JP2015166287A - Method for producing laminate, and laminate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for producing a laminate, in which the laminate has a titanium oxide layer consisting mainly of rutile type titanium dioxide and the temperature when a film is deposited and the temperature when heat treatment is performed after the film is deposited can be made comparatively lower.SOLUTION: The method for producing the laminate comprises a film deposition step and a heat treatment step. At the film deposition step, a precursor layer is deposited on a transparent substrate at a temperature of 150°C or lower by a sputtering method by using a titanium target containing 1-5 atomic% of at least one additional element selected from among Ni, Fe, and Cu. At the heat treatment step, the precursor layer-deposited transparent substrate is heat-treated at a temperature of 550-750°C to obtain the titanium oxide layer consisting mainly of rutile type titanium dioxide.

Description

  The present invention relates to a method for producing a laminate for producing a laminate having a titanium oxide layer mainly composed of rutile-type titanium oxide, and a laminate produced by the production method.

  In order to enhance the functionality of the display and the aperture member, for example, an optical coating is provided on the display screen of the display and the aperture surface of the aperture member. Examples of the optical coating include an antireflection film for reducing reflection and an infrared reflection film for preventing a temperature rise in a room or the like. Examples of the optical coating such as an antireflection film and an infrared reflection film include a dielectric multilayer film in which a high refractive index dielectric layer and a low refractive index dielectric layer are alternately laminated.

  The larger the refractive index difference between the high-refractive-index dielectric layer and the low-refractive-index dielectric layer, the lower the total number and thickness of the dielectric multilayer film. It is possible to improve the optical characteristics. For this reason, a material having a high refractive index is required more than ever as a high refractive index dielectric.

  Examples of the high refractive index dielectric include tantalum oxide, niobium oxide, titanium oxide, silicon nitride, and the like. Among these, titanium oxide is exemplified as one having a high refractive index. Examples of the low refractive index dielectric include magnesium fluoride and silicon oxide. Among these, silicon oxide is exemplified as a material having good heat resistance.

  The refractive index of titanium oxide varies depending on the crystal structure. For example, the refractive index at a wavelength of 550 nm, the refractive index of the amorphous type is 2.2 to 2.32, the refractive index of the anatase type is 2.53, and the refractive index of the rutile type. The rate is 2.66. From the viewpoint of improving optical characteristics, a rutile type capable of obtaining a high refractive index is preferable. Conventionally, a method of heat-treating at a high temperature of 900 ° C. or higher is known to obtain rutile-type titanium oxide, but it has not always been easy to obtain rutile-type titanium oxide by heat treatment at a relatively low temperature. For this reason, it is known to obtain a rutile type titanium oxide by containing various dopants.

  For example, a dopant group consisting of Nb, Ta, Mo, As, Sb, Al, Hf, Si, Ge, Zr, W, Co, Fe, Cr, Sn, Ni, V, Mn, Tc, Re, P, and Bi It is known that rutile-type titanium oxide is obtained by adding one or two or more selected from (for example, see Patent Document 1). However, it is heated to 150 ° C. or higher at the time of film formation, and is not heat-treated after film formation, and the influence of the dopant on the heat treatment is not necessarily clear.

  In addition, it is known to form a photocatalytic film using a sputtering source containing titanium oxide and a small amount of Cr, V, Fe, or Ni (see, for example, Patent Document 2). However, general anatase type titanium oxide is used for the photocatalyst, and it is not always clear that rutile type titanium oxide can be obtained. Furthermore, the film is heated to 200 ° C. or higher at the time of film formation, and is not heat-treated after film formation, and the influence of the dopant on the heat treatment is not necessarily clear.

Furthermore, it is known that sputtering is performed using a metal-doped TiO _x target containing a dopant (where x is 0.5 to 1.99) (see, for example, Patent Document 3). However, the specific effects of dopants other than Nb are not always clear. Furthermore, the film is heated to 200 ° C. or higher at the time of film formation, and is not heat-treated after film formation, and the influence of the dopant on the heat treatment is not necessarily clear.

  It is also known that after forming a precursor layer made of titanium oxide to which a dopant is added, the precursor layer is heat-treated in a reducing atmosphere to obtain a metal oxide layer (see, for example, Patent Document 4). . However, the specific effects of dopants other than Nb are not always clear. Further, the film is heated to 200 ° C. or more during film formation, and anatase-type titanium oxide is obtained by heat treatment, but it is not necessarily clear that rutile-type titanium oxide is obtained.

International Publication No. 2009/028569 Pamphlet Japanese Patent Laid-Open No. 2001-104798 JP 2006-144052 A JP 2008-084824 A

  The present invention has been made to solve the above problems, and is a method for producing a laminate having a titanium oxide layer mainly composed of rutile-type titanium oxide, and the temperature during film formation can be made 150 ° C. or lower. And it aims at providing the manufacturing method of the laminated body which can make heat processing temperature after film-forming into comparatively low temperature like 750 degrees C or less. Moreover, an object of this invention is to provide the laminated body manufactured by such a manufacturing method.

  The manufacturing method of the laminated body of this invention has a film-forming process and a heat treatment process. The film forming step uses a titanium target containing 1 to 5 atomic% of at least one additive element selected from Ni, Fe, and Cu on a transparent substrate having a temperature of 150 ° C. or lower, and is a precursor by sputtering. Deposit layers. In the heat treatment step, the transparent substrate on which the precursor layer is formed is heat treated at a temperature of 550 to 750 ° C. to obtain a laminate having a titanium oxide layer mainly composed of rutile titanium oxide.

  The laminate of the present invention has an optical film composed of a dielectric multilayer film in which high refractive index dielectric layers and low refractive index dielectric layers are alternately laminated on a transparent substrate. The high refractive index dielectric layer is composed of a titanium oxide layer formed by the above-described laminate manufacturing method of the present invention.

  According to the method for manufacturing a laminate of the present invention, titanium oxide mainly composed of rutile titanium oxide at a relatively low temperature, such as a film forming temperature of 150 ° C. or lower and a heat treatment temperature after film formation of 750 ° C. or lower. A laminate having layers can be produced. Moreover, according to the laminated body of this invention, since it has the titanium oxide layer formed by the manufacturing method of this invention, it is excellent in productivity.

Sectional drawing which shows typically one Embodiment of a laminated body. Sectional drawing which shows an example of the usage example of a laminated body typically. Sectional drawing which shows the other example of the usage example of a laminated body typically.

Hereinafter, the manufacturing method of the laminated body of this invention and embodiment of a laminated body are demonstrated.
The manufacturing method of the laminated body of embodiment has a film-forming process and a heat treatment process. The film forming step is performed from a titanium oxide by a sputtering method using a titanium target containing 1 to 5 atomic% of at least one element selected from Ni, Fe, and Cu on a transparent substrate having a temperature of 150 ° C. or lower. A main precursor layer is formed. In the heat treatment step, the transparent substrate on which the precursor layer is formed is heat treated at a temperature of 550 to 750 ° C. to obtain a titanium oxide layer mainly composed of rutile type titanium oxide.

  Here, mainly consisting of rutile type titanium oxide means that the ratio of rutile type titanium oxide to the total amount of anatase type titanium oxide and rutile type titanium oxide in the titanium oxide layer (rutile type titanium oxide / (anatase type titanium oxide). + Rutile type titanium oxide)) means 80% or more.

  According to the laminate manufacturing method of the embodiment, the precursor layer is formed by sputtering using a titanium target containing 1 to 5 atomic% of at least one element selected from Ni, Fe, and Cu. Thus, the temperature of the transparent substrate during film formation of the precursor layer can be made 150 ° C. or lower, and a titanium oxide layer mainly composed of rutile-type titanium oxide can be obtained at a relatively low temperature such as a subsequent heat treatment temperature of 750 ° C. or lower. Can do. Hereinafter, each step will be specifically described.

  As already described, the film forming step uses a titanium target containing 1 to 5 atomic% of at least one additive element selected from Ni, Fe, and Cu on a transparent substrate having a temperature of 150 ° C. or lower. A precursor layer is formed by sputtering.

The precursor layer becomes a titanium oxide layer mainly composed of rutile-type titanium oxide by a heat treatment step which is a subsequent step. Examples of the precursor layer include those made of amorphous titanium oxide, those made of anatase-type titanium oxide, and those made of anatase-type titanium oxide and a small amount of rutile-type titanium oxide. Also good. Moreover, the precursor layer may have an oxygen defect, for example, it may be represented by a general formula: TiO _2-x (x is a real number satisfying 0 <x ≦ 1). Good. Furthermore, the precursor layer may be formed directly on the transparent substrate, or may be formed on the transparent substrate via another layer.

  The transparent substrate is not particularly limited, and for example, there is an inorganic transparency such as window glass for vehicles, particularly automobiles, commonly used float glass, or soda lime glass produced by a roll-out method. Some glass plates can be used. The glass plate can be used with clear glass, colorless glass such as high transmission glass, or green colored glass such as heat ray absorbing glass, but considering visible light transmittance, clear glass, high transmission glass, etc. Colorless glass is preferred. Various tempered glasses such as air-cooled tempered glass and chemically tempered glass can also be used. Furthermore, various glasses such as borosilicate glass, low expansion glass, zero expansion glass, low expansion crystallized glass, and zero expansion crystallized glass can be used. Although the thickness of a transparent base | substrate is not necessarily restrict | limited, For example, 1-20 mm is preferable.

  In the film forming step, a titanium target containing 1 to 5 atomic% of at least one additive element selected from Ni, Fe, and Cu is used as a sputtering target. That is, a titanium target in which the ratio of the total amount of additive elements to the total amount of Ti and at least one additive element selected from Ni, Fe, and Cu is 1 to 5 atomic% is used. An additive element may contain only 1 type and may contain 2 or more types. In addition, although it is preferable that a titanium target does not contain additive elements other than Ni, Fe, and Cu fundamentally, you may contain it in the range which has no influence (for example, 1 atomic% or less).

  Although the effects of the additive elements are not necessarily the same, when the ratio of the additive elements in the total amount is less than 1 atomic%, there is a possibility that a titanium oxide layer mainly composed of rutile-type titanium oxide cannot be obtained by the heat treatment process which is a subsequent process. is there. On the other hand, when the ratio of the total amount of the additive elements exceeds 5 atomic%, the visible light absorptance of the titanium oxide layer increases and the generation of haze increases. In addition, the titanium oxide layer may not be a dielectric. From the viewpoint of efficiently obtaining a titanium oxide layer mainly composed of rutile-type titanium oxide, the ratio of the additive element is preferably 1.5 atomic% or more, and more preferably 2 atomic% or more. In addition, the ratio of the total amount of the additive elements is preferably 4.5 atomic percent or less, and more preferably 4 atomic percent or less, from the viewpoint of optical properties such as visible light absorption rate and haze.

  The sputtering method is not particularly limited, and various methods such as a DC (direct current) sputtering method, an AC (alternating current) sputtering method, a high frequency sputtering method, and a magnetron sputtering method can be applied. Among these, the DC sputtering method and the AC sputtering method are preferable because the process is stable and film formation on a large area is easy.

The sputtering method is preferably a reactive sputtering method performed by introducing a reactive gas. The sputtering pressure during film formation is preferably from 0.1 to 3 Pa, more preferably from 0.2 to 0.5 Pa. As the reactive gas, a gas containing at least an oxidizing gas is used, and a mixed gas of an inert gas and an oxidizing gas is preferably used. As the inert gas, one or more selected from Ar, He, Ne, Kr, and Xe can be used. As the oxidizing gas, one or more selected from O ₂ , O ₃ , H ₂ O, and CO ₂ can be used. Among these, O ₂ is preferable from the viewpoint of safety and maintenance of the film forming apparatus.

  The concentration of the oxidizing gas in the reactive gas can be adjusted by adjusting the ratio between the flow rate of the inert gas and the flow rate of the oxidizing gas. The flow rate of the oxidizing gas is preferably 20 to 100% by volume and more preferably 20 to 30% by volume in the reactive gas.

  The temperature of the transparent substrate is not particularly limited as long as it is 150 ° C. or lower. Here, the temperature of the transparent substrate rises as the film formation time becomes longer. In this case, the temperature when the temperature is highest is set to 150 ° C. or lower. If the temperature exceeds 150 ° C., a separate heating facility may be required, which is not efficient from the viewpoint of cost and productivity. The temperature of the transparent substrate is not necessarily limited as long as it is 150 ° C. or lower, and also varies depending on the type of additive element, but is preferably 100 ° C. or higher from the viewpoint of efficiently obtaining a titanium oxide layer mainly composed of rutile-type titanium oxide. 105 ° C. or higher is more preferable, and 110 ° C. or higher is more preferable.

  The thickness of the precursor layer varies slightly depending on the type of additive element, but is preferably 300 nm or less. The thickness is a geometric thickness unless otherwise specified. By setting the thickness of the precursor layer to 300 nm or less, it can be made suitable for a dielectric multilayer film, and the temperature of the transparent substrate can be maintained at 150 ° C. or less. The thickness of the precursor layer is preferably 10 nm or more, more preferably 50 nm or more, from the viewpoint of efficiently obtaining a titanium oxide layer mainly composed of rutile-type titanium oxide. In addition, also about the thickness of the titanium oxide layer obtained by heat-processing a precursor layer, 10 nm or more and 300 nm or less are preferable.

  In the heat treatment step, the transparent substrate on which the precursor layer is formed is heat treated at 550 to 750 ° C., and the titanium oxide of the precursor layer is phase-shifted to form a titanium oxide layer mainly composed of rutile titanium oxide. The heat treatment step can be performed in the atmosphere. When the heat treatment temperature is less than 550 ° C., the phase transition to the rutile type titanium oxide cannot be sufficiently performed. A heat treatment temperature of 750 ° C. is sufficient for the phase transition to rutile-type titanium oxide, and it is preferable to set the heat treatment temperature below this. Moreover, if it is 600-700 degreeC, since the manufacturing process of the conventional curved glass, especially a bending process can be applied as it is, it is more preferable.

  Here, it is mainly composed of rutile-type titanium oxide, as already described, the ratio of rutile-type titanium oxide to the total amount of anatase-type titanium oxide and rutile-type titanium oxide in the titanium oxide layer (rutile-type titanium oxide). / (Anatase type titanium oxide + rutile type titanium oxide)) means 80% or more. In general, when titanium oxide in an amorphous state or the like is heat-treated, one containing only anatase-type titanium oxide, one containing only rutile-type titanium oxide, or one containing both of these is often obtained. .

The ratio by mass of rutile type titanium oxide in the titanium oxide layer is determined by observing the crystal structure with an X-ray diffractometer. Specifically, in the diffraction spectrum obtained by the X-ray diffractometer, the integrated intensity I _A of the diffraction peak of the (101) plane of anatase type titanium oxide and the integrated intensity of the diffraction peak of the (110) plane of rutile type titanium oxide. the I _R calculated respectively, are calculated from the resulting integrated intensity by the following equation.
R = {1 / (1 + 0.79I A / I R)} × 100

  From the viewpoint of making the titanium oxide layer have a high refractive index, the ratio by mass of the rutile-type titanium oxide in the titanium oxide layer is preferably 85% or more, more preferably 90% or more, and further preferably 95% or more. The said ratio can be adjusted with the content of the additive element in the titanium target used for a film-forming process, the temperature of the transparent base | substrate in the process, the heat processing temperature and heat processing time in a heat processing process, for example.

  The heat treatment time is not necessarily limited as long as the titanium oxide of the precursor layer is phase-shifted to obtain a titanium oxide layer mainly composed of rutile-type titanium oxide, but from the viewpoint of sufficient phase-transition to rutile-type titanium oxide, One minute or more is preferable. The heat treatment time is more preferably 1 minute or more, and further preferably 5 minutes or more. A heat treatment time of 30 minutes is sufficient for phase transition to the rutile titanium oxide, and productivity can be improved by setting it below this time. The heat treatment time is more preferably 20 minutes or less, and further preferably 15 minutes or less.

  Note that the heat treatment process is not necessarily performed for each film formation process. For example, after performing only a plurality of film forming steps, that is, after stacking a plurality of precursor layers directly or indirectly through other films, a heat treatment step is performed to heat the plurality of precursor layers together. A plurality of titanium oxide layers mainly composed of rutile-type titanium oxide may be obtained. According to such a method, a dielectric multilayer film having a plurality of titanium oxide layers can be efficiently manufactured.

  Further, the heat treatment step is not necessarily limited to the purpose of phase transition of titanium oxide, and can be a predetermined heat treatment temperature and can be sufficiently phase-transformed into rutile titanium oxide. There is no particular limitation. For example, as the heat treatment step, bending heating accompanied by heating performed when manufacturing curved glass such as an automobile windshield may be used.

  A curved glass such as a windshield for an automobile is formed by, for example, forming an optical film such as a dielectric multilayer film on a flat glass, then cutting the flat glass having the optical film and bending it in a high temperature environment of 550 ° C. or higher. Manufactured by performing. By utilizing such heating for bending as a heat treatment step, it is not necessary to newly provide a heat treatment step, and a conventional manufacturing process can be applied as it is. According to the manufacturing method of the embodiment, since the heat treatment temperature is 750 ° C. or lower, heating for bending can be suitably used.

Hereinafter, the specific example of the laminated body manufactured by the manufacturing method of embodiment is demonstrated.
FIG. 1 is a cross-sectional view showing an embodiment of a laminate.

  The laminate 10 includes a transparent substrate 11 and an optical film 12 laminated on the transparent substrate 11. The optical film 12 is, for example, a dielectric multilayer film, and has an alternately laminated structure in which high refractive index dielectric layers 121 and low refractive index dielectric layers 122 are alternately laminated. Among these, at least a part, preferably all, of the high refractive index dielectric layer 121 is a titanium oxide layer formed by the manufacturing method of the embodiment, that is, a titanium oxide layer mainly composed of rutile type titanium oxide.

  Examples of the optical film 12 include an infrared reflection film for preventing an increase in the in-vehicle temperature and an antireflection film for reducing the reflection of a dashboard.

  Although the infrared reflective film as the optical film 12 is not necessarily limited, it is preferable that the total number of the high refractive index dielectric layer 121 and the low refractive index dielectric layer 122 is five or more. By setting the total number of the high refractive index dielectric layer 121 and the low refractive index dielectric layer 122 to 5 or more, the visible light transmittance and the reflectance in the near infrared region can be increased. The total number of layers of the high-refractive index dielectric layer 121 and the low-refractive index dielectric layer 122 is preferably 13 or less from the viewpoint of achieving both optical characteristics and productivity.

  When a plurality of high-refractive index dielectric layers 121 are present in the infrared reflective film, at least one high-refractive index dielectric layer 121 may be a titanium oxide layer formed by the manufacturing method of the embodiment. The high refractive index dielectric layer 121 is preferably a titanium oxide layer formed by the manufacturing method of the embodiment.

  When a dielectric layer other than the titanium oxide layer formed by the manufacturing method of the embodiment is used as the high refractive index dielectric layer 121, the refractive index (refractive index at a wavelength of 550 nm, the same applies hereinafter) is 1.90 or higher. Those made of a refractive index dielectric are preferred. Examples of such a dielectric include various metal oxides.

  Examples of the metal oxide include those containing as a main component an oxide of at least one metal selected from tin, zinc, niobium, tantalum, zirconium, and hafnium. The at least one high refractive index dielectric layer 121 is a titanium oxide layer formed by the manufacturing method of the embodiment, and preferably all the high refractive index dielectric layers 121 are formed by the manufacturing method of the embodiment. It is a titanium oxide layer.

  The low refractive index dielectric layer 122 is preferably made of a low refractive index dielectric having a refractive index of 1.5 or less, preferably 1.2 to 1.5. Such a dielectric is preferably made of at least one selected from low refractive index dielectrics such as silicon oxide and magnesium fluoride.

  The thickness of the high refractive index dielectric layer 121 is not necessarily limited, but is preferably 90 to 120 nm, and more preferably 90 to 115 nm. The thickness of the low refractive index dielectric layer 122 is not necessarily limited, but is preferably 150 to 190 nm, and more preferably 155 to 185 nm. With such a thickness, the visible light transmittance is high and the infrared reflectance can be improved.

  In the case where there are a plurality of high refractive index dielectric layers 121, the thickness of the uppermost layer is preferably 5 to 30 nm, more preferably 6 to 25 nm. Further, when there are a plurality of low refractive index dielectric layers 122, the thickness of the uppermost layer is preferably 8 to 50 nm, more preferably 10 to 45 nm. By setting it as such, the surface color tone can be set to an intermediate color tone that does not have a stimulating color.

  The antireflection film as the optical film 12 is not necessarily limited, but preferably has a total number of layers of 4 or more including the high refractive index dielectric layer 121 and the low refractive index dielectric layer 122. The total number of the high-refractive index dielectric layer 121 and the low-refractive index dielectric layer 122 is preferably 10 or less from the viewpoint of achieving both optical properties and productivity.

  When a plurality of high refractive index dielectric layers 121 are present in the antireflection film, at least one high refractive index dielectric layer 121 may be a titanium oxide layer formed by the manufacturing method of the embodiment, preferably All the high refractive index dielectric layers 121 are titanium oxide layers formed by the manufacturing method of the embodiment. The high-refractive index dielectric layer 121 and the low-refractive index dielectric layer 122 other than the titanium oxide layer formed by the manufacturing method of the embodiment of the antireflection film can be made of the same material as that of the infrared reflection film.

  The thickness of the high refractive index dielectric layer 121 in the antireflection film is not necessarily limited, but is preferably 80 to 120 nm, and more preferably 90 to 110 nm. The thickness of the low refractive index dielectric layer 122 in the antireflection film is not necessarily limited, but is preferably 80 to 120 nm, and more preferably 90 to 110 nm. In addition, when there are a plurality of high refractive index dielectric layers 121, the thickness of the lowermost layer is preferably 5 to 30 nm, and more preferably 6 to 25 nm. In the case where there are a plurality of low refractive index dielectric layers 122, the thickness of the uppermost layer is preferably 10 to 50 nm, and more preferably 15 to 45 nm.

  The infrared reflection film as the optical film 12 is not necessarily limited to the infrared reflection film made of a dielectric multilayer film, and for example, an oxide layer and a metal layer may be alternately laminated. The total number of oxide layers and metal layers is preferably 3 or more. The total number of oxide layers and metal layers is preferably 9 or less.

  For those having an oxide layer and a metal layer, the oxide layer is a titanium oxide layer formed by the manufacturing method of the embodiment. When there are a plurality of oxide layers, at least one oxide layer may be a titanium oxide layer formed by the manufacturing method of the embodiment, and all oxide layers are formed by the manufacturing method of the embodiment. It may be a titanium oxide layer.

  When an oxide layer other than the titanium oxide layer formed by the manufacturing method of the embodiment is used as the oxide layer, an oxide layer made of a high refractive index material having a refractive index of 1.90 or more is preferable. As such an oxide layer, what consists of various metal oxides is mentioned.

  Examples of the metal oxide constituting the oxide layer include an oxide mainly composed of an oxide of at least one metal selected from tin, zinc, niobium, tantalum, zirconium, indium, and hafnium. On the other hand, the metal constituting the metal layer is mainly composed of silver and can be composed of only silver or an alloy composed mainly of silver. Constituent components other than silver are, for example, palladium, gold, copper, etc., and the content of these constituent components other than silver is preferably 0.3 to 10 atomic% in total.

  The thickness of the oxide layer and the metal layer varies depending on the total number of layers and the constituent materials of each layer. For example, each oxide film is preferably 5 to 100 nm, each metal film is preferably 5 to 20 nm, and all oxides are oxidized. The total layer thickness of the physical film and the metal film is preferably 50 to 400 nm, more preferably 150 to 300 nm.

  FIG. 2 shows an example of use of the laminate 10 and shows an example of use for a laminated glass having an infrared reflecting film as a windshield for vehicles, particularly for automobiles.

  In the laminated glass 30, another transparent substrate 14 is bonded to the optical film 12 side of the laminate 10 via an intermediate film 13 such as polyvinyl butyral (PVB). The laminated body 10 has an infrared reflecting film as the optical film 12, and is provided, for example, in a curved shape such that the optical film 12 side is concave, and the optical film 12 side is the vehicle interior side. As the other transparent substrate 14, the same transparent substrate 11 as that of the laminate 10 can be used.

Such a laminated glass 30 can be manufactured as follows, for example.
First, the optical film 12 is formed by alternately laminating the high refractive index dielectric layers 121 and the low refractive index dielectric layers 122 on the flat transparent substrate 11. At this time, the precursor layer is formed by performing the film forming step in the manufacturing method of the embodiment on at least a part, preferably all, of the plurality of high refractive index dielectric layers 121. The other high refractive index dielectric layer 121 and low refractive index dielectric layer 122 can be manufactured by a known manufacturing method. Hereinafter, the transparent substrate 11 on which the optical film 12 is formed is referred to as a laminate precursor 10.

  Thereafter, a release agent is applied onto the optical film 12 of the laminate precursor 10, and another uncurved flat plate-like transparent substrate 14 is overlaid on the release agent, and then the whole is bent. Place on mold. The mold has, for example, a shape that supports the peripheral edge of the laminate precursor 10 from below. In this state, the laminated body precursor 10 and the other transparent substrate 14 have a flat plate shape that is not curved.

  Next, the laminated body precursor 10 and the other transparent substrate 14 are softened by heating to 600 ° C. or higher while the peripheral portions of the laminated body precursor 10 and the other transparent substrate 14 are supported from below by the molding die. Is bent by its own weight bending. Note that bending by press bending may be performed instead of bending by self-weight bending. As a result, the laminate precursor 10 and the other transparent substrate 14 have a curved shape similar to the product shape. At this time, the heat treatment step in the manufacturing method of the embodiment is performed at the same time, and the titanium oxide of the precursor layer undergoes phase transition to obtain a titanium oxide layer mainly composed of rutile titanium oxide. As a result, the laminate 10 is obtained. It is done. Thereafter, the laminate 10 and the other transparent substrate 14 are cooled and separated, and then washed to remove the release agent.

  After removal of the release agent, an intermediate film 13 such as flexible PVB is overlaid on the optical film 12 of the laminate 10, and another transparent substrate 14 is further overlaid, and thermocompression bonding is performed. Thus, the laminated glass 30 can be manufactured. The laminated body precursor 10 and the other transparent substrate 14 do not necessarily need to be overlapped and bend, and may be bent by self-weight bending or press bending with a single plate.

  FIG. 3 shows another example of use of the laminated body 10, and shows a laminated glass having an antireflection film as a windshield for vehicles, particularly for automobiles. In the laminated glass 40, another transparent substrate 14 is bonded to the transparent substrate 11 side of the laminate 10 via an intermediate film 13 such as PVB. The laminated body 10 has an antireflection film as the optical film 12, and is provided, for example, in a curved shape such that the optical film 12 side is concave and the optical film 12 side is the vehicle interior side. Such a laminated glass 30 can also be manufactured by performing a bending process in the same manner as in the method for manufacturing the laminated glass 30 having the infrared reflecting film.

  As mentioned above, although the manufacturing method of embodiment was demonstrated, as a laminated body manufactured by the manufacturing method of embodiment, it does not necessarily restrict | limit to the thing in which a several titanium oxide layer is provided on a transparent substrate, A single on a transparent substrate The titanium oxide layer may be provided. In addition, the laminate manufactured by the manufacturing method of the embodiment is not necessarily limited to a windshield for automobiles, and may be a side glass or a rear glass for automobiles, for railway vehicles, and further for aircraft and architecture. There may be. Furthermore, a front plate or the like in a flat display such as a liquid crystal display or a plasma display may be used.

Next, specific examples of the present invention and evaluation results thereof will be described.
In addition, the following description does not limit this invention, The modification | change in the form along the meaning of this invention is possible.

(Example 1)
A soda lime glass (100 mm × 100 mm) as a transparent substrate is formed by a reactive sputtering method using a DC pulse power source (manufactured by Advanced Energy) using a titanium target (Ti-3 at% Ni) containing 3 atomic% of Ni as a sputtering target. 100 nm × 2 mmt), a titanium oxide layer doped with Ni was formed as a precursor layer. The precursor layer was formed by setting the total pressure to 0.3 Pa, the applied power to 1000 W, and introducing 40 sccm of argon and 10 sccm of oxygen as inert gases.

  At this time, the film was formed by changing the temperature of the transparent substrate within a range of 90 to 150 ° C. In addition, as the temperature of the transparent substrate, the surface temperature of the precursor layer was measured with a thermo label (manufactured by NOF Corporation). The surface temperature of the precursor layer was adjusted by changing the film formation time by changing the thickness of the precursor layer, and the temperature when the temperature was highest was defined as the surface temperature.

  After film formation of the precursor layer, the transparent substrate provided with the precursor layer was heat-treated at 700 ° C. for 17 minutes using a belt furnace (manufactured by DENKO) to obtain a laminate.

(Example 2)
A laminate was obtained in the same manner as in Example 1 except that a titanium target containing 3 atomic% Fe (Ti-3 at% Fe) was used as the sputtering target.

(Example 3)
A laminate was obtained in the same manner as in Example 1 except that a titanium target containing 3 atomic% of Cu (Ti-3 at% Cu) was used as the sputtering target.

(Example 4)
A laminate was obtained in the same manner as in Example 1 except that a titanium target (Ti) was used as the sputtering target.

  About the laminated body obtained by the manufacturing method of Examples 1-4, the crystal structure was evaluated as shown below.

(Crystal structure)
The crystal structure of the titanium oxide layer in the laminate was measured using an X-ray diffractometer (manufactured by Shimazdu, trade name: RINT-2500). As the X-ray source, a tube current of 200 mA, a tube voltage of 200 V, and CuKα rays were used. The incident angle ω was fixed at 0.5 degrees, and the measurement was performed in the range of 20 to 40 degrees.

The obtained diffraction spectrum was subjected to background removal and diffraction peak search using analysis software (JADE 6.0), and the integrated intensity I _A of the diffraction peak on the (101) plane of anatase-type titanium oxide, the integrated intensity I _R of the diffraction peak of the (110) plane of rutile-type titanium oxide was calculated. The mass ratio was calculated from the obtained integrated intensity by the following formula.
R = {1 / (1 + 0.79I A / I R)} × 100

  Table 1 summarizes the temperature of the transparent substrate during deposition (surface temperature of the precursor layer) and the crystal structure and thickness of the titanium oxide layer after heat treatment. In addition, about a part, the ratio in the mass of the rutile type titanium oxide with respect to the total amount of anatase type titanium oxide and a rutile type titanium oxide was written together.

  In Table 1, “An” indicates that only anatase-type titanium oxide, “An + R” indicates that anatase-type titanium oxide and rutile-type titanium oxide, and “−” indicates that production and evaluation are not performed. The numerical value in parentheses written together with “An + R” indicates the ratio of the mass of rutile type titanium oxide to the total amount of anatase type titanium oxide and rutile type titanium oxide.

  Of Examples 1 to 3, the crystal structure is represented by “An + R” and the numerical value in parentheses is 80% or more is an example of the present invention.

  As is apparent from Table 1, according to the production methods of Examples 1 to 3 using a titanium target containing 3 atomic% of Ni, Fe, or Cu as a sputtering target, it also depends on the temperature of the transparent substrate during film formation. However, the heat treatment temperature is set to 700 ° C., and only the rutile type titanium oxide, or the anatase type and the rutile type titanium oxide, and the ratio of the rutile type titanium oxide by mass is 80% or more can be obtained. I understand that.

  In particular, by using a titanium target containing Ni as in the production method of Example 1, an anatase-type and rutile-type titanium oxide having a ratio by mass of rutile-type titanium oxide of 80% or more is obtained. It turns out that it is easy.

  On the other hand, in the production method of Example 4 using a titanium target that does not contain any of Ni, Fe, and Cu as the sputtering target, only a rutile type titanium oxide having a mass ratio of 40% or less can be obtained. I understand that. Although not shown in the table, even when a titanium target containing 3 atomic% of Nb is used, only a rutile type titanium oxide having a mass ratio of 40% or less can be obtained. It can be seen that the use of a titanium target containing at least one selected from Cu and Cu is effective for obtaining a titanium oxide layer mainly composed of rutile titanium oxide.

  DESCRIPTION OF SYMBOLS 10 ... Laminated body, 11 ... Transparent base | substrate, 12 ... Optical film, 13 ... Intermediate film, 14 ... Other transparent base | substrates, 30 ... Laminated glass, 121 ... High refractive index dielectric film, 122 ... Low refractive index dielectric film,

Claims (7)

On a transparent substrate having a temperature of 150 ° C. or lower, a precursor layer is formed by sputtering using a titanium target containing 1 to 5 atomic% of at least one additive element selected from Ni, Fe, and Cu. A film forming process;
A heat treatment step of heat-treating the transparent substrate on which the precursor layer is formed at a temperature of 550 to 750 ° C. to obtain a titanium oxide layer mainly composed of rutile-type titanium oxide. .   The method for manufacturing a laminate according to claim 1, wherein the titanium oxide layer is a dielectric.   The method for manufacturing a laminate according to claim 1 or 2, wherein the titanium oxide layer has a thickness of 10 to 300 nm.   The method for producing a laminate according to any one of claims 1 to 3, wherein the transparent substrate is soda lime glass.   The method for producing a laminate according to any one of claims 1 to 4, wherein the transparent substrate is glass for automobiles. A laminate having an optical film composed of a dielectric multilayer film in which a high refractive index dielectric layer and a low refractive index dielectric layer are alternately laminated on a transparent substrate,
The laminated body, wherein the high refractive index dielectric layer is a titanium oxide layer formed by the method for producing a laminated body according to any one of claims 1 to 5.   The laminate according to claim 6, wherein the optical film is an infrared reflection film or an antireflection film.

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