CN101243022B - Infrared reflection glass plate and laminated glass for vehicle window - Google Patents

Infrared reflection glass plate and laminated glass for vehicle window Download PDF

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CN101243022B
CN101243022B CN2006800300550A CN200680030055A CN101243022B CN 101243022 B CN101243022 B CN 101243022B CN 2006800300550 A CN2006800300550 A CN 2006800300550A CN 200680030055 A CN200680030055 A CN 200680030055A CN 101243022 B CN101243022 B CN 101243022B
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tunicle
film
layer
infrared reflection
range
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CN101243022A (en
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矢尾板和也
见矢木崇平
片山佳人
木村幸雄
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AGC Inc
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Asahi Glass Co Ltd
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Abstract

A laminated glass for vehicle window capable of preventing an in-car temperature increase. There is provided an infrared reflective glass plate consisting of a glass plate with infrared reflective film, characterized in that the infrared reflective film has laminated coating (X) composed of coatings (1) of an inorganic material whose refractive index is as high as 1.90 or higher and coatings (2) of an inorganic material whose refractive index is as low as 1.56 or below, alternately superimposed on each other in the above order from the glass plate side, and that the sum of the number of coatings (1) and the number of coatings (2) is 3 or greater, and that the geometrical thickness of each of the coatings (1) is in the range of 70 to 150 nm while the geometrical thickness of each of the coatings (2) is in the range of 100 to 200 nm.

Description

Infrared reflection glass plate and laminated glass for vehicle window
Technical field
The present invention relates to infrared reflection glass plate and laminated glass for vehicle window.
Background technology
The window glass of vehicle, particularly automobile can possess infrared reflection film in order to prevent vehicle interior temperature from rising.In the past, in order to bring into play high IR line reflection performance, infrared reflection film can use with the mf of the silver type conductive membrane as representative.But if at sheet glass laminated conductive membrane, then electric wave-transparent can significantly descend.And under this situation, the decline of electric wave-transparent ability is the wide band decline of covering near infrared region to electric wave zone.Electric wave-transparent can decline cause the decline of the receptivity of the work of infrared detection instruments such as light beacon, misty rain transmitter not normal or TV, receiving set etc.Therefore, the vehicle that has these functions is difficult to carry the window glass with high IR line reflection performance.
So; As guaranteeing that electric wave-transparent can and shield ultrared window glass, begin to adopt the laminated glass that has used the intermediate coat that forms by the polyvinyl butyral acetal that disperses to have mixed infrared shield property particulate etc. (below be called " microparticulate intermediate coat ") gradually (for example with reference to patent documentation 1; Laminated glass to call the type in the following text is " laminated glass that contains particulate ").Contain in the laminated glass of particulate; For example through using tin-doped indium oxide (below be called " ITO ") particulate as infrared shield property particulate; Can give intermediate coat infrared shield performance by the ITO particulate, and pass through the dispersion of ITO particulate, can increase the sheet resistance value of intermediate coat.Therefore, the laminated glass that contains particulate can be used as guarantees that electric wave-transparent can and shield ultrared window glass.
But for the window glass that requires higher infrared shield performance, the laminated glass that contains particulate is considered to exist following weakness.One of which, the shielding of light that is considered near the wavelength region of ultra-red only, the for example the 1000nm very not high prior art of patent documentation 2 (for example with reference to).Its two, be considered in the microparticulate intermediate coat, infra-red absorption take place, therefore absorbed sunshine, energy was discharged in the car prior art of patent documentation 3 (for example with reference to) again.
Patent documentation 1: Japanese Patent Laid is opened the 2001-151539 communique
Patent documentation 2: Japanese Patent Laid is opened the 2005-89244 communique
Patent documentation 3: Japanese Patent Laid is opened the 2004-26547 communique
The announcement of invention
In the patent documentation 2, constitute that 1 sheet glass in the sheet glass of the laminated glass contain particulate has been provided with low-index layer periodically range upon range of and the infrared reflection film of the structure of high refractive index layer.Thus, can realize high heat-proof quality.
As this infrared reflection film, use metal, oxide compound, the unitary film of nitride or their stacked film, the thickness of each layer is recited as, and metallic membrane is below 10nm, and nitride is below 15nm.In addition, if with reference to embodiment, used oxide compounds such as ZnO, CrO, NiCrO, TiO, SSTO (stainless oxide compound), SnO and SiO, their thickness all is number nanometer～tens nanometer (maximum 38nm).
But the laminated glass of being put down in writing in the patent documentation 2 that contains particulate does not have the such high heat-proof quality of being thought.That is,, also can't make transsmissivity T at sunshine even possess the laminated glass that this contains particulate eEnough little and sunshine reflectivity R eEnough big.That is, these laminated glass that contain particulate are used under the situation of vehicle window because reflectivity is low, if therefore hope to suppress transsmissivity, then must increase laminated glass sunshine energy absorbed dose.Consequently, because the energy at sunshine that is absorbed by laminated glass is discharged into the car inboard again, thereby can't fully suppress the rising of vehicle interior temperature.
Sunshine, reflectivity was considered to owing to following reason for a short time.The film that is used to reflect the light of particular wavelength region need make its " optical thickness " to be the integral multiple of λ/4 (λ represent to hope reflect light wavelength).If the light with the 800nm of the short wavelength side of infrared spectral range is that example describes, then the optical thickness of infrared reflection film (being each layer under the situation of stacked film) is at least 200nm.
" optical thickness " of each layer is with the product representation of its " geometry thickness " and " specific refractory power of the stratified material of structure ".Therefore, use under the situation of the material high like specific refractory poweres such as titanium oxide (supposing that specific refractory power is 2.4), the geometry thickness of film also reaches about 80nm at least.That is,, think to obtain the required optical thickness of infrared reflection according to the geometry thickness of the film of being put down in writing in the patent documentation 2 and the specific refractory power of material.Therefore, infer the infrared reflection performance deficiency of the infrared reflection film of being put down in writing in the patent documentation 2.
In addition; In the patent documentation 3; When making the microparticulate intermediate coat between car outside sheet glass and car inner glass plate, make the film formed infrared reflection film of optical interference multilayer by 2 kinds of different polymeric films of multilayer laminated specific refractory power again between car outside sheet glass and microparticulate intermediate coat.Thus, suppress to be released to the inboard energy (, having quoted No. 6049419 communiques of U.S. Patent bulletin in the patent documentation 3) of car as the example of this infrared reflection film.
But the weather resistance of the end of the infrared reflection film between car outside sheet glass and microparticulate intermediate coat is not good.Therefore, in order to improve weather resistance, need film be cut the operation (return and cut (cut back)) about several centimetres from the end to central part.In addition, infrared reflection film is generally hard film.Vehicle, particularly automobile often are crooked with window, so mostly sheet glass is curved shape.Therefore, if make laminated glass with this film, then the film shape of sheet glass of can't fitting may produce problem of appearance such as forming wrinkle on the film.In addition, also need at the circumference of sheet glass pigmented layer (ceramic coloring layer) be set in order to cover wrinkle.As stated, there is apparent problem in the laminated glass that comprises infrared reflection film, also has the numerous and diverse problem of ME.
In addition, the present inventor finds to turn white after attempting the sample with the film production laminated glass that is equivalent to employed infrared reflection film in the patent documentation 3, and mist degree is big.In addition, the deformation of image that forms through this sample reflection is remarkable, and there is the problem in the visual field in prediction when being used as the windshield glass of automobile.
In addition, employed infrared reflection film may be the film that has mixed dyestuffs such as phthalocyanine in the patent documentation 3.Resinous infrared rays film vibrates in transmitted spectrum, and the reflected colour phenomenon different with the input angle of sunshine (dependence of angle) perhaps takes place.Mixing colouring agent is in order to suppress these phenomenons in film.But dyestuffs such as phthalocyanine have absorption in the ultra-violet region, thus may be because of being exposed to deterioration under the sunshine, and the vibration of reflection spectrum or the dependence of angle of reflected colour become problem.
Therefore, use infrared reflection glass plate to obtain laminated glass among the present invention with specific membrane structure.That is, the present invention has following technology contents.
[1]Infrared reflection glass plate; It is the sheet glass with infrared reflection film; It is characterized in that; This infrared reflection film have the tunicle (1) that forms at the high refractive index inanimate matter material more than 1.90 by specific refractory power and the tunicle (2) that forms at the low-refraction inanimate matter material below 1.56 by specific refractory power from the sheet glass side with this sequence alternate range upon range of and range upon range of tunicle (X); The summation of the quantity of the quantity of aforementioned tunicle (1) and aforementioned tunicle (2) is more than 3, and the geometry thickness of aforementioned tunicle (1) is 70～150nm, and the geometry thickness of aforementioned tunicle (2) is 100～200nm.
[2]Like [1] described infrared reflection glass plate, wherein, at least 1 road in the tunicle (1) is the unitary film (1a) of titanium oxide or titanium oxynitrides.
[3]Like [1] described infrared reflection glass plate; Wherein, The high refractive index multilayer film (1b) that at least 1 road in the tunicle (1) constitutes for the multilayered structure more than 2 layers that is formed by different types of high refractive index inanimate matter material, at least 1 layer in this high refractive index multilayer film (1b) is the layer of titanium oxide or titanium oxynitrides.
[4]Like [3] described infrared reflection glass plate, wherein, at least 1 layer in the high refractive index multilayer film (1b) is the layer of titanium oxide or titanium oxynitrides, and other at least 1 layer is zirconic layer in this high refractive index multilayer film (1b).
[5]Like [1] described infrared reflection glass plate; Wherein, range upon range of tunicle (X) by 2 roads comprise zirconic layer and titanium oxide or titanium oxynitrides layer geometry thickness add up to the high refractive index multilayer film (1b-1) of 70～150nm and the tunicle (2) that is present between this 2 road high refractive index multilayer film (1b-1) forms.
[6]Like each the described infrared reflection glass plate in [1]～[5], wherein, tunicle (2) is the layer of silicon oxide.
[7]Like [1] described infrared reflection glass plate; Wherein, Infrared reflection film has the single layer structure that formed by inanimate matter material or the film (Y) of multilayered structure the sheet glass side of range upon range of tunicle (X) and at least one side in the non-glass plate side, all not enough 70nm of geometry thickness of each of this film layer.
[8]Like [7] described infrared reflection glass plate, wherein, the refringence of the layer of the film that joins (Y) and the tunicle of range upon range of tunicle (X) is more than 0.3.
[9]Like [7] or [8] described infrared reflection glass plate; Wherein, Film (Y) comprises that the geometry thickness that is formed at the high refractive index inanimate matter material more than 1.90 by specific refractory power is the high refractive index layer (c) of 5～40nm and is that the alternately laminated total number of plies that gets of low-index layer (d) of 5～40nm is the even multilayer film by the geometry thickness that specific refractory power forms at the low-refraction inanimate matter material below 1.56, and the layer that joins with the tunicle (1) of range upon range of tunicle (X) is low-index layer (d).
[10]Like [9] described infrared reflection glass plate, wherein, the high refractive index layer (c) of film (Y) is the layer of titanium oxide, and the low-index layer (d) of film (Y) is the layer of silicon oxide.
[11]The precursor of infrared reflection glass plate; It is to form the precursor of each the described infrared reflection glass plate in [1]～[10] through carrying out heat treated; It is characterized in that; All layers corresponding to " titanium oxide or titanium oxynitrides layer " in the tunicle (1) of the infrared reflection glass plate after the heat treated all be the layer of titanium oxynitrides, this titanium oxynitrides layer in titanium oxynitrides be the high titanium oxynitrides of titanium oxynitrides in the infrared reflection glass plate after the ratio heat treated of nitrogen-atoms.
[12]The method of manufacture of infrared reflection glass plate; It is a method of making each the described infrared reflection glass plate in [1]～[10]; It is characterized in that; With the heating of [11] described precursor, the titanium oxynitrides of the layer of the titanium oxynitrides in this precursor is converted into the few titanium oxynitrides or the titanium oxide of titanium oxynitrides in this precursor of ratio that contain of nitrogen-atoms.
[13]Through the method for manufacture of [12] of bending machining described infrared reflection glass plate, wherein,, carry out bending machining with the precursor heating.
[14]Laminated glass for vehicle window; It is to possess the 1st sheet glass, have 2nd sheet glass and the intermediate coat between 1st sheet glass and 2nd sheet glass between of sheet resistance value at the infrared reflection film more than 1k Ω/; And the 1st sheet glass is located at the inboard laminated glass for vehicle window of car; Wherein, the 2nd sheet glass that has an infrared reflection film is each the described infrared reflection glass plate in [1]～[10].
[15]Like [14] described laminated glass for vehicle window, wherein, for from the 2nd sheet glass side incident light, transmission of visible light is more than 70%.
The infrared reflection glass plate of the application of the invention is processed laminated glass for vehicle window, can make not taken in excess and reflect the energy at sunshine as far as possible of laminated glass.Thus, can obtain to suppress to incide the seeing through of energy at sunshine in the car, suppress the laminated glass for vehicle window of the rising of vehicle interior temperature.That is, can when guaranteeing electric wave-transparent, make the energy reflection at sunshine, can reduce the energy at sunshine that is absorbed by laminated glass, suppress the release again of energy at absorbed sunshine, can prevent that the temperature in the car from rising.In addition, the outward appearance of laminated glass of the present invention is good, and manufacturing process also obtains simplifying.The good visual field in addition, can prevent to haze, also not have the distortion of reflected image, so can be provided.
The simple declaration of accompanying drawing
Fig. 1 is the perspective cross-sectional slice of an example of expression laminated glass for vehicle window of the present invention.
Fig. 2 is the perspective cross-sectional slice of an example of expression infrared reflection glass plate of the present invention.
Fig. 3 is the figure (a) of the spectral-transmission favtor of expression sheet glass of the present invention, the figure (b) of expression spectral reflectivity.
Fig. 4 is the figure of the spectral reflectivity of the infrared reflection glass plate of expression example 1,4.
Fig. 5 is the figure of the spectral reflectivity of the infrared reflection glass plate of expression example 2,3,5,6.
Fig. 6 is the figure of the spectral reflectivity of the infrared reflection glass plate of expression example 7,8.
Fig. 7 is the figure of the spectral-transmission favtor of the laminated glass of expression example 1,4.
Fig. 8 is the figure of the spectral reflectivity of the laminated glass of expression example 1,4.
Fig. 9 is the figure of the spectral absorption of the laminated glass of expression example 1,4.
Figure 10 is the figure (a) of the spectral-transmission favtor of the laminated glass of expression example 2,3,5,6,9, the figure (b) of expression spectral reflectivity, the figure (c) of expression spectral absorption.
Figure 11 is the figure (a) of the spectral-transmission favtor of the laminated glass of expression example 7,8,10,11, the figure (b) of expression spectral reflectivity, the figure (c) of expression spectral absorption.
The explanation of symbol
1: laminated glass, 11: the 1 sheet glass, 12: the 2 sheet glass, 20: infrared reflection glass plate, 21: infrared reflection film, 30: intermediate coat.
The best mode that carries out an invention
In the following explanation of the present invention, short of special instruction, infrared rays is meant the long and hertzian wave below 2000nm of its wavelength ratio visible light.Infrared reflection film particularly of the present invention is mainly with the infrared rays of the wavelength of the 800～1600nm object as reflection.The infrared rays of this wavelength region may also is called as near infrared ray.
Sheet glass as the substrate of infrared reflection glass plate of the present invention can be the plate glass plate, also can be processing glass sheets.Among the present invention, processing glass sheets be meant with the plate glass plate be shaped and formed glass sheets strengthen with heat and strengthening glass sheets, can be shaped and heat strengthen and sheet glass.Processing glass sheets gets the hot-work of plate glass plate usually.As hot-work, for example have under heating bending machining plate glass plate, will be through the high temp glass plate chilling of bending machining and processing such as reinforcement.Infrared reflection film is present in the one side of these sheet glass usually.The plate glass plate that bending machining sheet glass with infrared reflection film can maybe will have infrared reflection film through the method that forms infrared reflection film in the one side of bending machining sheet glass carries out the method for bending machining etc. and obtains.Among the present invention, better be to obtain through a kind of method in back, one of the object of the invention is to provide the plate glass plate of the band infrared reflection film that is suitable for this method.
Among the present invention, thermal treatment is meant the heating in the above-mentioned hot-work, but is not limited thereto, and can be meant for certain purpose sheet glass is heated to more than 400 ℃, better is more than 500 ℃.Be limited to the temperature of the glass melting of sheet glass on the thermal treatment temp.In addition, as being used for hot worked infrared reflection glass plate, below the sheet glass that also will implement before the hot-work be called precursor.In addition, among the present invention, veneer is meant 1 sheet glass, also refers to have 1 sheet glass of infrared reflection film sometimes.
Infrared reflection glass plate of the present invention can be well as the window material of vehicles such as automobile.In the vehicle window material, can be laminated glass like windshield glass etc., can be veneer like door glass etc.These window materials have normally been implemented the sheet glass of hot-work (bending machining, reinforcement processing etc.).That is the sheet glass that the reinforcement processing of, carrying out glass sheets bending processing or being used to make laminated glass or veneer glass intensity to improve according to the shape of laminated glass is made.The infrared reflection glass plate of unwarped processing (can process through strengthening) is suitable as the window material of buildings.
Below, the present invention will be described in more detail based on accompanying drawing.
Fig. 2 is the perspective cross-sectional slice of an example of expression the 2nd sheet glass with infrared reflection film of the present invention.This routine infrared reflection glass plate 20 is formed by sheet glass 12 and the infrared reflection film 21 of being located at sheet glass 12.Infrared reflection film 21 is formed by the range upon range of tunicle (X) that the total that is followed successively by tunicle (1), tunicle (2) and tunicle (1) from sheet glass 12 sides 3 road tunicles constitute.In this form, the non-glass side of range upon range of tunicle (X) is range upon range of film (Y).Film (Y) is by high refractive index layer (c) and these 2 layers of formations of low-index layer (d), and low-index layer (d) joins with the tunicle (1) of range upon range of tunicle (X).
As the sheet glass among the present invention, can use soda-lime glass usually.Under this situation, can be in colourless transparent glass, colored transparent glass, the dark transparent glass any.As colored transparent glass, better be that green is a colored transparent glass, this green is that colored transparent glass better is to have UV absorbing properties and infra-red absorption performance.Thus, can reduce the transmitance at sunshine of laminated glass.
As green is colored transparent glass, and ferruginous soda-lime glass is for example arranged.That is, represent with mass percent, in as the soda-lime glass of parent for example iron be scaled Fe 2O 3Total content be 0.3～1% soda-lime glass.In addition, the absorption of the light of the wavelength of near infrared region mainly is based on the absorption of the divalent iron in all iron.Therefore, be more preferably and be scaled Fe 2O 3The quality of FeO (divalent iron) be the Fe that is scaled of iron 2O 3 Total mass 20～40%.In order to give UV absorbing properties, can give an example in as the soda-lime glass of parent adds the method for cerium etc.Specifically, better be to use in fact with mass percent and represent the soda-lime glass that forms by following forming.
SiO 2: 65～75%, Al 2O 3: 0.1～5%, Na 2O+K 2O:10～18%, CaO:5～15%, MgO:1～6% is scaled Fe 2O 3Total iron amount: 0.3～1%, be scaled CeO 2Total cerium amount and/or TiO 2: 0.5～2%.
Dark transparent glass is not special to be limited, and for example preferably gives an example and contains the soda-lime glass of iron with high density.
The spectral-transmission favtor of used sheet glass among Fig. 3 (a) expression the present invention, the spectral reflectivity of used sheet glass among Fig. 3 (b) expression the present invention.The transmittance of confirming the colored transparent sheet glass is littler than colourless transparent glass plate.
The thickness of sheet glass better is 1.5～3.0mm.In addition, sheet glass can be tabular or bending.But vehicle, particularly automotive window often are crooked, so sheet glass also better is a curved shape.
Infrared reflection glass plate of the present invention be have the tunicle (1) that forms at the high refractive index inanimate matter material more than 1.90 by specific refractory power and the tunicle (2) that forms at the low-refraction inanimate matter material below 1.56 by specific refractory power from the sheet glass side with this sequence alternate range upon range of and range upon range of tunicle (X); The summation of the quantity of the quantity of aforementioned tunicle (1) and aforementioned tunicle (2) is more than 3; The geometry thickness of aforementioned tunicle (1) is 70～1S0nm, and the geometry thickness of aforementioned tunicle (2) is the infrared reflection glass plate of 100～200nm.
Among the present invention, the high refractive index inanimate matter material is meant the inanimate matter material that has than the specific refractory power of glass plate hight.The value of its specific refractory power better is 1.90～2.60 more than 1.90, and good especially is 2.00～2.55 (in addition, the value the when value of specific refractory power is wavelength 550nm is descended together).In addition, under the situation about being formed by the multilayer tunicle like the said tunicle in back (1), the specific refractory power of the material of the main layer in this multilayer tunicle (layer of geometry thickness maximum) better is 2.35～2.55.In addition, the low-refraction inanimate matter material among the present invention is meant the low inanimate matter material of the aforementioned high refractive index inanimate matter material of refractive index ratio.The value of specific refractory power better is 1.40～1.56 below 1.56, and good especially is 1.45～1.50.
As the tunicle (1) of high refractive index tunicle with as the refringence of the tunicle (2) of low refractive index film better is more than 0.5, and good especially is more than 0.8.Of the back, a certain at least side in two tunicles is under the situation of multilayer tunicle, not this restriction of refringence of the material of the part layer in the multilayer tunicle and the material of other layer (other layer is the material of its part layer under the situation of multilayer tunicle).But even in this case, the refringence of the material of the main layer in the multilayer tunicle and the material of other layer (other layer is the material of its main layer under the situation of multilayer tunicle) also better is more than 0.5.The refringence of tunicle (1) and tunicle (2) is the bigger the better usually, but because the restriction of material, usually refringence on be limited to about 1.5 (particularly about 1.2).
For the interference effect of the range upon range of tunicle (X) through alternately laminated tunicle (1) and tunicle (2) makes infrared reflection, if ultrared wavelength is made as λ, the optical thickness of tunicle (1) and tunicle (2) must be respectively the integral multiple of λ/4.Therefore, for example in order to make the infrared reflection of 800～1600nm, the optical thickness of tunicle is necessary for 200～400nm.Therefore, if consider the specific refractory power of the material of each tunicle, the geometry thickness of the tunicle of specific refractory power 1.90～2.60 is 77～211nm, and the geometry thickness of the tunicle of specific refractory power 1.40～1.56 is 128～286nm.
Consider the reflection that can have the long wavelength side of visible region slightly, the optical thickness of tunicle among the present invention (1) and tunicle (2) all better is 180～400nm, and good especially is 190～350nm.Therefore, the geometry thickness of the tunicle among the present invention (1) is 69～211nm, and the geometry thickness of tunicle (2) is 115～286nm.But, under the big situation of geometry thickness, not only being difficult to form the tunicle (film-forming properties is low) of homogeneous, productivity is low, and produces defectives such as crack probably.The material of tunicle (1) particularly, especially titanium oxide is because heat-shrinkable produces the crack greatly and easily when thermal treatment.Therefore, the geometry thickness of the tunicle among the present invention (1), tunicle (2) must be below to a certain degree.So the geometry thickness of the tunicle among the present invention (1) adopts 70～150nm, the geometry thickness of the tunicle among the present invention (2) adopts 100～200nm.If consider aforementioned theoretical value, the geometry thickness of preferred tunicle (1) is 80～150nm, and the geometry thickness of preferred tunicle (2) is 130～200nm.
As the high refractive index inanimate matter material, better be titanium oxide, zinc oxide, tantalum oxide, zirconium white, niobium oxides, White tin oxide, titanium nitride, silicon nitride, zirconium nitride, aluminium nitride AlN, titanium oxynitrides, nitrogen zirconium white, nitrogen White tin oxide etc.As the low-refraction inanimate matter material, the composite oxides of silicon oxide, Sellaite or silicon oxide and other material (Al, F, C, B, P etc.) etc. of can preferably giving an example.Wherein, better be the composite oxides of silicon oxide or silicon oxide and Al, good especially is silicon oxide.In addition, if consider electric wave-transparent, these materials better are to have low electric conductivity.Therefore, as the high refractive index inanimate matter material, better be titanium oxide, zirconium white and titanium oxynitrides, as the low-refraction inanimate matter material, better be silicon oxide.
In the infrared reflection glass plate of the present invention, because there are 2 road tunicles (1) in the summation of the quantity of the quantity of tunicle (1) and tunicle (2) at least more than 3.They can be respectively the tunicles that is formed by same material, also can be the tunicles that is formed by differing materials.For tunicle (2) also is same.Existing under the situation of the above tunicles in 2 roads (2) in the infrared reflection film, can be respectively the tunicle that is formed by same material, also can be the tunicle that is formed by differing materials.
In addition; Consider under the situation of 1 road tunicle (1); Tunicle (1) can be the unitary film that is formed by independent high refractive index inanimate matter material, also can be the high refractive index multilayer film (1b) that is made up of the multilayered structure more than 2 layers that different types of high refractive index inanimate matter material forms.Better be that at least 1 road tunicle (1) is a high refractive index multilayer film (1b).In addition, high refractive index multilayer film (1b) is good especially is double membrane structure.
Tunicle (1) is under the situation of unitary film, better is the unitary film (1a) of titanium oxide or titanium oxynitrides.Titanium oxide is transparent, and specific refractory power is high especially in the high refractive index inanimate matter material, therefore has the advantage of the geometry thickness that can reduce film.Titanium oxynitrides also has high refractive index, so be favourable.In addition, of the back, through using titanium oxynitrides, also have and can when thermal treatments such as bending machining or reinforcement processing, suppress to produce on the film fissured advantage.Here, the unitary film of titanium oxynitrides layer is for only by titanium oxynitrides (TiO xN y) layer film that forms.Below, titanium oxide and titanium oxynitrides are referred to as " titanium compound ".
As high refractive index multilayer film (1b), better be that at least 1 layer of this high refractive index multilayer film (1b) of formation is the layer of titanium compound.As other layer except that the layer of titanium compound; The layer of the zirconic layer of zirconic layer, the layer of White tin oxide, the layer of tantalum oxide, the layer of zinc oxide, the layer of niobium oxides, the layer of titanium nitride, the layer of silicon nitride, the layer of zirconium nitride, the layer of aluminium nitride AlN, nitrogen, nitrogen White tin oxide etc. of can giving an example better is zirconic layer.Tunicle (1) is under the situation of high refractive index multilayer film (1b), and the whole optical thickness of multilayer film (optical thickness of each layer with) is that the integral multiple of λ/4 gets final product, and the geometry thickness is also counted 70～150nm with the total film thickness of multilayer film and got final product.
As high refractive index multilayer film (1b), better be layer high refractive index multilayer film (1b-1) that forms by zirconic layer and titanium compound.The order of the layer of range upon range of zirconic layer and titanium compound is not special to be limited; Can give an example from the sheet glass side with the situation of the sequential cascade of the layer of zirconic layer, titanium compound, from the situation of sheet glass side with the sequential cascade of the layer of titanium compound, zirconic layer, better be the former.In addition, also can adopt the 3-tier architecture of 2 layers of zirconic layer and the layer that is present in titanium compound therebetween.
As tunicle (1), preferred as previously mentioned the use by the unitary film of titanium oxynitrides or by layer high refractive index multilayer film (1b-1) that forms of zirconic layer and titanium compound is based on following reason.
Infrared reflection glass plate of the present invention can be made through the precursor (afterwards stating) of infrared reflection glass being implemented thermal treatments such as bending machining or reinforcement processing.According to the difference of the material of tunicle, add the thermal treatment in man-hour through bending machining or reinforcement, infrared reflection film may produce the crack.Particularly under the situation of the geometry thickness big (for example more than the 300nm) of infrared reflection film integral body, produce the crack probably.
It mainly is because the volumetric shrinkage of the film that the crystallization during thermal treatment causes that fissured generation is considered to.Therefore, can suppress methods such as volumetric shrinkage, suppress fissured generation through using the tunicle that forms by the high material of Tc, the multilayer film of the range upon range of differing materials of use.Titanium oxynitrides is compared with titanium oxide, more is difficult for taking place crystallization during thermal treatment.Therefore, if adopt the constituent material of titanium oxynitrides, then can suppress fissured generation as tunicle (1).
In addition, produce in order to suppress the crack, it also is effectively that tunicle (1) adopts the method for multilayer film (1b), and good especially is the multilayer film (1b-1) that adopts the layer that comprises zirconic layer and titanium compound.
Zirconic layer is most of monocline crystallization when film forming.In addition, the character of zirconic layer size is an equal extent with the layer of titanium oxide, and lattice match takes place easily.Think because so zirconic layer adjacency reset a crystalline situation at the layer internal crystal framework of titanium oxide during thermal treatment and be inhibited, so be difficult for shrinking (being difficult for crystallization) during thermal treatment.Therefore, the layer through range upon range of zirconic layer and titanium oxide can suppress the crack and produce.In addition, the multilayer film of the layer through adopting zirconic layer and titanium compound can obtain this two kinds of effects, so better.
High refractive index multilayer film (1b) is under the situation by layer high refractive index multilayer film that forms of zirconic layer and titanium compound; The crack that can bring into play based on zirconic layer suppresses effect; Therefore the geometry thickness of zirconic layer better is 5～35nm, is more preferably 10～25nm.The optical thickness of the zirconic layer (specific refractory power 2.06) of geometry thickness 5～35nm is 10～70nm, is equivalent to the layer (specific refractory power is made as 2.4～2.48) of the titanium compound of geometry thickness 4～29nm.Therefore, better be to make the layer of the layer of the titanium compound in zirconic layer the high refractive index multilayer film (1b) with 5～35nm for the little 4～29nm of the single film of titanium compound of geometry thickness zirconic layer than not having.
For tunicle (2); Consider under the situation of 1 road tunicle (2); Tunicle (2) can be the unitary film that is formed by independent low-refraction inanimate matter material, also can be the low-refraction multilayer film that is made up of the multilayered structure more than 2 layers that different types of low-refraction inanimate matter material forms.Under the situation of tunicle (2), better be the unitary film that is formed by independent low-refraction inanimate matter material, good especially is the unitary film that is formed by silicon oxide.
The tunicle (2) that infrared reflection glass plate of the present invention has sheet glass and the tunicle (1) that formed by aforementioned high refractive index inanimate matter material and aforementioned low-refraction inanimate matter material form from the sheet glass side with this sequence alternate range upon range of and range upon range of tunicle (X), the summation of the quantity of the quantity of tunicle (1) and tunicle (2) is more than 3.Sum get final product 3 or more, not especially qualification, if but excessive, then process laminated glass after transmission of visible light may descend, so the upper limit better is 9, good especially is 7.
The summation of the quantity of the quantity of tunicle (1) and tunicle (2) can be odd number or even number, gets final product according to the conditional decision of using infrared reflection glass plate.For example; So that infrared reflection glass plate is processed under the situation of laminated glass as the face of the glass in the car outside and range upon range of tunicle (X) and state configuration that intermediate coat joins, what constitute range upon range of tunicle (X) better is the tunicle (1) that is formed by the high refractive index inanimate matter material apart from sheet glass tunicle farthest.Therefore, under this situation, sum better is an odd number, better is 3,5,7 specifically, is more preferably 3 or 5, and good especially is 3.
On the other hand, (as veneer) uses under the situation of infrared reflection glass plate of the present invention separately, better is the tunicle (2) that is formed by the low-refraction inanimate matter material apart from sheet glass tunicle farthest.Therefore, sum better is an even number, specifically better is 4,6.
Be present in tunicle (1), tunicle (2) in the infrared reflection film and better be separately optical thickness about equally.If there is deviation in optical thickness separately, then may produce deviation by reflected colour, perhaps transmission of visible light descends.The variation range that is present in the optical thickness separately of the tunicle more than 2 layers (1) in the infrared reflection film better is ± scope of 50nm; If consider the specific refractory power of the high refractive index inanimate matter material that constitutes tunicle (1), the variation range of geometry thickness better is ± scope of 20nm.In addition, if consider the specific refractory power of high refractive index inanimate matter material and the specific refractory power of low-refraction inanimate matter material, the ratio of the geometry thickness of the geometry thickness of tunicle (1) and tunicle (2) note is made tunicle (1)/tunicle (2), better is 1/2～3/4.
As range upon range of tunicle (X), better be by 2 road tunicles (1) and be present in the 3 road structures that the tunicle (2) between this 2 road tunicle (1) constitutes.Tunicle (1) is under the situation of unitary film (1a) of (nitrogen) titanium oxide, forms the 3-tier architecture from sheet glass side (1a)/(2)/(1a).Being more preferably at least 1 road tunicle (1) is high refractive index multilayer film (1b), under this situation, forms from sheet glass side (1b)/(2)/(1a), (1a)/(2)/(1b) or 3-tier architecture (1b)/(2)/(1b).Wherein, better be (1b)/3-tier architecture of (2)/(1b).High refractive index multilayer film (1b) better is an aforementioned high refractive index multilayer film (1b-1).Therefore, among the present invention most preferred range upon range of tunicle (X) for by the range upon range of tunicle of 2 floor height specific refractory power multilayer films (1b-1) with the 3 road structures that are present in tunicle (2) formation between this 2 floor height specific refractory power multilayer film (1b-1).
In addition, from making the good angle of weather resistance, the whole geometry thickness (total film thickness) of range upon range of tunicle (X) better is 240～650nm, and good especially is 300～500nm.
As range upon range of tunicle (X), the structure shown in following of for example can giving an example.In addition, in the following structure, G representes sheet glass.
[1]G/ tunicle (1)/tunicle (2)/tunicle (1),
[2]G/ tunicle (1)/tunicle (2)/tunicle (1)/tunicle (2),
[3]G/ tunicle (1)/tunicle (2)/tunicle (1)/tunicle (2)/tunicle (1),
[4]G/ tunicle (1)/tunicle (2)/tunicle (1)/tunicle (2)/tunicle (1)/tunicle (2),
[5]G/ tunicle (1)/tunicle (2)/tunicle (1)/tunicle (2)/tunicle (1)/tunicle (2)/tunicle (1).
More specifically, for example can the give an example range upon range of tunicle (X) of the structure shown in following.
[1-1]：G/TiO 2/SiO 2/TiO 2、
[1-2]：G/TiO xN y/SiO 2/TiO 2、
[1-3]：G/TiO 2/SiO 2/TiO xN y、
[1-4]：G/TiO xN y/SiO 2/TiO xN y、
[1-5]：G/ZrO 2/TiO 2/SiO 2/TiO 2、
[1-6]：G/ZrO 2/TiO 2/SiO 2/ZrO 2/TiO 2、
[1-7]：G/ZrO 2/TiO 2/SiO 2/TiO xN y、
[1-8]：G/ZrO 2/TiO 2/SiO 2/ZrO 2/TiO xN y、
[1-9]：G/ZrO 2/TiO xN y/SiO 2/TiO 2、
[1-10]：G/ZrO 2/TiO xN y/SiO 2/ZrO 2/TiO 2、
[1-11]：G/ZrO 2/TiO xN y/SiO 2/TiO xN y、
[1-12]：G/ZrO 2/TiO xN y/SiO 2/ZrO 2/TiO xN y、
[1-13]：G/TiO xN y/SiO 2/ZrO 2/TiO 2、
[1-14]：G/TiO xN y/SiO 2/ZrO 2/TiO xN y、
[1-15]：G/TiO xN y/ZrO 2/SiO 2/TiO xN y、
[1-16]：G/TiO xN y/SiO 2/TiO xN y/ZrO 2、
[1-17]：G/TiO xN y/ZrO 2/SiO 2/TiO xN y/ZrO 2、
[1-18]：G/ZrO 2/TiO xN y/SiO 2/TiO xN y/ZrO 2、
[1-19]：G/TiO xN y/ZrO 2/SiO 2/ZrO 2/TiO xN y、
[3-1]：G/TiO xN y/SiO 2/TiO xN y/SiO 2/TiO 2、
[3-2]：G/TiO xN y/SiO 2/TiO xN y/SiO 2/TiO xN y、
[3-3]：G/ZrO 2/TiO xN y/SiO 2/TiO xN y/SiO 2/TiO xN y。
Infrared reflection glass plate of the present invention has sheet glass and range upon range of tunicle (X) as previously mentioned, can have the single layer structure that formed by inanimate matter material or the film (Y) of multilayered structure the sheet glass side of range upon range of tunicle (X) and at least one side in the non-glass plate side.In the film (Y), constituting all not enough 70nm of geometry thickness of each layer of film (Y), better is not enough 50nm.In addition, the film of distinguishing the not enough 70nm that joins with range upon range of tunicle (X) with its specific refractory power is the film (part of aforementioned multilayer film) in the range upon range of tunicle (X), or film (Y).For example; Under the situation that the film of the tunicle (1) of range upon range of tunicle (X) and the not enough 70nm that is formed by the material of specific refractory power more than 1.90 joins; This film is the part of high refractive index multilayer film (1b); Under the situation that the film of the tunicle (1) of range upon range of tunicle (X) and the not enough 70nm that is formed by the material of specific refractory power less than 1.90 joins, this film is film (Y).
In addition, film (Y) is not the main film that is used to give sheet glass infrared reflection performance, but there is influence in the infrared reflection performance.In addition, owing to play the effect of confirming reflected colour and transmission of visible light etc., so under the situation of laminate film (Y), optical characteristics is relevant with all films that comprise this film (Y).
As film (Y), the adjustment of can giving an example is adjusted film with the bonding force of the cementability of intermediate coat.Infrared reflection glass plate of the present invention is suitable for vehicle window (the particularly laminated glass of automobile), better is to form laminated glass with the face of the non-glass side of range upon range of tunicle (X) and the structure that intermediate coat joins.The penetration resistance that laminated glass is asked to stipulate, one of factor that determines this penetration resistance is the bonding force of intermediate coat and range upon range of tunicle (X).Therefore, better be that the bonding force of the bonding force of adjusting intermediate coat and range upon range of tunicle (X) is adjusted film-stack in the non-glass plate side of range upon range of tunicle (X).As bonding force adjustment film, the film that forms by chromic oxide of can giving an example etc.In addition, the geometry thickness of bonding force adjustment film better is 5～40nm.
In addition, as film (Y), the film of the reflected colour of the adjustment laminated glass of can also giving an example etc.When giving sheet glass infrared reflection function; For merely to stack gradually the tunicle (1) that forms by the high refractive index inanimate matter material and the tunicle (2) that is formed by the low-refraction inanimate matter material obtains required optical characteristics; The membrane structure number of plies is many more, and then its range of choice is wide more.But as previously mentioned, total film thickness is thick more when multilayer laminated, and then therefore the easier deterioration of the weather resistance of film needs appropriate membrane structure.On the other hand, in a large amount of selections, may in the reflection spectrum in the zone of wavelength 400～800nm, particularly 400～600nm, produce the ripple (below be called ripple) of minimax.
If the generation ripple, then the great wavelength of reflection (transmission) departs from because of the Thickness Variation in the face (deviation), forms the brilliance of reflection (transmission) look; Be color phase place uneven (iris); By the eyes perception, may produce distribution by reflected colour, perhaps the infrared reflection performance descends.So, can form film (Y) through non-glass plate side at range upon range of tunicle (X), thus the ripple in the inhibitory reflex spectrum.That is, form film (Y) through non-glass plate side at range upon range of tunicle (X), can be with T eMaintain below 45%, the ripple in the inhibitory reflex spectrum can obtain the infrared reflection glass plate of the good and optical characteristics of outward appearance good (heat-proof quality is good).
The film that forms in order to suppress ripple (Y) better is to be employed in the structure that has refringence with the interface of range upon range of tunicle, and the refringence of the layer of the film that joins (Y) and the tunicle of range upon range of tunicle (X) better is more than 0.3, and good especially is more than 0.5.The multilayered structure of the film that in addition, film (Y) specific refractory power that is range upon range of better is different.
As the film that is used to suppress ripple (Y); Infrared reflection glass plate of the present invention is being used under the situation of laminated glass; Better be to be the high refractive index layer (c) of 5～40nm and to be alternately laminated the getting of low-index layer (d) of 5～40nm by the geometry thickness that specific refractory power forms at the low-refraction inanimate matter material below 1.56 by the geometry thickness that specific refractory power forms at the high refractive index inanimate matter material more than 1.90; Total number of plies is an even number, and the layer that joins with the tunicle (1) of range upon range of tunicle (X) is the film (Y) of low-index layer (d).
As the high refractive index layer (c) in the film (Y); Can the give an example layers, the layer of titanium nitride, the layer of silicon nitride, the layer of zirconium nitride, the layer of aluminium nitride AlN, the zirconic layer of nitrogen, nitrogen White tin oxide etc. of layer, White tin oxide of layer, the layer of zinc oxide, the layer of tantalum oxide, zirconic layer, niobium oxides of layer, titanium oxynitrides of titanium oxide better are titanium oxide layers.As low-index layer (d), the layer of the layer of the layer of the silicon oxide of can preferably giving an example, Sellaite or the composite oxides of silicon oxide and other material (Al, F, C, B, P etc.) etc. better are the layers of silicon oxide.
In addition, as film (Y), can be the non-glass face side of the film of aforementioned inhibition ripple range upon range of the multilayer film of bonding force adjustment film of bonding force of adjustment and intermediate coat.
In addition, from the angle of weather resistance, comprise that the whole geometry thickness (total film thickness) of infrared reflection film of film (Y) better is 250～700nm, good especially is 300～500nm.
As infrared reflection glass plate of the present invention, the example shown in following of can giving an example.Wherein, from suppressing ripple effectively and keeping the angle of the weather resistance of film, better be (2)～(4), (6)～(8) that good especially is (2) and (3), preferably (3).In addition, in the following example, sheet glass representes with G, and the tunicle (1) that is formed by the high refractive index inanimate matter material in the range upon range of tunicle (X) is represented with H, is represented with L by the tunicle (2) that the low-refraction inanimate matter material forms.In addition, the high refractive index layer in the film (Y) is with H ' expression, and low-index layer is with L ' expression.In addition, represent with subscript from the lamination order of sheet glass.The layer that constitutes laminate film (X) is drawn together [] expression, and the layer that constitutes film (Y) is drawn together { } expression.
(1): G/ [range upon range of tunicle (X) (H 1/ L 2/ H 3)],
(2): G/{ film (Y) (H ' 1/ L ' 2)/[range upon range of tunicle (X) (H 3/ L 4/ H 5)],
(3): G/ [range upon range of tunicle (X) (H 1/ L 2/ H 3)]/film (Y) (L ' 4/ H ' 5),
(4): G/{ film (Y) (H ' 1/ L ' 2)/[range upon range of tunicle (X) (H 3/ L 4/ H 5)]/film (Y) (L ' 6/ H ' 7),
(5): G/ [range upon range of tunicle (X) (H 1/ L 2/ H 3/ L 4/ H 5)],
(6): G/{ film (Y) (H ' 1/ L ' 2)/[range upon range of tunicle (X) (H 3/ L 4/ H 5/ L 6/ H 7)],
(7): G/ [range upon range of tunicle (X) (H 1/ L 2/ H 3/ L 4/ H 5)]/film (Y) (L ' 6/ H ' 7),
(8): G/{ film (Y) (H ' 1/ L ' 2)/[range upon range of tunicle (X) (H 3/ L 4/ H 5/ L 6/ H 7)]/film (Y) (L ' 8/ H ' 9).
Specifically, for example can the give an example infrared reflection glass plate of the structure shown in following.
(1-1)：G/[ZrO 2/TiO xN y/SiO 2/ZrO 2/TiO xN y]、
(1-2)：G/[ZrO 2/TiO xN y/SiO 2/ZrO 2/TiO xN y]/{SiO 2/TiO 2}、
(1-3)：G/[ZrO 2/TiO xN y/SiO 2/ZrO 2/TiO xN y]/{SiO 2/TiO 2/CrO x}、
(1-4)：G/{SiO 2/TiO 2}/[ZrO 2/TiO xN y/SiO 2/ZrO 2/TiO xN y]、
(1-5)：G/{SiO 2/TiO 2}/[ZrO 2/TiO xN y/SiO 2/ZrO 2/TiO xN y]/{SiO 2/TiO 2}、
(1-6)：G/[TiO xN y/SiO 2/ZrO 2/TiO xN y]、
(1-7)：G/[TiO xN y/SiO 2/ZrO 2/TiO xN y]/{SiO 2/TiO 2}、
(1-8)：G/[ZrO 2/TiO xN y/SiO 2/TiO xN y]、
(1-9)：G/[ZrO 2/TiO xN y/SiO 2/TiO xN y]/{SiO 2/TiO 2}、
(1-10)：G/[TiO xN y/SiO 2/ZrO 2/TiO 2]、
(1-11)：G/[ZrO 2/TiO 2/SiO 2/TiO xN y]、
(1-12)：G/[ZrO 2/TiO 2/SiO 2/ZrO 2/TiO xN y]、
(3-1)：G/[TiO xN y/SiO 2/TiO xN y/SiO 2/TiO 2]、
(3-2)：G/[TiO xN y/SiO 2/TiO xN y/SiO 2/TiO xN y]/{SiO 2/TiO 2}、
(3-3)：G/[ZrO 2/TiO xN y/SiO 2/TiO xN y/SiO 2/TiO xN y]/{SiO 2/TiO 2}、
(3-4)：G/[ZrO 2/TiO xN y/SiO 2/TiO xN y/SiO 2/TiO xN y]/{SiO 2/TiO 2/CrO x}。
Infrared reflection glass plate of the present invention is through forming infrared reflection film aforesaid structure, can the electric wave-transparent when guaranteeing to process laminated glass in, increase the sunshine reflectivity and also reduce the transmitance at sunshine, weather resistance is also good.
Infrared reflection glass plate of the present invention is preferred for vehicle window, so better be that electric wave-transparent is fully guaranteed.Specifically, the sheet resistance value of its infrared reflection film better is more than 1k Ω/.Preferred sheet resistance value is more preferably more than 1G Ω/ more than 1M Ω/.Sheet resistance value is the bigger the better, and does not limit so its higher limit is special.In addition, if the material that forms aforesaid infrared reflection film through heat-treated, therefore the then oxidation of generating material can have than sheet resistance value big before the thermal treatment.
Infrared reflection glass plate of the present invention also refers to through the precursor of infrared reflection glass plate being implemented the infrared reflection glass plate that thermal treatments such as bending machining or reinforcement processing are processed.(infrared reflection glass plate) of the present invention precursor is meant the infrared reflection glass plate of the present invention before the thermal treatment.Infrared reflection glass plate (being precursor) before the thermal treatment and the infrared reflection glass plate after the thermal treatment are except the variation as the shape of heat treated purpose etc., and the material in the common infrared reflection film also changes.The variation of material mainly is the oxidation of generating material, and for example the ratio of the nitrogen-atoms of titanium oxynitrides descends, and the ratio of Sauerstoffatom increases.But even precursor, itself also has the function as infrared reflection glass plate.In addition, infrared reflection glass plate of the present invention be not limited to through thermal treatment and sheet glass.
Through thermal treatment and infrared reflection glass plate of the present invention can be through the precursor of infrared reflection glass plate being implemented bending machining or being strengthened thermal treatments such as processing and make.Thermal treatment can be through in common bending machining or strengthen the condition that is adopted in the processing and carry out, can be in 550～700 ℃ TR, better be to carry out in 600～700 ℃ the TR.Specifically, for example can under 650 ℃ of design temperatures, 15 minutes condition of heat treatment time, carry out.
In the thermal treatment of precursor, the film forming material generation of the structure of precursor oxidation if oxidation does not perhaps further take place, just can not change.The film forming material of structure before the thermal treatment is under the situation of metallic compounds such as silicon oxide, titanium oxide, zirconium white and chromic oxide, may oxidation take place because of thermal treatment.In addition, the film forming material of structure before the thermal treatment is under the situation of nitride such as oxynitride such as titanium oxynitrides or titanium nitride, liberating nitrogen when because of thermal treatment oxidation taking place.Therefore, under the situation of oxynitride or nitride, the ratio of contained nitrogen-atoms reduces because of thermal treatment in this material, and the ratio of Sauerstoffatom increases, and forms the oxide compound of nonnitrogenous in fact atom sometimes.
The material of the tunicle in the infrared reflection glass plate after the thermal treatment (1) is under the situation of titanium oxide, and the material of the tunicle of the correspondence in the precursor (1) better is a titanium oxynitrides.Under the situation that the material of the tunicle in the infrared reflection glass plate after the thermal treatment (1) is formed by titanium oxynitrides, the material of the tunicle of the correspondence in the precursor (1) better is the titanium oxynitrides high titanium oxynitrides of nitrogen-atoms after with respect to the ratio thermal treatment of titanium atom.Through using the material of such titanium oxynitrides as the tunicle in the precursor (1), fissured as previously mentioned generation reduces.Tunicle (1) is that the layer of the correspondence before the thermal treatment also better is the layer of aforesaid titanium oxynitrides under high refractive index multilayer film (1b) and the situation of its main layer for the layer of titanium compound.
On the other hand, film (Y) comprises under the situation of layer of titanium oxide, and the layer of the correspondence in the precursor needs not be the layer of titanium oxynitrides.Because the layer of the titanium oxide in the film (Y) be the layer thinner than tunicle (1), though in precursor be titanium oxide layer, to produce fissured possibility less because of thermal treatment.Adopt in the precursor under the situation of layer as the high refractive index layer of film (Y) of titanium oxynitrides, with above-mentioned same, the layer of the titanium oxynitrides that ratio that this layer forms nitrogen-atoms because of thermal treatment has descended or the layer of titanium oxide.
In addition; Under the situation of the high refractive index multilayer film (1b) of the layer that tunicle (1) is served as reasons tunicle that material except that titanium compound forms or comprised this material; Usually the volumetric shrinkage of this material in the thermal treatment is few, thereby need not change material in order to adapt to thermal treatment.But the degree of oxidation of oxide compound can improve.For example, the zirconic layer after the thermal treatment also can be zirconic layer in precursor.Likewise, the material of the low-index layer (d) in the material of tunicle (2) and the film (Y) the also volumetric shrinkage owing to this material in the thermal treatment is few, thereby need not change material in order to adapt to thermal treatment.
As the precursor among the present invention, better be all layers corresponding to " titanium oxide or titanium oxynitrides layer " in the tunicle (1) of the infrared reflection glass plate after the thermal treatment (being the layer of titanium compound) all be titanium oxynitrides layer.This is common under the situation of tunicle (1) for unitary film and multilayer film.In addition; Like oxynitride such as titanium oxynitridess because of the thermal treatment liberating nitrogen; The ratio of nitrogen-atoms reduces, thus aforementioned better be the high titanium oxynitrides of titanium oxynitrides in this infrared reflection glass plate of ratio of nitrogen-atoms preferably corresponding to the titanium oxynitrides in the precursor of infrared reflection glass plate (sheet glass after the thermal treatment).
In the infrared reflection glass plate after the thermal treatment, tunicle (1) comprises titanium oxynitrides (TiO xN y) situation under, in order to make optical characteristics such as reflectivity, transsmissivity good, the nitrogen of titanium oxynitrides better is 0.1～20% with respect to the ratio of titanium, good especially is 1～15%, preferably 1～10%.
In order after thermal treatment, to obtain the infrared reflection glass plate of so nitrogenous rate, the nitrogenous rate of the layer of the titanium oxynitrides in the tunicle of precursor (1) and the nitrogenous rate of the tunicle (1) in the infrared reflection glass plate after the thermal treatment are on an equal basis or more than it.Usually, nitrogen is 0.1～80% with respect to the ratio of titanium.The effect of the fissured generation when in addition, suppressing thermal treatment is relevant with the nitrogen content of titanium oxynitrides.Suppress fissured effect in order to strengthen, the nitrogen before the thermal treatment is good especially with respect to the ratio of titanium to be 1～20%, preferably 2～15%.
Among the present invention, the composition of titanium oxynitrides layer can through and with RBS (Rutherford backscattering spectroscopy; Rutherford Backscattering Spectrometry) and NRA (nuclear reaction analysis; NuclearReaction Analysis) method is directly measured.
In addition, through X-ray photoelectron spectroscopy (XPS), ESCA (ESCA; Electron Spectroscopy for Chemical Analysis) etc., be difficult to directly measure the composition (oxygen in the titanium oxynitrides layer, the ratio of nitrogen are specially the value of x and y) of titanium oxynitrides layer, but can measure the ratio (N/Ti (%)) of nitrogen with respect to titanium.Even be difficult to directly measure under the situation about forming, also can try to achieve nitrogen and get roughly 1.8～2.1 methods such as value with respect to the ratio of titanium, the value of supposing (x+y) and come roughly to infer its value through mensuration.For example, nitrogen is under 0.1% the situation with respect to the amount of titanium, if the fixing value of y, can think x=1.799～2.099, y=0.001.
As an example, x in the preferred composition of aforesaid titanium oxynitrides layer and the value of y are shown in table 1.This value based on aforementioned identical prerequisite, put down in writing with the value that the fixing value of y is calculated.
[table 1]
Figure 2006800300550A00800181
Such infrared reflection glass plate can be through the precursor of the aforementioned infrared reflection glass plate of heating, the titanium oxynitrides of the layer of the titanium oxynitrides in this precursor is converted into the few titanium oxynitrides of titanium oxynitrides in this precursor of ratio of nitrogen-atoms, thereby processes.In addition, be under the situation of layer of titanium oxide corresponding to the layer of the layer of the titanium compound in the infrared reflection glass plate, can be heated to layer being converted into till the titanium oxide of titanium oxynitrides in the precursor.
Infrared reflection glass plate of the present invention (comprising precursor) can be through making in the method for aforesaid tunicle of glass pane surface laminated or film.As the formation method of each tunicle or film, not special the qualification better is sputtering method.
Sputtering method for example can give an example DC (direct current) sputter mode, AC (interchange) sputter mode, high-frequency sputtering mode, magnetron sputtering mode.Wherein, because have process stabilization, the easy advantage of large-area film forming, so better be DC magnetron sputtering method and AC magnetron sputtering method.
The material of target and the composition of sputter gas are selected according to the kind of the film forming film of need.In addition, the condition of sputter (pressure, temperature etc.) can suitably be confirmed according to the kind of the film forming film of need, thickness etc.The stagnation pressure of sputter gas is that the stable pressure that carries out of photoglow gets final product.
Below, be that example describes with the situation that forms 3 kinds of tunicles.
In the forming of the tunicle that is formed by titanium oxide, the target of preferably giving an example uses TiO x(1＜x＜2), sputter gas uses the gas that comprises the gas that contains Sauerstoffatom, implements the method for reactive sputtering method.
In the forming of the tunicle that is formed by titanium oxynitrides, the target of preferably giving an example uses TiO x(1＜x＜2), sputter gas uses the gas of the gas that comprises nitrogen atom, implements the method for reactive sputtering method.
In the forming of the tunicle that is formed by silicon oxide, the target of preferably giving an example uses silit (SiC) or polysilicon, and sputter gas uses the gas that comprises the gas that contains Sauerstoffatom, implements the method for reactive sputtering method.
In the forming of the tunicle that is formed by zirconium white, the target of preferably giving an example uses Zr, and sputter gas uses the gas that comprises the gas that contains Sauerstoffatom, implements the method for reactive sputtering method.
Can be in the scope of not destroying characteristic of the present invention in the target known doping agents such as doped with Al, Si, Zn.
As long as the gas that comprises the gas of nitrogen atom comprises the gas of nitrogen atom, not special qualification, the gas of the nitrogen atom of for example can giving an example, the gas of nitrogen atom and the mixed gas of rare gas element.As the gas of nitrogen atom, for example can exemplified by nitrogen (N 2), N 2O, NO, NO 2, NH 3As rare gas element, the rare gas such as helium, neon, argon, krypton, xenon of for example can giving an example.Wherein, from the angle of the difficulty of economy and discharge, better be argon.The gas that comprises the gas of nitrogen atom can use separately, also can more than 2 kinds and use.
Comprise the gas that contains Sauerstoffatom as long as comprise the gas of the gas that contains Sauerstoffatom, not special the qualification, contains the gas of Sauerstoffatom and the mixed gas of rare gas element at the gas that contains Sauerstoffatom of for example can giving an example.As the gas that contains Sauerstoffatom, oxygen (O for example can give an example 2), dioxide gas (CO 2).For rare gas element, with aforementioned identical.The gas that comprises the gas that contains Sauerstoffatom can use separately, also can more than 2 kinds and use.
Infrared reflection glass plate of the present invention can be used for laminated glass for vehicle window well.Promptly; The present invention provides to be possessed the 1st sheet glass, has the intermediate coat that sheet resistance value has been mixed infrared shield property particulate in the 2nd sheet glass and the dispersion between the 1st sheet glass and the 2nd sheet glass of the infrared reflection film more than 1k Ω/, and the 1st sheet glass is located at the inboard laminated glass for vehicle window of car.
Fig. 1 is the perspective cross-sectional slice of an example of expression laminated glass for vehicle window of the present invention.The basic comprising of this routine laminated glass 1 is 2 sheet glass 11,12 and intermediate coat 30. Sheet glass 11,12 is range upon range of across intermediate coat 30.Be provided with infrared reflection film 21 in intermediate coat 30 sides on the sheet glass 12, form infrared reflection glass plate 20.Intermediate coat 30 is for disperseing to have mixed the infrared shield property intermediate coat of infrared shield property particulate.
The thickness of the 1st sheet glass and the 2nd sheet glass all better is 1.5～3.0mm.Under this situation, the 1st and the 2nd sheet glass can adopt equal thickness, also can adopt different thickness.When laminated glass is used for automotive window, for example can gives an example and the 1st and the 2nd sheet glass all is made as the scheme of thickness of thickness or the 2.1mm of 2.0mm.In addition, for example be made as not enough 2mm and the thickness of the 2nd sheet glass is made as greater than 2mm, can reduce the total thickness of laminated glass, and antagonism is from the external force in the car outside through thickness with the 1st sheet glass.1st, the 2nd sheet glass can be tabular or bending.Vehicle, particularly automotive window often are crooked, so mostly the shape of the 1st, the 2nd sheet glass is curved shape.Under this situation, infrared reflection film is located at the concave side of the 2nd sheet glass.In addition, can also use the sheet glass more than 3 as required.
In addition; Among the present invention, be colored transparent glass or dark glass if the 1st sheet glass uses green, the 2nd sheet glass uses water white soda-lime glass; Then can be when reflecting the energy at sunshine as much as possible; Doing one's utmost to suppress to incide the seeing through of energy at sunshine in the car, can bring into play the function as infrared reflection film fully, is ideal therefore.
In addition; When laminated glass of the present invention is installed in vehicle; The state that is arranged at the car outside with the 2nd sheet glass constitutes laminated glass of the present invention, better is for from the 2nd sheet glass side incident light, and the reflection of light rate that makes all wavelengths in the scope of 900～1100nm is 30～50%; The specific absorption of the light of all wavelengths in the scope of 1100～1300nm is 35～60%, and the optical transmission rate of all wavelengths in the scope of 900～1300nm is below 30%.Thus, can make not taken in excess and reflect the energy at sunshine as far as possible of laminated glass, and can be when guaranteeing electric wave-transparent, with sunshine transmitance suppress lowlyer.
If laminated glass for vehicle window then can be given full play to heat-proof quality for having aforesaid characteristic from the 2nd sheet glass side incident light.But,, then have the big tendency of transsmissivity change at sunshine if the specific absorption of the light of all wavelengths in the scope of 1100～1300nm is little.Therefore; In order to realize better heat-proof quality; For from the 2nd sheet glass side incident light; Better be that to make the reflection of light rate of all wavelengths in the scope of 900～1100nm be 30～50%, the specific absorption of the light of all wavelengths in the scope of 1100～1300nm is 40～60%, and the optical transmission rate of all wavelengths in the scope of 900～1500nm is below 30%.
In addition, work well, need to suppress the reflection of light of wavelength 850nm, keep enough transsmissivities in order to make infrared detection instruments such as light beacon.Spectral response curves such as reflectivity change continuously, so the reflection of light rate of wavelength 850nm receives near the influence of the reflectivity of its wavelength.Therefore, for the work of infrared detection instruments such as light beacon, need make the reflection of light rate of wavelength 900nm also be little value extremely to a certain degree.For reliable operation and the heat-proof quality that realizes the infrared detection instrument simultaneously; Better be that to make the reflection of light rate of wavelength 900nm be 20～40%; The reflection of light rate of all wavelengths in the scope of 1000～1100nm is 30～50%; The specific absorption of the light of all wavelengths in the scope of 1100～1300nm is 35～60%, and the optical transmission rate of all wavelengths in the scope of 900～1500nm is below 30%.In this form, the reflection of light rate that surpasses the zone of 900nm, not enough 1000nm changes between the reflection of light rate of the reflection of light rate of wavelength 900nm and wavelength 1000nm continuously.In this form, also better be to make the specific absorption of light of all wavelengths in the scope of 1100～1300nm 40～60%.
Intermediate coat among the present invention can be the intermediate coat that disperses to have mixed infrared shield property particulate, also can be common intermediate coat, better is the former.The material of intermediate coat uses polyvinyl butyral acetal usually.In addition, the vinyl-vinyl-acetic ester multipolymer etc. of can also giving an example.In addition,, process film, can obtain to disperse to mix the intermediate coat of infrared shield property particulate at these intermediate coat dispersion of materials infrared shield property particulates.As infrared shield property particulate, particulate that the hotchpotch by metal, oxide compound, nitride, the sulfide of Sn, Ti, Si, Zn, Zr, Fe, Al, Cr, Co, Ce, In, Ni, Ag, Cu, Pt, Mn, Ta, W, V, Mo etc. or mixed in them Sb or F of can giving an example forms etc.In these materials, better be to use at least a of White tin oxide (ATO) particulate, ITO particulate and the zinc oxide fine particles that are selected from the antimony that mixed.This is because the infrared shield of ATO, ITO, zinc oxide fine particles is functional, thereby can reduce the incorporation to intermediate coat.Wherein, the infrared shield of ITO particulate is functional, is to use the ITO particulate as infrared shield property particulate therefore well especially.
In order to suppress only scattering, the particle diameter of these infrared shield property particulates is more little good more.Particle diameter better is below 0.2 μ m, and good especially is 0.001～0.15 μ m.In addition, the content of infrared shield property particulate better is 0.1～1 quality % with respect to the total mass of intermediate coat usually, is more preferably 0.1～0.5 quality %, and good especially is 0.2～0.3 quality %.
Disperseed the intermediate coat of infrared shield property particulate to obtain through the method for making for example.That is, at first make infrared shield property microparticulate in the softening agent of intermediate coat.Then, in the resin solution of intermediate coat, disperse to add the softening agent that has disperseed infrared shield property particulate, mixed milling obtains film and uses resin raw material.Then, film is processed film with resin raw material, obtained disperseing to mix the intermediate coat of infrared shield property particulate with extrusion molding etc.In addition, when the dispersion of softening agent is added, also can in the resin solution of intermediate coat, add various additives.As additive, the various pigment of can giving an example, organic type of UV light absorber, organic type of infrared absorbent etc.In addition, the solvent as the resin solution of softening agent and intermediate coat is used can use known reagent.
The thickness of the intermediate coat that obtains as previously mentioned better is about 0.5～1mm, to be generally 0.76mm.
The method of manufacture of laminated glass for vehicle window of the present invention is not special to be limited, and for example can give an example is sandwiched in intermediate coat between the infrared reflection film and the 1st sheet glass on the 2nd sheet glass with infrared reflection film, makes its incorporate method through compacting.
In addition, in order to make its windshield glass that also can be used for automobile, the transmission of visible light of laminated glass for vehicle window of the present invention better is more than 70%, and good especially is more than 75%.
Embodiment
Below, the embodiment that gives an example specifies the present invention, but the present invention is not limited to these embodiment.Example 1～example 8 is embodiment, and example 9～example 12 is a comparative example.
Among the present invention, specific absorption is represented with specific absorption=1-(reflectivity+transsmissivity).Strictly speaking, also there be " scattering " in the light that incides glass article except " reflection ", " absorption ", " transmission ".But under the situation of glasswork, the loss that " scattering " produces is very little, therefore can specific absorption be represented with 1-(reflectivity+transsmissivity).
In addition, based on mimic embodiment with for the material that will constitute each tunicle with individual layer on sheet glass film forming and each wavelength of sample determination specific refractory power and each wavelength optical extinction coefficient and data implement.
(glass example)
With the size of 100mm * 100mm (example 1～3), 200mm * 200mm (example 4～6), about 1200mm * about 1650mm (example 7,8), prepare the sheet glass of 3 kinds of thick 2mm.The detail of 3 kinds of sheet glass as follows.For example 7,8, after forming infrared reflection film on the sheet glass of above-mentioned size, use the sample of the size that is cut into 100mm * 100mm, carry out the manufacturing of evaluation, laminated glass, as the evaluation of laminated glass as infrared reflection glass plate.In addition, the evaluation of the spectral response curve of sheet glass itself also uses the sample of 100mm * 100mm to carry out.
(1) water white transparency soda-lime glass (Asahi Glass company (Asahi Glass society) system below is called " FL1 "),
(2) water white transparency soda-lime glass (lattice draw Weibull company (グ ラ バ one ベ Le society) system, below are called " FL2 "),
(3) green that has a UV absorbing properties is colored transparent soda-lime glass (Asahi Glass company (Asahi Glass society) system below is called " UVFL1 ").
Then, suppose that car outside sheet glass uses FL1, FL2, car inner glass plate uses UVFL1, and when making the laminated glass of structure shown in Figure 1, sheet glass 11 uses UVFL1, and sheet glass 12 uses FL1 or FL2.
In addition, for these glass plates, (Hitachi Ltd. (Hitachi society) system, U4100) transmissivity, the reflectivity between mensuration wavelength 300～2100nm according to the regulation of JIS R3106, tried to achieve transmission of visible light T by spectrophotometer v(%), sunshine transmissivity T e(%), visible reflectance R v(%), sunshine reflectivity R e(%).The result is shown in table 2.
In addition, the figure of the spectral-transmission favtor of expression sheet glass among Fig. 3 (a), the figure of the spectral reflectivity of expression sheet glass among Fig. 3 (b).The longitudinal axis is respectively transsmissivity (%), reflectivity (%), and transverse axis is wavelength (nm).Among Fig. 3, FL1 is with colourless transparent glass 1 expression, and FL2 is with colourless transparent glass 2 expressions, and UVFL1 is with 1 expression of colored transparent glass, and UVFL2 is with 2 expressions of colored transparent glass.UVFL2 does not use in the present embodiment, but this sheet glass also can be used for enforcement of the present invention.
[table 2]
Figure 2006800300550A00800221
(infrared reflection film example)
Sheet glass 20 by the band infrared reflection film of 8 kinds of the preparations of the structure shown in following (film example 1～8) structure shown in Figure 1.The geometry thickness (nm) of each tunicle of numeral in the bracket.The specific refractory power of the material that uses in the film example 1～8 in addition, is shown in table 3.Value when these values all are wavelength 550nm is the value under the state of not heat-treating.
[table 3]
[film example 1]
FL1/TiO xN y(92)/SiO 2(179)/TiO xN y(92)/SiO 2(35)/TiO xN y(10)
[film example 2]
FL1/TiO xN y(96)/SiO 2(170)/TiO xN y(95)/SiO 2(28)/TiO xN y(11)
[film example 3]
FL1/TiO xN y(114)/SiO 2(150)/TiO xN y(113)/SiO 2(25)/TiO xN y(11)
[film example 4]
FL1/TiO xN y(104)/SiO 2(176)/TiO xN y(104)/SiO 2(30)/TiO xN y(11)
[film example 5]
FL1/TiO xN y(110)/SiO 2(178)/TiO xN y(111)/SiO 2(30)/TiO xN y(11)
[film example 6]
FL1/TiO xN y(95)/SiO 2(180)/TiO xN y(103)/SiO 2(26)/TiO xN y(11)
[film example 7]
FL1/ZrO 2(20)/TiO xN y(120)/SiO 2(185)/ZrO 2(20)/TiO xN y(120)/SiO 2(30)/TiO 2(8)
[film example 8]
FL2/ZrO 2(17)/TiO xN y(102)/SiO 2(182)/ZrO 2(17)/TiO xN y(100)/SiO 2(28)/TiO 2(7)
For the titanium oxynitrides layer in the film example 1～6, measure the ratio of nitrogen through ESCA with respect to titanium, try to achieve the value of x and y with the precondition of putting down in writing in this specification sheets.Its result is based on the data that record for the sample that on sheet glass, only forms the titanium oxynitrides layer.Even think the sample of the film that only formed titanium oxynitrides, nitrogen is also identical when in infrared reflection glass plate, measuring with respect to the ratio of titanium.In the table, nitrogen is made N/Ti (%) with respect to the ratio note of titanium.
[table 4]
Figure 2006800300550A00800241
In addition,, measure the composition of thermal treatment front and back, try to achieve the value of nitrogen with respect to ratio, x and the y of titanium for the titanium oxynitrides layer in the infrared reflection glass plate of film example 8.The mensuration of forming adopts and with the method for RBS and NRA.If adopt this method, then can directly measure composition, error is about ± 10%.
[table 5]
Figure 2006800300550A00800242
Infrared reflection film carries out film forming as follows.
(film example 1～6)
The infrared reflection film of film example 1～6 is through stacking gradually 5 layers of TiO altogether on sheet glass xN yLayer and SiO 2The layer and process.
<tiO xN yLayer>
In vacuum tank with TiO x(1＜x＜2) target is arranged on the negative electrode as sputtering target material, and vacuum tank is vented to 1.3 * 10 -3Below the Pa.Then, import the mixed gas of argon gas and nitrogen as sputter gas.At this moment, pressure reaches 7.0 * 10 -1Pa.Under this state, use the DC pulse power to implement the reactive sputtering method, the 2nd sheet glass (FL) in being arranged at vacuum tank is gone up and is formed TiO xN yFilm.In addition, the sputter gas as film example 1～6 uses following sputter gas respectively.Film example 1: argon gas 90sccm, nitrogen 10sccm; Film example 2,4～6: argon gas 95sccm, nitrogen 15sccm; Film example 3: argon gas 80sccm, nitrogen 20sccm.
<siO 2Layer>
In vacuum tank, the SiC target is arranged on the negative electrode as sputtering target material, vacuum tank is vented to 1.3 * 10 -3Below the Pa.Then, import the mixed gas of 40sccm argon gas and 60sccm oxygen as sputter gas.At this moment, pressure reaches 6.0 * 10 -1Pa.Under this state, use the DC pulse power to implement the reactive sputtering method, the tunicle of the handled object in being arranged at vacuum tank (1) is gone up and is formed SiO 2Film.
(film example 7,8)
The infrared reflection film of film example 7,8 is through form ZrO by the step shown in following successively on sheet glass 2Film, TiO xN yFilm, SiO 2Film, ZrO 2Film, TiO xN yFilm, SiO 2Film, TiO 2Film and getting.
<zrO 2Layer>
In vacuum tank, the Zr target is arranged on the negative electrode as sputtering target material, vacuum tank is vented to 1.3 * 10 -3Below the Pa.Then, import oxygen as sputter gas with 70: 30 ratio (volume ratio) and argon gas to pressure reaches 4.0 * 10 -1Pa.Under this state, use the DC pulse power to implement the reactive sputtering method, form ZrO on the handled object in being arranged at vacuum tank 2Layer.
<tiO xN yLayer>
In vacuum tank with TiO x(1＜x＜2) target is arranged on the negative electrode as sputtering target material, and vacuum tank is vented to 1.3 * 10 -3Below the Pa.Then, import argon gas, nitrogen and oxygen to pressure as sputter gas with 70: 13: 17 ratio (volume ratio) and reach 4.0 * 10 -1Pa.Under this state, use the DC pulse power to implement the reactive sputtering method, form TiO on the handled object in being arranged at vacuum tank xN yLayer.
<siO 2Layer>
In vacuum tank, the Si target is arranged on the negative electrode as sputtering target material, vacuum tank is vented to 1.3 * 10 -3Below the Pa.Then, import argon gas as sputter gas with 39: 61 ratio (volume ratio) and oxygen to pressure reaches 4.0 * 10 -1Pa.Under this state, use AC power supplies to implement the reactive sputtering method, form SiO on the handled object in being arranged at vacuum tank 2Layer.
<tiO 2Layer>
In vacuum tank with TiO x(1＜x＜2) target is arranged on the negative electrode as sputtering target material, and vacuum tank is vented to 1.3 * 10 -3Below the Pa.Then, import argon gas as sputter gas with 30: 70 ratio (volume ratio) and oxygen to pressure reaches 4.0 * 10 -1Pa.Under this state, use the DC power supply to implement the reactive sputtering method, form TiO on the handled object in being arranged at vacuum tank 2Layer.
For the infrared reflection glass that has formed infrared reflection film as previously mentioned; By spectrophotometer (Hitachi Ltd. (Hitachi society) system; U4000) reflectivity between mensuration wavelength 300～2100nm according to the regulation of JIS R3106, is tried to achieve visible reflectance R v(%), sunshine reflectivity R e(%).In the table 6, the infrared reflection glass that will have film example 1 is called the infrared reflection glass of example 1, and other example too.Measure the sample before the thermal treatment for example 1～6, example 7 and example 8 are measured the sample that gets with 620 ℃ design temperature thermal treatment 7 minutes with roller kiln.Even the infrared reflection glass of example 7 and 8 is implemented also not produce the crack on the Heat treating film.
Represent these infrared reflection glass plates spectral reflectivity be illustrated in Fig. 4～Fig. 6.
[table 6]
Figure 2006800300550A00800261
(laminated glass example)
Process the laminated glass of structure shown in Figure 1.The 1st sheet glass 11 is pre-prepd UVFL sheet glass, and the 2nd sheet glass 12 is pre-prepd FL sheet glass, has the infrared reflection film 21 of film example 1～8.PVB (polyvinyl butyral acetal) intermediate coat of ITO particulate has been mixed in employed dispersion in intermediate coat 30 use Network one Le ベ, one Le (Cool verre) (Asahi Glass company (Asahi Glass society) system, registered trademark).Below, the laminated glass that will have film example 1 is called the laminated glass of example 1, and other example is too.The thickness of this PVB intermediate coat is 0.76mm.In addition, the containing ratio of ITO particulate is 0.2 quality % with respect to the PVB intermediate coat.
For the laminated glass of the example that obtains like this 1～8, try to achieve from the transmission of visible light T of the 2nd sheet glass 12 side incident light v(%), sunshine transsmissivity T e(%), visible reflectance R v(%), sunshine reflectivity R e(%).For example 1～6, the value that the simulation based on the spectral characteristic data of infrared reflection glass plate of serving as reasons obtains; For example 7,8, for (Hitachi Ltd. (Hitachi society) system U4000) is measured transmissivity, reflectivity between wavelength 300～2100nm, the value of trying to achieve according to the regulation of JIS R3106 by spectrophotometer.
In addition, before laminated glass is made (film form back, thermal treatment before) uses 2 probe resistance meters (HirestaIP, Mitsubishi Petrochemical Co., Ltd (oiling society of Mitsubishi) system) to measure the sheet resistance value of the infrared reflection film of film example 1～8 (G Ω/).After the thermal treatment, because therefore mould material generation oxidation reaches the resistance value bigger than this measured value, so the sheet resistance value of the infrared reflection film of the example of the film after the laminated glassization 1～8 is all at (more than 1G Ω/) more than 1k Ω/.
In addition, in order to compare, use the FL sheet glass that does not form infrared reflection film, other is likewise operated with example 1～8, processes comparative sample (example 9～example 11).The structure of comparative sample is FL1/ITO microparticulate PVB intermediate coat/UVFL1.
For the sample of example 9～example 11, also try to achieve from the transmission of visible light T of the 2nd sheet glass 12 side incident light v(%), sunshine transsmissivity T e(%), visible reflectance R v(%), sunshine reflectivity R e(%).In addition, try to achieve visible-light absorptivity A y(%), sunshine specific absorption A c(%).The result is shown in table 7.Fig. 7～9 are the figure of expression spectral-transmission favtor, spectral reflectivity, spectral absorption.
[table 7]
Figure 2006800300550A00800271
As stated, the laminated glass of the infrared reflection glass plate of the application of the invention even use the infrared reflection film with electric wave-transparent, also can make T eMake R when following 45% eMore than 20%.Use the laminated glass of infrared reflection glass plate of the present invention can reflect the energy at sunshine efficiently, can suppress to incide the seeing through of energy at sunshine in the car, so heat-proof quality is good.In addition, if T eValue little of about 1%, then the skin burning sensation of incident light obtains reducing, so use the laminated glass of infrared reflection glass plate of the present invention to compare with the common laminated glass that does not have infrared reflection film, can alleviate occupant's sense of discomfort.
In addition, R vBe suppressed to below 12%, so think that the very big peak of reflection spectrum in the zone that can suppress visible region, particularly 400～600nm, affirmation can obtain the uneven few laminated glass of color phase place that the generation of ripple is inhibited.Particularly the laminated glass of example 2,4,5,8 can be with R vBeing suppressed to below 10%, can be the good example of outward appearance therefore, also is the laminated glass that is suitable for automotive window.
The possibility of utilizing on the industry
Use the laminated glass for vehicle window that infrared reflection glass plate of the present invention constitutes owing to laminated glass is not absorbed and reflect the energy at sunshine as far as possible, can suppress to incide the seeing through of energy at sunshine in the car, suppress the rising of vehicle interior temperature.Through such laminated glass is used for vehicle window; Under the sun, go or parking etc. receives in the environment at sunshine at vehicle; Can prevent that the temperature in the car from rising, can reduce the frequency of utilization and the load of air-conditioning, help the inhibition that fuel cost improves or fuel cost increases of vehicle.
Laminated glass for vehicle window of the present invention can also be used for drop window, sidepiece fixed window, rear window, roof window etc. except particularly being used for well the windshield glass of automobile.If be used for the window of all these automobiles, the temperature that can further suppress in the automobile rises.
In addition, quote the announcement of all the elements of Japanese patent application 2005-235726 number of filing an application on August 16th, 2005 and Japanese patent application 2005-254905 number specification sheets, claims, accompanying drawing and the summary of filing an application on September 2nd, 2005 here as specification sheets of the present invention.

Claims (13)

1. infrared reflection glass plate, it is the sheet glass with infrared reflection film, it is characterized in that, this infrared reflection film has range upon range of tunicle (X) and film (Y),
The 1st tunicle that said range upon range of tunicle (X) is formed at the high refractive index inanimate matter material more than 1.90 by specific refractory power and the 2nd tunicle that formed at the low-refraction inanimate matter material below 1.56 by specific refractory power are range upon range of and get with this sequence alternate from the sheet glass side; The summation of the quantity of the quantity of aforementioned the 1st tunicle and aforementioned the 2nd tunicle is more than 3; The geometry thickness of aforementioned the 1st tunicle is 70～150nm; The geometry thickness of aforementioned the 2nd tunicle is 100～200nm
Said film (Y) has the multilayered structure that is formed by inanimate matter material in the non-glass plate side of range upon range of tunicle (X); The 1st tunicle of film (Y) and range upon range of tunicle (X) joins; And film (Y) is to comprise that the geometry thickness that is formed at the high refractive index inanimate matter material more than 1.90 by specific refractory power is the high refractive index layer (c) of 5～40nm and is that the alternately laminated total number of plies that gets of low-index layer (d) of 5～40nm is the even multilayer film by the geometry thickness that specific refractory power forms at the low-refraction inanimate matter material below 1.56, and the layer that joins with the 1st tunicle of range upon range of tunicle (X) is low-index layer (d).
2. infrared reflection glass plate as claimed in claim 1 is characterized in that, at least 1 road in the 1st tunicle is the unitary film (1a) of titanium oxide or titanium oxynitrides.
3. infrared reflection glass plate as claimed in claim 1; It is characterized in that; The high refractive index multilayer film (1b) that at least 1 road in the 1st tunicle constitutes for the multilayered structure more than 2 layers that is formed by different types of high refractive index inanimate matter material, at least 1 layer in this high refractive index multilayer film (1b) is the layer of titanium oxide or titanium oxynitrides.
4. infrared reflection glass plate as claimed in claim 3 is characterized in that, at least 1 layer in the high refractive index multilayer film (1b) is the layer of titanium oxide or titanium oxynitrides, and other at least 1 layer is zirconic layer in this high refractive index multilayer film (1b).
5. infrared reflection glass plate as claimed in claim 1; It is characterized in that, range upon range of tunicle (X) by 2 roads comprise zirconic layer and titanium oxide or titanium oxynitrides layer geometry thickness add up to the high refractive index multilayer film (1b-1) of 70～150nm and the 2nd tunicle that is present between this 2 road high refractive index multilayer film (1b-1) forms.
6. like each the described infrared reflection glass plate in the claim 1～5, it is characterized in that the 2nd tunicle is the layer of silicon oxide.
7. infrared reflection glass plate as claimed in claim 1 is characterized in that, the refringence of the layer of the film that joins (Y) and the tunicle of range upon range of tunicle (X) is more than 0.3.
8. infrared reflection glass plate as claimed in claim 1 is characterized in that, the high refractive index layer (c) of film (Y) is the layer of titanium oxide, and the low-index layer (d) of film (Y) is the layer of silicon oxide.
9. the precursor of infrared reflection glass plate; This precursor forms each described infrared reflection glass plate in the claim 1～8 through heat treated; It is characterized in that; All layers corresponding to the layer of titanium oxide in the 1st tunicle of the infrared reflection glass plate after the heat treated or titanium oxynitrides all be the layer of titanium oxynitrides, this titanium oxynitrides layer in titanium oxynitrides be the high titanium oxynitrides of titanium oxynitrides in the infrared reflection glass plate after the ratio heat treated of nitrogen-atoms.
10. the method for manufacture of infrared reflection glass plate; It is a method of making each the described infrared reflection glass plate in the claim 1～8; It is characterized in that; With the heating of the described precursor of claim 9, the titanium oxynitrides of the layer of the titanium oxynitrides in this precursor is converted into the few titanium oxynitrides or the titanium oxide of titanium oxynitrides in this precursor of ratio that contain of nitrogen-atoms.
11. the method for manufacture through the described infrared reflection glass plate of claim 10 of bending machining is characterized in that, with the precursor heating, carries out bending machining.
12. laminated glass for vehicle window; It is to possess the 1st sheet glass, have 2nd sheet glass and the intermediate coat between 1st sheet glass and 2nd sheet glass between of sheet resistance value at the infrared reflection film more than 1k Ω/; And the 1st sheet glass is located at the inboard laminated glass for vehicle window of car; It is characterized in that the 2nd sheet glass with infrared reflection film is each the described infrared reflection glass plate in the claim 1～8.
13. laminated glass for vehicle window as claimed in claim 12 is characterized in that, for from the 2nd sheet glass side incident light, transmission of visible light is more than 70%.
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