CN1189563A - Curtain wall glass without white light pollution - Google Patents

Abstract

A curtain wall glass without white light pollution structurally features that the high-refractivity film and low-refractivity film are alternatively deposited on glass substrate for reducing the reflection of visual light and the film whose reflectivity to infrared light is greater than 70% is then deposited. Its advantages are high reflectivity to infrared light but low reflectivity to visual light (less than 2%).

Description

The cladding glass of no white light pollution

The present invention relates to a kind of cladding glass that does not have white light pollution.

No white light pollution cladding glass is meant that cladding glass is less than the reflectivity (as be less than with the crown glass be the cladding glass substrate, the reflectivity of its single face is 4.2%) of substrate of glass for the reflectivity of visible region, and infrared light region has very big reflectivity.Be mainly used in building.

In the prior art, coated glass product for building generally is divided into two big classes: anti-sunlight type and high-transmission rate/low-E coated glass.

Anti-sunlight type glass normally is substrate (usually being with look) with glass, be coated with a kind of band look film of low visible light transmissivity, this film has reduced to see through prevents that sunlight type glass enters the solar energy of interior of building, thereby reduced the temperature in the building, saved the air-conditioning expense in season at summer high temperature.These anti-sunlight type glass products are the most effective at warm weather, and are modal by being used on the business buildings.

In the place of more being concerned about the heating expense especially dwelling house, need the coated glass of high-transmission rate/low-E, make visible light with in the high transmissivity inlet chamber, the while infrared radiation reflecting, thus keep the interior heat of building.The coated glass of high-transmission rate/low-E, on substrate of glass topped rete multilayer film normally, it is that the metal film (for example, Ag, Au, or Cu film) of reflected infrared ray is clipped between the metal oxide rete of two anti-visible lights reflections that one deck is wherein arranged.

The rete that anti-sunlight type glass is plated generally is the monofilm such as one or more metals such as cobalt, iron, titanium, chromium, nickel, copper or metal oxide.

The metal film of the anti-sunlight type glass of preparation adopts chemical method such as U.S. Pat 3846152, US4091172, US3723158 and US3457138, the metal oxide film of the anti-sunlight type glass of preparation adopts pyrolysismethod such as U.S. Pat 3660061, US3658568, US3978272 and US4100330 report.

Described the sputtering technology of the plural layers of manufacturing high-transmission rate/low-E among U.S. Pat 4462884 and the US4508789.Also having disclosed the plated film of making anti-sunlight type glass employing in U.S. Pat 4512863 and US4594137 is to use sputtering technology.

U.S. PPG Industries Inc. discloses a kind of sputtered film of metal alloy oxide at Chinese patents CN 85109342A, and the oxide that wherein adopts Zn and Sn alloy is as anti--constructional materials that the reflective metal oxide combines with transparent metal film.This metal-oxide film must have suitably high refractive index, its refractive index more preferably greater than 2.0 with reflection that reduces metal level and the light transmission of strengthening coating.But the alloyed oxide that adopts Zn and Sn is the antireflection with respect to the infra-red reflective metal film as anti--reflective metal sull, rather than the antireflection of relative substrate of glass, therefore can not eliminate substrate of glass to visible reflection of light.

U.S. PPG Industries Inc. is at Chinese patents CN88101654A, a kind of plural layers that form a kind of low radiation with titanium oxynitrides and an infrared reflection film (as Ag) combined deposition are disclosed, the titanium oxynitrides film can use with other metal film with various thickness and structure, thus the very wide a series of reflected colour glass of formation scope.It is to utilize the not reflection of coated surface, makes this constructional materials have color, and the minimum reflectivity of not plated film substrate surface described here is 5%.

U.S. PPG Industries Inc. discloses a kind of multilayer high transmission rate, low emissivity film at Chinese patents CN86108656, is a kind of with Zn ₂SnO ₄Be the antireflection metal oxide, improved its resistance to chemical corrosion with existing of titanium oxide outer coating.Its structure is that first floor is the first transparent antireflection metal-oxide film Zn ₂SnO ₄, the second layer is a transparent red external reflectance metal silverskin, the 3rd layer is transparent antireflection metal-oxide film Zn ₂SnO ₄The 4th layer is the metal oxide titanium oxide of deposition after the 3rd layer of antireflection metal-oxide film, because the refractive index of thin film of titanium oxide is greater than 2.0, it is greater than the refractive index of substrate of glass, so it can not make film low to the reflectivity that is less than substrate of glass at the reflectivity of visible region.The product that adopts this method to obtain is 5% from the reflectivity of plated film one sidelight of glass, and the reflectivity of plated film one side is not 6%, so it does not thoroughly eliminate visible reflection of light.

U.S. PPG Industries Inc. is at Chinese patents CN87105971A, the high/low radiation coating goods of a kind of multi-layer transparent degree are disclosed, its processing of can heating, as bending, annealing, lamination, glass welding etc., coating is used for heatable antifreeze, defrosting, demist transparency as high-temperaure coating, adopts two-layer antireflection metal oxide in this invention.Also be antireflection, do not have the antireflection of relative substrate of glass with respect to the infra-red reflective metal film.Therefore do not eliminate visible reflection of light yet.

U.S. PPG Industries Inc. is at Chinese patents CN1105712A, a kind of method and product obtained by this method are disclosed, the technology that particularly prepares durable metal-oxide film with magnetron sputtering, this invention relate to a kind of under the atmosphere of enough inertia the method for splash-proofing sputtering metal target, make sputter carry out in the metal mode, and the deposition film be metallic state basically, yet, in gas, also add enough active gases, make metallic film be amorphous state rather than crystalline state.Amorphous sputtered metal film, than in the gas that has only the inert gas component, the metallic film hardness height and the good endurance of sputter, amorphous sputtered metal film can more effectively carry out thermal oxide than the metallic film that deposits in only by inert gas, the result obtains a kind of crystalline state metal-oxide film, and such metal-oxide film has higher chemical stability than the amorphous metal oxide film of the deposition of splash-proofing sputtering metal in oxidizing atmosphere.Its objective is that such product can in very large range be made the very on a large scale interior desired reflection colour of different-thickness to obtain to cause owing to interference effect, illustrates that it has bigger reflection in order to obtain the durability product that high hardness is become reconciled.

U.S. PPG Industries Inc. is at Chinese patents CN1037550A; a kind of visually be neutral high-transmission rate, low scattered power coated article and preparation method are disclosed; comprise three kinds of membrane structures in this invention; wherein have a structure to be: first floor is that refractive index is about 2.0 transparent antireflection metal oxide; the second layer is a refractive index greater than 2.0 transparent neutral metal oxide; the 3rd layer is the metal film of anti-infrared light; the 4th layer is transparent neutral metal titanium; layer 5 is transparent antireflection metal-oxide film, wherein also comprises titanium dioxide protective layer.The refractive index of the first floor transparent membrane in this structure is about 2.0, the refractive index of second layer film is greater than 2.0, titanium dioxide for example, this is in order to improve caking property between metal and the metal oxide, improve the durability of metal alloy oxide film, especially improve the durability of the plural layers of forming by metal alloy oxide and metal (as silver).But it can not make film be less than the reflectivity of substrate of glass at the reflectivity of visible region.Adopt two-layer antireflection metal oxide in this invention.Also be antireflection, do not have the antireflection of relative substrate of glass with respect to the infra-red reflective metal film.In this invention, be 5% at the visible reflectance of coating one side, the visible reflectance of coating one side is not 6%, illustrates that its reflection is not lower than the reflectivity of general substrate of glass (4.2%), does not eliminate visible reflection of light.

As mentioned above, high-transmittance, the coating of low diathermaneity, common thin metal layer by reflects infrared light and low radiation is clipped in order to institute in the non-conductive layer of the metal oxide that reduces the visible light reflection to be formed.The typical production method of these multilayer films is cathodic sputtering, and metal level can be gold or copper, and normally silver-colored, metal oxide layer comprises tin oxide, titanium oxide, zinc oxide, indium oxide, bismuth oxide, alumina or zirconia.

The film article that is obtained in the above various technology, the metal oxide of every employing minimizing visible light reflection, all be the reflection that reduces transparent metal layer, and fail to reduce the reflection of substrate of glass.Be to have strong dazzle in the sun in the time of on being used for building.This white light pollution has brought new public hazards to modern city, and gives the navigation of aircraft, and the driving of automobile has brought difficulty, and makes observatory have to move out of the city.

Purpose of the present invention is eliminated visible reflection of light as far as possible, and infrared light is had higher reflection for overcoming above-mentioned several weak point, does not have visible reflection of light when product of the present invention is used as curtain wall and does not have white light pollution thereby reach.

The present invention utilizes transparent metal silverskin or dielectric material titanium nitride and transparent dielectric film to mate, regulate the thickness of each layer film, make film have high reflectance in infrared light region, and reach extremely low limit at the visible region reflectivity, be less than cladding glass that the reflectivity of coated glass not promptly contains film to the reflectivity of visible light reflectivity, to eliminate white light pollution less than substrate glasses.

The cladding glass of no white light pollution of the present invention is the structure that adopts deposit film 2 in the substrate 1 of glass, and Fig. 1 is a structural representation of the present invention.Substrate of glass can be colourless also can be colored.

The film system design of film will be satisfied two conditions:

The one, have low reflectivity in the visible region.

The 2nd, have high reflectivity in the infrared light district.

For satisfying above-mentioned two conditions by the film structure design to film, the thickness of regulating each tunic in the film system makes the visible region have low reflectivity, and has high reflectivity in the infrared light district.

Film layer structure of the present invention is in proper order:

By substrate of glass 1 beginning, be deposited on substrate of glass 1 lip-deep first floor film 21 and be by refractive index greater than 2.0 metal oxide, as TiO ₂Constitute.Second layer film 22 is to be deposited on the first floor film 21, is the silicon oxide film of refractive index less than the refractive index (1.5) of substrate of glass 1, as SiO ₂(refractive index is 1.46).Three-layer thin-film 23 is to be deposited on the second layer film 22, is made of the material that infrared light is had high reflectance, and promptly reflectivity is greater than 70%, as metal A g or TiN.Four-level membrane 24 is to be deposited on the three-layer thin-film 23, is made of greater than 2.0 metal oxide refractive index, as TiO ₂Layer 5 film 25 is to be deposited on the four-level membrane 24, is made of the material of refractive index less than the refractive index (1.5) of substrate of glass, as SiO ₂As shown in Figure 1.

The first floor refractive index is arranged greater than 2.0 material such as TiO in the film layer structure ₂The film that is constituted has the reflection of the rete of high reflectance at visible region to reduce the 3rd layer to infrared light.Second layer refractive index is less than the material such as the SiO of the refractive index 1.5 of substrate of glass ₂The film that is constituted is to reduce the reflection of substrate of glass.The 3rd layer purpose is to reach by infrared light being had high reflectance promptly to adopt reflectivity greater than 70%, constitutes as metal A g or TiN.The 4th layer identical with first floor.The 5th is identical with the second layer.Crux is to mate between each rete in the structure, and mutually alternately stack and make monolithic film membrane have antireflection characteristic at visible region has high reflection characteristic in the infrared light district.

Expression film structure feature major parameter comprises thicknesses of layers d, and rete is counted m, film material, and reflectivity R and transmissivity T, they should satisfy following formula.

The refractive index of substrate and all retes is represented phase place thickness with plural form $\mathrm{\&delta;}=\frac{2\mathrm{\&pi;}}{\mathrm{\&lambda;}}(n-\mathrm{ik})d=\frac{2\mathrm{\&pi;}}{\mathrm{\&lambda;}}\mathrm{nd}-i\frac{2\mathrm{\&pi;}}{\mathrm{\&lambda;}}\mathrm{kd}----\left(1\right)$ D is the thickness of rete, and n is the refractive index order of rete ${\mathrm{\&delta;}}_1=\frac{2\mathrm{\&pi;}}{\mathrm{\&lambda;}}\mathrm{nd},$ ${\mathrm{\&delta;}}_2=\frac{2\mathrm{\&pi;}}{\mathrm{\&lambda;}}\mathrm{kd}----\left(2\right)$ δ ₁, δ ₂All be real number, so δ=δ ₁-i δ ₂Cos δ=cos δ ₁.ch δ ₂+ isin δ ₁.sh δ ₂. make c ₁=cos δ ₁.ch δ ₂, c ₂=sin δ ₁.sh δ ₂Thereby cos δ=c ₁+ ic ₂Same sin δ=sin δ ₁.ch δ ₂-icos δ ₁.sh δ ₂Make s ₁=sin δ ₁.ch δ ₂, s ₂=-cos δ ₁.sh δ ₂So s ₁+ is ₂. recurrence formula $Y_j=\frac{Y_{j+1}\cos {\mathrm{\&delta;}}_j+i{\mathrm{\&eta;}}_j\sin {\mathrm{\&delta;}}_j}{\cos {\mathrm{\&delta;}}_j+i{Y}_{j+1}/{\mathrm{\&eta;}}_j\sin {\mathrm{\&delta;}}_j}----\left(3\right)$ Corresponding being write as: $Y_j=\frac{(y_{j+1}^{\left(1\right)}{c}_1-y_{j+1}^{\left(2\right)}{c}_2+k_i{s}_1-n_j{s}_2)+i(y_{j+1}^2{\mathrm{<figure-callout\; id="1"\; label="c"\; filenames="A9710625400112.png"\; state="\{\{state\}\}">c</figure-callout>}}_1+y_{j+2}^{\left(1\right)}{c}_2+{\mathrm{<figure-callout\; id="1"\; label="n\; j\; s"\; filenames="A9710625400112.png"\; state="\{\{state\}\}">n</figure-callout>}}_j{s}_{}{}_1+k_j{s}_2)}{{\mathrm{<figure-callout\; id="1"\; label="c"\; filenames="A9710625400112.png"\; state="\{\{state\}\}">c</figure-callout>}}_1+i{c}_2-[y_{j+1}^{\left(2\right)}{\mathrm{<figure-callout\; id="1"\; label="s"\; filenames="A9710625400112.png"\; state="\{\{state\}\}">s</figure-callout>}}_1+y_{j+1}^{\left(1\right)}{s}_2+i(y_{j+1}^{\left(2\right)}{s}_2-y_{j+1}^{\left(1\right)}{s}_1)]/(n_j-i{k}_j)}$ Order $b_1=y_{j+1}^{\left(2\right)}{\mathrm{<figure-callout\; id="1"\; label="s"\; filenames="A9710625400112.png"\; state="\{\{state\}\}">s</figure-callout>}}_1+y_{j+1}^{\left(1\right)}{s}_2,$ $b_2=y_{j+1}^{\left(2\right)}{s}_2-y_{j+1}^{\left(2\right)}{s}_1$ ${\mathrm{<figure-callout\; id="1"\; label="q"\; filenames="A9710625400112.png"\; state="\{\{state\}\}">q</figure-callout>}}_1=\frac{n_j{b}_1-k_j{b}_2}{n_j^2+k_j^2},$ $q_2=\frac{k_j{b}_1+n_j{b}_2}{n_j^2+k_j^2}$ So $Y_j=\frac{(y_{j+1}^{\left(1\right)}{c}_1-y_{j+1}^{\left(2\right)}{c}_2+k_j{s}_1-n_j{s}_2)+i(y_{j+1}^{\left(2\right)}{\mathrm{<figure-callout\; id="1"\; label="c"\; filenames="A9710625400112.png"\; state="\{\{state\}\}">c</figure-callout>}}_1+y_{j+1}^{\left(1\right)}{c}_2+{\mathrm{<figure-callout\; id="1"\; label="n\; j\; s"\; filenames="A9710625400112.png"\; state="\{\{state\}\}">n</figure-callout>}}_j{s}_{}{}_1+k_j{s}_2)}{(c_1-q_1)+i(c_2-q_2)}----\left(4\right)$ Order $a_1=y_{j+1}^{\left(1\right)}{c}_1-y_{j+1}^{\left(2\right)}{c}_2+k_j{s}_1-n_j{s}_2,$ $a_2=y_{j+1}^{\left(2\right)}{\mathrm{<figure-callout\; id="1"\; label="c"\; filenames="A9710625400112.png"\; state="\{\{state\}\}">c</figure-callout>}}_1+y_{j+1}^{\left(1\right)}{c}_2+{\mathrm{<figure-callout\; id="1"\; label="n\; j\; s"\; filenames="A9710625400112.png"\; state="\{\{state\}\}">n</figure-callout>}}_j{s}_{}{}_1+k_j{s}_2.$ a ₃=c ₁-q ₁, a ₄=c ₂-q ₂ $Y_j=y_j^{\left(1\right)}+i{y}_j^{\left(2\right)},$ Here $y_j^{\left(1\right)}=\frac{a_1{a}_3+a_2{a}_4}{a_3^2+a_4^2},$ $y_j^{\left(2\right)}=\frac{a_2{a}_3-a_1{a}_4}{a_3^2+a_4^2}.$ The ratio ψ of the energy-flux density on adjacent two interfaces of rete ₁For: ${\mathrm{\&psi;}}_j=y_{j+1}^{\left(1\right)}/\left[y_j^{\left(1\right)}{|\cos {\mathrm{\&delta;}}_j+i{Y}_{j+1}\sin {\mathrm{\&delta;}}_j/N_j|}^2\right]----\left(5\right)$ Correspondingly can be write as: ${\mathrm{\&psi;}}_j=y_{j+1}^{\left(1\right)}/\left[y_j^{\left(1\right)}(a_3^2+a_4^2)\right].$ Like this, begin recursion to top layer, obtain the combination admittance that whole film is at last from substrate: ${\mathrm{<figure-callout\; id="1"\; label="Y"\; filenames="A9710625400112.png"\; state="\{\{state\}\}">Y</figure-callout>}}_1=y_1^{\left(1\right)}+i{y}_1^{\left(2\right)}.$ Amplitude reflectance is: $r=\frac{{(N_0-y_1^{\left(1\right)})}^2-i{y}_1^{\left(2\right)}}{{({\mathrm{<figure-callout\; id="0"\; label="N"\; filenames="A9710625400111.png"\; state="\{\{state\}\}">N</figure-callout>}}_0+y_1^{\left(1\right)})}^2+i{y}_1^{\left(2\right)}}----\left(6\right)$ Reflectivity: $R=\frac{{(N_0-y_1^{\left(1\right)})}^2+{\left(y_1^{\left(2\right)}\right)}^2}{{({\mathrm{<figure-callout\; id="0"\; label="N"\; filenames="A9710625400111.png"\; state="\{\{state\}\}">N</figure-callout>}}_0+y_1^{\left(1\right)})}^2+{\left(y_1^{\left(2\right)}\right)}^2}----\left(7\right)$ The transmissivity that whole film is is: $T=(1-R)\underset{j=1}{\overset{m}{\mathrm{\&Pi;}}}{\mathrm{\&psi;}}_j----\left(8\right)$

(8) m is the number of plies of rete in the formula

Film will reach the design that meets film system by the control to film thickness d in preparation process.In the depositing of thin film process, select different sedimentary conditions according to different materials.The structure of film 2 has multiple.

Advantage of the present invention: cladding glass of the present invention, can have high reflectance in infrared light region, and reach extremely low limit at the visible region reflectivity, be less than cladding glass surface that the reflectivity of coated glass not promptly deposits film to the reflectivity of visible light reflectivity less than substrate glasses, therefore can reach reflectivity less than 2%, eliminate the public hazards that white light pollution brings modern city.

Description of drawings:

Fig. 1 is a structural representation of the present invention

Fig. 2 is the reflectance curve of the cladding glass of no white light pollution of the present invention

Fig. 3 is the transmittance graph of the cladding glass of no white light pollution of the present invention

Fig. 4 is the reflectance curve of the cladding glass of no white light pollution of the present invention in the visible region

Embodiment: the reflectivity that table 1 is pairing visible light and infrared light region for several different films.

Film layer structure in the table 1 as shown in Figure 1.

With the film of table 1 is 1 to be example, and when reflectivity R 〉=85% of infrared rays wave band, the reflectivity of visible light is R≤1% o'clock.Extrapolate the film structure of film according to above-mentioned formula (1)-(8) formula, wherein rete is counted m=5, and window glass is adopted in substrate 1, and its refractive index is 1.52, and the material of film system: rete 21 is TiO ₂, rete 22 is SiO ₂, rete 23 is Ag, rete 24 is TiO ₂, rete 25 is SiO ₂The thickness d of each tunic layer is respectively: substrate of glass/d ₁25nm/d ₂5nm/d ₃10nm/d ₄25nm/d ₅50nm.Magnetron sputtering deposition is adopted in the preparation of film.Architectural is to adopt large-scale magnetic control sputtering system with cladding glass, and sputtering system has full automatic control device.

The rete 21TiO of film ₂Deposition adopts reactive sputter-deposition, and during splash-proofing sputtering metal Ti target, sputter gas is an argon gas, and reacting gas is an oxygen, and the flow of oxygen is controlled by gas flow meter.The flow of oxygen is 0.8cm ³/ sccm (25 ℃, 1 atmospheric pressure), sputtering power is 400W, operating air pressure is 2Pa.

The rete 22SiO of film ₂The direct sputter SiO of deposition ₂Material does not charge into reacting gas, and sputtering power is 900W, and operating air pressure is 2Pa.

The direct splash-proofing sputtering metal silver of the deposition of the rete 23Ag of film target does not charge into reacting gas, and sputtering power is 500W, and operating air pressure is 2Pa.

The rete 24TiO of film ₂With rete 21TiO ₂Sedimentary condition identical.

The rete 25SiO of film ₂With rete 22SiO ₂Sedimentary condition identical.

The thickness of each layer film of the present invention should satisfy (1)-(8) formula, as long as in the lower scope of the luminance factor of visible region, the thickness of each tunic has certain excursion.The variable thickness of each tunic is calculated value surely, but each listed thicknesses of layers shows second layer thicknesses of layers d from table 1 ₂〉=0, and the thickness of other each retes all must be simultaneously greater than 0, i.e. d simultaneously ₁＞0, d ₃＞0, d ₄＞0, d ₅＞0.And the structure difference of each rete, then the thickness of each rete is also inequality, as: film is 1 the 3rd layer of 23d ₃At 5-30nm

Film is 2 the 3rd layer of 23d ₃At 40-80nm

Film is 3 the 3rd layer of 23d ₃At 5-30nm

Film is 4 the 3rd layer of 23d ₃At 40-80nm

Change in the scope, the thickness of other each layer film is changing in corresponding scope, can obtain the film article at the low reflectivity of visible region, reflectivity that infrared light region is high equally, helps the suitability for industrialized production of cladding glass like this.

Its result of the cladding glass that is obtained records reflectance curve as shown in Figure 2.

Transmittance graph as shown in Figure 3.

The visible region reflectance curve as shown in Figure 4.

The above results has proved the advantage of the no white light pollution that the present invention had.

Claims (6)

1, a kind of cladding glass that does not have white light pollution comprises substrate of glass (1) and is deposited on the lip-deep film of substrate (1) (2), it is characterized in that the structural order of concrete film (2) is:

[1], is deposited on the lip-deep first floor film of substrate of glass (1) (21) and is refractive index greater than 2.0 metal oxide film by substrate of glass (1) beginning;

[2] being deposited on the lip-deep second layer film of above-mentioned first floor film (21) (22) is the silicon oxide film of refractive index less than substrate of glass (1) refractive index;

[3] being deposited on above-mentioned second layer film (22) lip-deep three-layer thin-films (23) is greater than 70% rete to infrared reflectivity;

[4] to be deposited on above-mentioned three-layer thin-film (23) lip-deep four-level membranes (24) be refractive index greater than 2.0 metal oxide film;

[5] being deposited on the lip-deep layer 5 film of above-mentioned four-level membrane (24) (25) is the silicon oxide film of refractive index less than substrate of glass (1) refractive index.

2,, it is characterized in that refractive index is titanium dioxide (TiO greater than 2.0 metal oxide film according to a kind of cladding glass of claim 1 ₂) film.

3,, it is characterized in that refractive index is silica (SiO less than the silicon oxide film of substrate of glass (1) refractive index according to a kind of cladding glass of claim 1 ₂) film.

4, according to a kind of cladding glass of claim 1, it is characterized in that be silver (Ag) to infrared reflectivity greater than 70% film, or titanium nitride (TiN) film.

5,, it is characterized in that being deposited on the thicknesses of layers d of second layer film (22) on first floor film (21) surface according to a kind of cladding glass of claim 1 ₂〉=0.

6,, it is characterized in that being deposited on the thicknesses of layers d of the surperficial upper film of substrate of glass (1) (21) according to a kind of cladding glass of claim 1 ₁, the thicknesses of layers d of three-layer thin-film (23) ₃, the thicknesses of layers d of four-level membrane (24) ₄, the thicknesses of layers d of layer 5 film (25) ₅All must be simultaneously greater than 0.

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