of the refractive index difference from the high refractive index layer 17, but it is sufficient when the high refractive index layer 17 is made of the above metal oxide. In order to exhibit a good enhanced reflection effect, it is preferably 1.80 or less, more preferably 1.46 or more and 1.70 or less.

  Moreover, as shown in FIG. 2, the reflective laminated film of this invention may form the overcoat layer 18 in the uppermost layer used as the layer which contact | connects the air farthest from the base material side. By forming the overcoat layer 18, it is possible to improve durability against physical damage such as blocking of water vapor in the air and friction. The overcoat layer 18 is not particularly limited as long as the reflectance is not impaired, but silicon nitride is particularly preferably used.

  When silicon nitride is used for the overcoat layer 18, the thickness is preferably 1 to 40 nm, and more preferably 2 to 15 nm. Although the overcoat layer 18 has a higher water vapor blocking performance as the film thickness increases, the reflectance tends to be lower. Therefore, when the thickness is less than 1 nm, the water vapor may not be blocked. In some cases, the decrease in reflectivity is increased.

  In the present invention, “on the substrate” may be in contact with the substrate or may have another layer interposed between the substrate and the substrate. Further, other layers may be interposed between the layers as long as the durability and the reflectance are not impaired.

  A plate glass is suitably used for the substrate in the present invention. There are no particular restrictions on the glass, but float plate glass made of quartz glass or soda lime silicate glass, alkali-free glass, borosilicate glass, low expansion glass, zero expansion glass, low expansion crystallized glass, zero expansion crystallized glass , TFT glass, PDP glass, optical film substrate glass, and the like. In addition, you may use a polymer film for a base material according to the objective.

  Moreover, the manufacturing method of suitable embodiment of the reflection laminated film of this invention shown in FIG. 1 is shown below. The reflective laminated film is formed by a sputtering method, and is preferably formed by a sputtering film forming machine as shown in FIG. This will be described with reference to FIG.

  First, the target 1 and the base material 3 are installed at predetermined positions in the sputter film forming machine. The base material 3 is held by the substrate holder 2. After holding the substrate 3, the main valve 6 is opened, and the vacuum chamber 8 is evacuated using the vacuum pump 5.

  The substrate holder 2 holding the base 3 has a movable structure, and the thickness of the layer during film formation can be changed by adjusting the moving speed of the substrate holder. It is preferable that the moving speed be constant and not changed while the substrate is moving in the apparatus.

  Next, an introduction gas corresponding to the target 1 is introduced from the gas introduction pipe 7 into the vacuum chamber 8 by a mass flow controller (not shown), and the pressure in the vacuum chamber 8 is adjusted. Moreover, the kind of vacuum pump should just be selected suitably, and is not specifically limited.

When forming the reflective layer 14, an Ag metal target is used as the target to be used, and a mixed gas of a rare gas and N ₂ is introduced from the gas introduction pipe 7. Further, the introduced gas may contain an optional third component other than the rare gas and N ₂ gas as long as it does not affect the reflective film to be formed. The mixed gas preferably contains 5 to 40% by volume of N ₂ in order to achieve both favorable durability and productivity.

When the protective layer 15 is formed, if a gas containing O ₂ is introduced, Ag of the reflective layer 14 formed in the lower layer may be oxidized by oxygen plasma generated during discharge. The film is formed using a gas in which the amount of O ₂ is adjusted to such an extent that it does not affect or a gas not containing O ₂ .

When forming the low refractive index layer 16 of the transparent reflection increasing layer 19, the target to be used may be either a ceramic target containing Si or an Si target. The amount of the rare gas represented by the rare gas / (rare gas + N ₂ + O ₂ ) × 100 is 40 to 70% by volume, and the mixing ratio of the N ₂ gas and the O ₂ gas is a desired refractive index. It is only necessary to be determined so as to obtain a rate film.

  In addition, any of He, Ne, Ar, Kr, and Xe can be used as the rare gas introduced into the vacuum chamber 8 when the reflective layer 14 and the low refractive index layer 16 are formed. In view of cost and cost, Ar is most preferably used.

  Next, power is applied to the target using the DC power source 10 and the transport roll 12 is operated to transport the plate glass 3 fixed to the base material holder 2.

Either a DC power supply, an AC power supply, or a power supply in which AC and DC are superimposed is used for supplying power to the target, but the DC power supply is preferably used because of its excellent continuous productivity. In addition, when a dielectric such as SiO ₂ or Si ₃ N ₄ is formed, if a direct current power source is used, abnormal discharge due to electrical breakdown of the dielectric deposited around the erosion of the target may occur. It is preferable to use an AC power source or a power source in which a pulse is applied to a DC power source.

  When a film other than the reflective layer 14 and the low refractive index layer 16 is formed, a target to be used may be appropriately selected according to a desired film, and any of a ceramic target and a metal target may be used. Absent. In addition, in any case of using any target, the introduced gas may be appropriately selected according to the type of film to be formed, and is not particularly limited. The introduced gas may contain an optional third component as long as it does not impair the reflectivity, durability, and the like.

  The reflective laminate of the present invention has high reflectivity and durability, and is suitably used as a reflective member for a display element such as a liquid crystal display or a projection television, or a condensing reflecting mirror.

  First, the durability of the reflective layer containing N was examined. A reference example is shown below.

  On a plate glass, a ZnO layer doped with Al having a thickness of 30 nm (hereinafter also referred to as AZO) and an Ag layer having a thickness of 150 nm were sequentially formed using a sputtering apparatus as shown in FIG. As the plate glass, soda lime glass having a thickness of 3 mm was used.

Reference example 1
After setting the target 1 in the vacuum chamber 8 and holding the plate glass 3 on the substrate holder 2, the inside of the vacuum chamber 8 was evacuated using the vacuum pump 5. The gas introduced every time one layer was formed was exhausted by a pump, and a gas corresponding to the type of film to be formed next was newly introduced.

First, an AZO layer was formed on a plate glass. In forming the AZO layer, a ZnAl (Al 4 mass% containing Zn) target was used as the target 1, O ₂ gas was introduced from the gas introduction pipe 7, and the pressure was adjusted to 0.3 Pa by the opening / closing valve 6. Furthermore, the output power of the DC power source was set to 1.0 kW, and an AZO film was obtained on the plate glass 3.

Next, an Ag layer was formed. In the formation of the Ag layer, an Ag target is used as the target 1, a mixed gas of Ar and N ₂ gas (20% by volume of N ₂ gas) is introduced from the gas introduction pipe 7, and the pressure is reduced to 0. The pressure was adjusted to 3 Pa. Further, the output power of the DC power source was set to 0.36 kW, and an Ag film was obtained on the plate glass 3.

Reference example 2
Film formation was performed in the same manner as in Reference Example 1 except that the Ar gas was used as the mixed gas introduced when forming the Ag film.

(Salt water immersion test)
The samples obtained in Reference Examples 1 and 2 were immersed together with the base material in salt water having a concentration of 5% by mass. After 1 hour and 5 hours from the start of immersion, each sample was taken out from salt water, the surface was washed with pure water, and then water droplets were removed with an air gun. After removing the water droplets, the reflectance was measured by entering light from the film surface side using visual observation and a spectrophotometer (U-4000, manufactured by Hitachi, Ltd.). Further, the visible light reflectance and the solar reflectance were calculated by the method described in JIS R3106 (1998). The results of measuring the reflectance are shown in Table 1.

  As a result of the salt water immersion test, in Reference Example 2 in which N was not contained in the Ag layer, white turbidity was observed after 1 hour, and the degree of white turbidity became stronger after 5 hours. Moreover, even if the reflectance of Table 1 was compared, Reference Example 1 containing N in the Ag layer maintained high visible light reflectance and solar reflectance even after the salt water immersion test.

  Based on the above results, examples of the present invention will be described below.

Example 1
On the plate glass 3, an Al-doped ZnO (AZO) layer 13 having a thickness of 30 nm, an Ag layer 14 having a thickness of 150 nm, an AZO layer 15 having a thickness of 3 nm, and an Si oxynitride layer (hereinafter sometimes referred to as SiON) having a thickness of 55 nm. 16, TiO ₂ layer 17 having a thickness of 45 nm was sequentially formed. The plate glass 3 was 3 mm thick soda lime glass.

  After setting the target 1 in the vacuum chamber 8 and holding the plate glass 3 on the substrate holder 2, the inside of the vacuum chamber 8 was evacuated using the vacuum pump 5. The gas introduced every time one layer was formed was exhausted by a pump, and a gas corresponding to the type of film to be formed next was newly introduced.

First, the underlayer 13 was formed. In forming the AZO layer as the underlayer 13, ZnAl is used as a target, O ₂ gas is introduced into the atmospheric gas in the vacuum chamber 8 from the gas introduction pipe 7, and the pressure in the vacuum chamber 8 during film formation is increased. Was adjusted to 0.3 Pa by the opening / closing valve 6. Furthermore, the output power of the DC power source was set to 1.0 kW to obtain an AZO film.

Next, the reflective layer 14 was formed. In the formation of the Ag layer as the reflective layer 14, Ag is used as a target, and a mixed gas of Ar and N ₂ (N ₂ gas 20 vol%) is supplied to the atmospheric gas in the vacuum chamber 8 from the gas introduction pipe 7. Introduced. The pressure in the vacuum chamber 8 during film formation was adjusted to 0.3 Pa by the opening / closing valve 6. Furthermore, the output power of the DC power source was 0.36 kW, and an Ag layer was obtained.

Next, the protective layer 15 was formed. In forming the AZO layer as the protective layer 15, ZnO—Al ₂ O ₃ is used as a target, Ar gas is introduced into the atmospheric gas in the vacuum chamber 8 through the gas introduction pipe 7, and the vacuum chamber during film formation is formed. The pressure in 8 was adjusted to 0.6 Pa by the opening / closing valve 6. Furthermore, the output power of the DC power source was 0.50 kW, and an AZO film was obtained.

Next, the low refractive index layer 16 was formed. In the formation of the SiON layer which is the low refractive index layer 16, Si is used as a target, and a mixed gas of Ar, N ₂ and O ₂ (Ar gas 65 volume) from the gas introduction pipe 7 is used as the atmospheric gas in the vacuum chamber 8. %, N ₂ gas 14% by volume, O ₂ gas 21% by volume). The pressure in the vacuum chamber 8 during film formation was adjusted to 0.3 Pa by the opening / closing valve 6. Furthermore, the output power of the DC power source was set to 2.0 kW, the frequency of the AC pulse applied in a superimposed manner on the DC power source was set to 20 kHz, and the SiON layer was obtained.

Next, a high refractive index layer 17 was formed. In the film formation of the TiO ₂ layer which is the high refractive index layer 17, Ti is used as a target, O ₂ gas is introduced into the atmospheric gas in the vacuum chamber 8 from the gas introduction pipe 7, and the vacuum chamber 8 during film formation is formed. The internal pressure was adjusted to 0.4 Pa by the opening / closing valve 6. Further, the output power of the DC power source was set to 3.0 kW, the frequency of the AC pulse applied superimposed on the DC power source was set to 20 kHz, and a TiO ₂ film was formed.

Example 2
A 5 nm thick Si ₃ N ₄ layer was formed as an overcoat layer 18 on the high refractive index layer 17, except that the low refractive index layer 16 had a thickness of 49 nm and the high refractive index layer 17 had a thickness of 41 nm. Film formation was performed in the same manner as in Example 1.

In the formation of the Si ₃ N ₄ layer, Si is used as a target, and a mixed gas of Ar and N ₂ (N ₂ gas 70% by volume) from the gas introduction pipe 7 is used as the atmospheric gas in the vacuum chamber 8. The pressure in the vacuum chamber 8 during film formation was adjusted to 0.3 Pa by the opening / closing valve 6. Furthermore, the output power of the DC power source was set to 2.0 kW, the frequency of the AC pulse applied in a superimposed manner on the DC power source was set to 20 kHz, and a Si ₃ N ₄ film was obtained.

Comparative Example 1
The low refractive index layer 16 was formed in the same manner as in Example 1 except that a 55 nm thick SiO ₂ layer was formed. The low refractive index layer 16 uses Si as a target, and introduces a mixed gas of Ar and O ₂ (70% by volume of O ₂ gas) from the gas introduction pipe 7 into the atmosphere gas in the vacuum chamber 8. The pressure in the vacuum chamber 8 during film formation was adjusted to 0.3 Pa by the opening / closing valve 6. Furthermore, the output power of the DC power source was set to 2.0 kW, the frequency of the AC pulse applied in a superimposed manner on the DC power source was set to 20 kHz, and an SiO ₂ film was obtained.

(Evaluation of optical properties)
Using a spectrophotometer (U-4000, manufactured by Hitachi, Ltd.), the reflectance of each sample was measured by entering light from the film surface side. Further, the visible light reflectance and the solar reflectance were calculated by the method described in JIS R3106 (1998).

(Durability evaluation)
The reflective laminated film was cut into a size of 15 cm × 4 cm, and a salt spray test was performed. The salt water had a concentration of 5% by mass and a temperature of 35 ° C. The test days were 3 days and 5 days. After the test was completed, the surface was rinsed with pure water, and then water drops were removed with an air gun. The tested sample was subjected to visual appearance observation, defect observation with a microscope, and reflectance measurement with a spectrophotometer.

Table 2 shows the film configuration, visible light reflectance, and solar reflectance of each sample. The numbers shown in parentheses in the film structure represent the thickness of the layer, and the unit is nm. Note that an Ag layer formed in a gas atmosphere containing N ₂ was described as Ag—N.

Since each example and each comparative example had the same reflectivity, even if N was contained in the reflective layer and the low refractive index layer, the change in optical characteristics was observed as in the case of the reflective laminated film to which a conventional metal was added. It was shown that it was not possible.

  Table 3 shows the number of defects, defect shape, visible light reflectance, and solar reflectance after the salt spray test of each sample. The appearance and defect shape of the film are the results of observation with a microscope. The appearance of the film is ○ when it is almost inconspicuous, and x when it is frequently seen. No peeling of the film is seen for the defect shape. In the case of ◯, the case where a defect accompanied by peeling of the film such as a circular shape or a polygonal shape is indicated as x.

In the reflective film of Example 1 and Example 2 having the SiON layer, no defect accompanied with film peeling was found, whereas in Comparative Example 1 using the SiO ₂ layer, film peeling with time. Circular or polygonal defects accompanied with a were observed.

  From the above, it was found that the highly reflective laminated film using the Ag layer containing N and the SiON layer has both high reflectance and good durability.

DESCRIPTION OF SYMBOLS 1 Target 2 Base material holder 3 Plate glass 4 Cathode magnet 5 Vacuum pump 6 On-off valve 7 Gas introduction pipe 8 Vacuum chamber 9 Power supply cord 10 DC power supply 11 Backing plate 12 Transport roll 13 Underlayer 14 Reflective layer 15 Protective layer 16 Low refractive index film Layer 17 High refractive index film layer 18 Overcoat layer 19 Transparent reflective layer

Claims (7)

A reflective laminated film formed on a base material, the reflective laminated film being a base layer on the base material, a reflective layer mainly composed of Ag on the base layer, a protective layer on the reflective layer, and the protective layer A reflective multilayer film comprising a transparent enhanced reflective layer on a layer, wherein the reflective layer contains N, and the transparent enhanced reflective layer is a laminate including a Si oxynitride layer. The transparent increased reflection layer includes a low refractive index layer made of Si oxynitride and a high refractive index layer made of a metal oxide, and the refractive index of the high refractive index layer is the refractive index of the low refractive index layer. The reflective laminated film according to claim 1, wherein the reflective laminated film is 0.4 or more higher than the rate. The protective layer is made of at least one metal selected from the group consisting of Zn, Sn, Ti, Al, NiCr, Cr, Zn alloy, and Sn alloy, or Al, Ga, and metal elements. The reflective laminated film according to claim 1, wherein the reflective laminated film is a Zn oxide or an In oxide containing 1 to 10% by mass of at least one selected from the group consisting of Sn. 4. The underlayer mainly comprises at least one selected from the group consisting of oxides of Al, Ti, Zn, In, Sn, oxynitrides, and nitrides. The reflective laminated film according to any one of the above. A method for producing a reflective laminated film according to any one of claims 1 to 4, wherein a sputtering method is used.
Forming a base layer on a substrate;
Forming a reflective layer mainly composed of Ag in a mixed gas of a rare gas and N ₂ on the underlayer;
Forming a protective layer on the reflective layer;
Forming a low refractive index layer made of Si oxynitride in a mixed gas containing a rare gas, N ₂ and O ₂ on the protective layer;
And a step of forming a transparent reflection-enhancing layer including a step of forming a high refractive index layer on the low refractive index layer. Mixed gas used in the step of forming the reflective layer, the manufacturing method of the reflective multilayer film according to claim 5, characterized in that N ₂ is contained 5 to 40% by volume. The method for producing a reflective laminated film according to claim 5 or 6, wherein the mixed gas used in the step of forming the low refractive index layer contains 40 to 70% by volume of a rare gas.