CN100447103C - colored soda lime glass - Google Patents

Abstract

The present invention relates to colored soda-lime glass comprising: iron in an amount expressed by weight of oxide Fe₂O₃ greater than or equal to 0.5, relative to the total weight of the glass %, and less than or equal to 1.0% (total iron content); Fe²⁺/total Fe (redox ratio) in the range of 20-65%; cerium, relative to the total weight of the glass The content expressed by weight of CeO₂ is greater than or equal to 0.1%; Titanium, the content expressed by weight of TiO₂ relative to the total weight of the glass is greater than or equal to 0% and less than 0.2%. The light transmission (TLA4) of the glass is in the range of 15-55%, the total transmission of ultraviolet light (TUV4) is less than or equal to 30%, and the dominant wavelength of transmission (λ_D) is less than or equal to 491 Nano. For example, the glass can be used as a side window or a rear view mirror or a roof window or an openable sunroof of a motor vehicle.

Description

colored soda lime glass

The present invention relates to colored soda lime glass.

Soda-lime glass can be clear or tinted, eg transmitting green, gray or blue.

The expression "soda-lime glass" as used herein is broad and relates to any glass which may contain (in weight percent) the following principal glass-forming components:

SiO ₂ 60-75%

_Na2O 10-20%

CaO 0-16%

K ₂ O 0-10%

MgO 0-10%

Al ₂ O ₃ 0-5%

BaO 0-2%

BaO+CaO+MgO 10-20%

K ₂ O+Na ₂ O 10-20%.

B ₂ O ₃ 0-5%

In some cases, the total weight percentage of BaO, CaO and MgO in soda lime glass can be greater than 10%, or even greater than 12%.

Such glasses are widely used, for example, in the field of glazing for motor vehicles or buildings. The glass is usually produced in the form of ribbons by the float process. Said strips can be cut into sheets, which can then be bent or treated to improve their mechanical properties, such as a thermal toughening step.

It is often necessary to correlate the optical properties of the glass sheet to a standard light source. In this specification, two standard illuminants are used: Illuminant C and Illuminant A as defined by the Commission Internationale de I'Eclairage (C.I.E.). Light source C represents: average daylight with a color temperature of 6700K. This light source is especially useful for evaluating the optical properties of glazing used in buildings. Light source A represents the radiation of a Planck radiator with a temperature of about 2856K. This illuminant describes the light emitted by automotive headlights and is primarily used to evaluate the optical properties of glazing for motor vehicles.

The Commission Internationale de l'Eclairage also published a document entitled "Colorimetrie, Recommendations Officielles de la CIE [Colorimetry and Official Recommendations of the CIE]" (May 1970), which describes the determination of the ratio of light rays of each wavelength in the visible spectrum. The color coordinates, as a result, can be represented by a diagram with orthogonal axes x and y, called the CIE tricolor diagram (1931). The three-color diagram shows representative trajectories of light rays at each wavelength (expressed in nanometers) of the visible spectrum. This locus is called the "spectral locus" and rays with coordinates lying on this locus are said to have 100% excitation purity for the appropriate wavelength. The spectral locus is closed by a line called the purple dividing line connecting the spectral loci whose coordinates correspond to wavelengths of 380 nanometers (purple) and 780 nanometers (red). The region between the spectral locus and the violet dividing line is valid for any trichromatic coordinates of visible light. For example, the coordinates of a ray emitted by light source C correspond to x=0.3101 and y=0.3162. This point C is considered white light and therefore has an excitation purity equivalent to zero for any wavelength. Lines can be drawn from point C to the spectral locus at any desired wavelength, and any point lying on these lines can be determined not only by its x and y coordinates, but also by the wavelength of the line lying on it and its from The distance of point C relative to the total length of the wavelength line is a function. Thus, the color of light transmitted by a colored glass sheet can be described by its dominant wavelength (λ _D ) and its excitation purity (P) expressed as a percentage.

The CIE coordinates of light transmitted through a sheet of colored glass will depend not only on the composition of the glass but also on its thickness. In this specification, as in the claims, all values of the excitation purity P and the dominant wavelength λ _D of the transmitted light are based on the specific internal transmission ( specific internal transmission) (SIT _λ ) to calculate. The spectral specific internal transmission of a glass sheet is governed solely by the absorptivity of the glass and can be expressed by the Beer-Lambert law:

${\mathrm{<span\; class="notranslate">\; SIT</span>}}_{\mathrm{<span\; class="notranslate">\; \&lambda;</span>}}<span\; class="notranslate">\; =</span>{\mathrm{<span\; class="notranslate">\; e</span>}}^{{<span\; class="notranslate">\; -</span>\mathrm{<span\; class="notranslate">\; EA</span>}}_{\mathrm{<span\; class="notranslate">\; \&lambda;</span>}}}$

where A _λ is the absorption coefficient (cm ⁻¹ ) of the glass at the wavelength in question and E is the thickness of the glass (cm). In an approximation, SIT _λ can also be expressed by:

(I ₃ +R ₂ )/(I ₁ -R ₁ )

In the formula, I ₁ is the intensity of visible light incident on the first surface of the glass sheet, R ₁ is the intensity of visible light reflected from this surface, I ₃ is the intensity of visible light transmitted from the second surface of the glass sheet, and R ₂ is the intensity of visible light transmitted through the glass sheet. Intensity of visible light reflected by the second plane on the inside of the glass sheet.

The following parameters are also used in the following description and claims:

- Total light transmission (TLA4) for light source A measured from a fixed viewing angle of 2 degrees for a thickness of 4 mm. This total light transmission is the result of integrating between the wavelengths of 380 and 780 nanometers: ∑T _λ E _λ S _λ /∑E _λ S _λ , where T _λ is the transmission at wavelength λ and E _λ is the light source The spectral distribution of A, while S _λ is the sensitivity of the normal human eye as a function of wavelength λ;

- Total energy transmission (TE4) measured for a thickness of 4 mm. This total energy transmission is _the result of integrating between the 300 and 2500 nanometer wavelengths: _ΣTλEλ / _ΣEλ . The energy distribution E _λ is the spectral energy distribution of the sun at 30 degrees above the horizon with an air mass of 2 and an inclination of 60 degrees relative to the horizontal glazing. This distribution, known as the "Moon distribution", is determined using the standard ISO9050;

- selectivity (SE) measured in terms of the ratio of total light transmission to total energy transmission (TLA/TE) of standard illuminant A;

- Total transmission of ultraviolet light (TUV4) measured for a thickness of 4 mm. This total transmission is the result of the integration between the wavelengths of 280 and 380 nm of the following formula: ∑T _λ U _λ /∑U _λ , where U _λ is the spectral distribution of ultraviolet radiation through the atmosphere, determined using standard DIN67507;

- Fe ²⁺ /total Fe ratio, sometimes called the redox ratio, which expresses the ratio of the Fe ⁺² atomic weight to the total iron atomic weight in the glass and is obtained by:

Fe ²⁺ /Total Fe=[24.4495x log(92/τ ₁₀₅₀ )]/t _Fe2O3

where τ ₁₀₅₀ transmits at 1050 nm wavelength, 5 mm thick glass ratio, t _Fe2O3 represents the total iron content in the _form of oxide _Fe2O3 and is measured by X-ray fluorescence.

Tinted glass is useful in architectural applications and as glazing in railroad cars and motor vehicles. In architectural applications, glass sheets with a thickness of 4-6 mm are usually used; while in the automotive sector, glass sheets with a thickness of 1-5 mm are usually used, especially for the production of monolithic glazing; and in the case of laminated glazing In particular windshields, between 1 and 3 mm in thickness, two glass sheets of said thickness are bonded together by an interlayer film usually made of polyvinyl butyral (PVB).

One of the objects of the present invention is to provide a soda-lime glass with low light transmission, preferably blue glass, which suppresses the unpleasant discoloration of objects located inside the area enclosed by said glass.

EP01013620Al and PCT/EP01/06861 respectively describe highly selective glasses comprising iron with a high redox ratio (Fe ²⁺ /total iron), and cobalt and/or chromium and/or vanadium. However, increasing the high redox ratio may be detrimental to other optical properties, such as total transmission of ultraviolet light causing discoloration of objects located inside the region enclosed by the glass.

The present invention proposes: a glass composition having all the desired properties, in particular filter properties for ultraviolet solar radiation.

The present invention provides a colored soda lime glass comprising glass-forming principal components and a colorant, the colorant comprising:

- iron in an amount greater than or equal to 0.5% and less _than or equal to 1.0% (total iron) expressed as oxide _Fe2O3 by weight relative to the total weight of the glass,

- ferrous iron in the range of 20-65% expressed as Fe ²⁺ atomic weight relative to the total weight of iron atoms present in the glass (ratio Fe ²⁺ /total Fe),

- cerium, in an amount greater than or equal to 0.1%, expressed as a weight of _CeO2 relative to the total weight of the glass,

- titanium, in a content expressed by weight of _TiO2 relative to the total weight of the glass, greater than or equal to 0% and less than 0.2%,

And the glass has the following properties:

- light transmission in the range of 15-55%, measured for illuminant A and calculated relative to a thickness of 4 mm (TLA4),

- a total transmission of ultraviolet light (TUV4) less than or equal to 30%, measured for a thickness of 4 mm,

- the transmitted dominant wavelength (λ _D ) is less than or equal to 491 nanometers.

It has been found that the glasses are capable of simultaneously satisfying commercially desired properties with regard to aesthetics and energy. In particular, in the field of motor vehicles, the colored glass according to the invention can be blue-shaded, with a transmission wavelength less than or equal to 491 nm, which is required by car manufacturers, and the low light transmission and low total transmission of ultraviolet rays make it possible Unpleasant discoloration of objects inside the glass-enclosed region is suppressed.

A cerium content greater than or equal to 0.1%, expressed in terms of _CeO2 weight relative to the total weight of the glass, which, in combination with the iron composition criteria, makes it possible to produce glasses that have an overall transmittance at the transmitted wavelength, light transmission and UV rays All aspects can meet the standards of aesthetics and energy, especially the standards required by automobile manufacturers.

Iron is present in the vast majority of glass sold today, especially colored glass. The presence of Fe ³⁺ makes the glass have light absorption ability to short-wavelength visible light (410 and 440 nanometers) and a very high absorption band of ultraviolet light (absorption band centered at 380 nanometers), while the presence of Fe ²⁺ ions Will cause high absorption of infrared rays (absorption band centered at 1050 nm). The presence of Fe ³⁺ will give the glass a yellowish tint, which is generally considered undesirable, while the presence of ferrous ions, Fe ²⁺ , will cause a distinct blue-green color. Therefore, a high concentration of Fe2 ⁺ in the glass will reduce the energy transmission TE and provide a pleasing color. However, the presence of iron in the molten glass bath will cause absorption of infrared radiation, which can inhibit thermal diffusion in glass production furnaces and thus make production more difficult. In addition, the light transmission of the glass will decrease when the iron concentration is increased.

The energetic and optical properties of glass, especially its colour, its light transmission and its total transmission of UV rays, result from complex interactions between its components. The properties of the individual components of the glass depend on their redox state and thus on other components which affect said redox state.

It has been found that by easily controlling its composition, especially iron and cerium, the glasses defined in the claims can be adapted to aesthetic criteria (colour) and optical/energy criteria (light transmission and total transmission of UV rays).

Preferably, the total iron content is less than or equal to 0.90%, preferably less than or equal to 0.89%. This will facilitate the transition from clear glass production to colored glass production.

Preferably, the total iron content is at least 0.7%, more preferably at least 0.75%. This not only facilitates the formation of pleasing colors, but also facilitates low light transmission as well as low energy transmission.

Preferably, the glass according to the invention contains ferrous iron in a content expressed as Fe2 ⁺ atomic weight relative to the total weight of iron atoms present in the glass in the range of 20-65%, preferably in the range of 35-55% In the range, advantageously in the range of 40-50%. Such a ratio makes it possible to obtain a glass combining good selectivity and low transmission of UV rays.

Preferably, the glass according to the invention contains cerium in an amount greater than 0.15%, preferably greater than 0.25%, expressed in terms of the weight of _CeO2 relative to the total weight of the glass, in order to suppress as far as possible, under the action of ultraviolet solar radiation, the Objects inside the area enclosed by the glass according to the invention discolor unpleasantly. The glass according to the invention preferably comprises cerium in an amount expressed as CeO ₂ weight of less than 1.0%, preferably less than or equal to 0.5%, relative to the total weight of the glass. In fact, when too large an amount of cerium is present, the dominant wavelength may be shifted towards green and yellow, which is contradictory to the preferred hue.

The present invention advantageously combines a high redox ratio with a cerium content that provides the desired properties without compromising the aesthetics of the glass.

Preferably, the glass according to the invention comprises titanium, relative to the total weight of the glass, with a titanium content greater than or equal to 0% and less than 0.2%, preferably less than 0.15%, more preferably less than 0.10% by weight of _TiO2 , relative to the total weight of the glass . In fact, high levels of _TiO2 risk developing an undesired yellow tint. In some cases, due to the presence of impurities, _TiO2 will only be contained in the glass without intentional addition.

In order to produce glasses having a commercially desirable color, such as is considered pleasing, the glasses according to the invention may comprise, in addition to those components already mentioned, one or more of the following colorants.

-cobalt

The presence of cobalt tends to give the glass a deep blue color. The glass according to the invention preferably comprises cobalt in an amount expressed as weight of Co of greater than 75 ppm, more preferably greater than 100 ppm, relative to the total weight of the glass. Preferably, the cobalt content is less than or equal to 350 ppm, more preferably less than or equal to 250 ppm. In fact, too high a cobalt content will impair the selectivity of the glass.

In a preferred form, the glass according to the present invention comprises a glass-forming main component and a colorant mainly composed of Fe, Ce and Co according to at least one of the above-mentioned ranges. Ti may also be added to the composition.

In another preferred form, the glass according to the invention comprises a glass-forming main component and a colorant consisting of Fe, Ce and Co according to at least one of the above ranges. Ti may also be added to the composition.

-chromium

The presence of Cr ^III tends to give the glass a light green color, while the presence of Cr ^VI will produce a strong absorption band at 365 nm and give the glass a yellow tint. Preferably, the glass comprises chromium in an amount of at least ₅ ppm expressed as _Cr2O3 by weight relative to the total weight of the glass. In some cases, the glass may contain chromium in an amount greater than or equal to 50 ppm, even greater than or equal to 100 ppm. Preferably, the chromium content is less than 1000 ppm, more preferably less than or equal to 500 ppm.

In a preferred form, the glass according to the present invention comprises a glass-forming main component and a colorant mainly composed of Fe, Ce, Co and Cr according to at least one of the above ranges. Ti may also be added to the composition.

In another preferred form, the glass according to the invention comprises a glass-forming main component and a colorant consisting of Fe, Ce, Co and Cr according to at least one of the above ranges. Ti may also be added to the composition.

-vanadium

The presence of vanadium tends to give the glass a greenish tint. The glass according to the invention preferably comprises vanadium in an amount expressed as V ₂ O ₅ by weight of less than 1000 ppm, preferably less than 500 ppm, relative to the total weight of the glass. In some cases, _V2O5 will be included in the glass only due to the presence of impurities, _without intentional addition.

The light transmission TLA4 of the colored glass according to the invention is in the range of 15-55%, preferably in the range of 20-45%, advantageously between 25-35%. This makes the glass very suitable for use, for example, as a glazing of a motor vehicle, in particular as a side glazing, a rear view window, a roof glazing or an openable sunroof.

The colored glass according to the invention has a total transmission of ultraviolet rays (TUV4) preferably less than or equal to 30%, but also less than or equal to 25%, advantageously less than or equal to 20%. Such a value of TUV4 will help prevent unpleasant discoloration of objects located in the area surrounded by the glass and exposed to ultraviolet solar radiation.

It would be desirable if the colored glass according to the invention had an energy transmission TE4 of less than 45%, preferably less than 35%, advantageously less than 25%. During exposure to the sun, the low energy transmission will help limit the temperature rise in interior areas surrounded by the glass of the invention, such as in buildings or motor vehicles.

The glasses according to the invention preferably have a selectivity greater than 1.0, more preferably greater than 1.1. High selectivity is advantageous both for applications in motor vehicles and for building applications as it will help limit the temperature rise due to solar radiation and thus enhance the thermal comfort of vehicle or building occupants , while providing high natural lighting and visibility through glass windows.

In view of the color of the glass of the present invention, it would be desirable if its transmission dominant wavelength λ _D was less than or equal to 489 nm. This is equivalent to glass whose transmission color is typically bluish, which would be pleasing to the human eye and highly acceptable commercially, especially for glazing in motor vehicles. It is advantageous if the glass has a λ _D of less than or equal to 487 nm.

The transmitted excitation purity of the glasses according to the invention is preferably greater than 10%, more preferably greater than 15%. This equates to a pronounced tint, which is commercially desirable. In some cases, the transmitted excitation purity can be greater than or equal to 20%, or even greater than 25%.

In some cases, the glass according to the invention comprises nickel in an amount expressed as NiO weight relative to the total weight of the glass of less than 200 ppm, preferably less than 100 ppm. The presence of nickel impairs the selectivity of glasses containing nickel because nickel does not absorb light in the infrared range, which results in significant energy transmission values. In addition, nickel will give the glass a yellow tint. Furthermore, the presence of nickel will cause difficulties in the production of the glass (formation of nickel sulfides, inclusions in the glass). In a particular embodiment, the glass according to the invention is free of nickel as colorant.

Preferably, the glass according to the invention contains manganese in an amount expressed as MnO ₂ weight relative to the total weight of the glass of less than 1500 ppm, preferably less than 500 ppm. Manganese in the form of _MnO2 has oxidizing properties, it is able to change the redox state of iron and produce a green tint.

Preferably, the glass according to the invention comprises more than 2% by weight of magnesium oxide MgO relative to the total weight of the glass. The presence of magnesium aids in the fusion of the components during glass melting.

Advantageously, the glass according to the invention comprises less than 30 ppm selenium, preferably less than 20 ppm selenium, relative to the total weight of the glass. As a colorant, the presence of selenium will promote low light transmission, but if the content is too large, it will give the glass an undesirable pink or red color.

According to a preferred form of the invention, the colorant is present in the following proportions (expressed as a percentage of the total weight of the glass in the form indicated):

_{Fe2O3 0.5-1.0} %

CeO ₂ 0.1-0.95%

Co 130-160ppm

Cr ₂ O ₃ 150-950ppm

Se 0-10ppm

TiO ₂ 0-0.15%

Fe ²⁺ / total Fe 30-50%

The glass preferably has the following optical properties:

TLA4 15-55%

TE4 ＜45%

TUV4 ≤30%

λ _D ≤491nm

P > 10% and < 35%

According to a particularly preferred form of the invention, the amount of colorant is present in the following proportions (expressed as a percentage of the total weight of the glass in the indicated form):

_{Fe2O3 0.7-0.9} %

CeO ₂ 0.2-0.7%

Co 135-150ppm

Cr ₂ O ₃ 300-500ppm

Se 0-10ppm

TiO ₂ 0-0.15%

Fe ²⁺ / total Fe 35-45%

The glass preferably has the following optical properties:

TLA4 25-40%

TE4 20-30%

TUV4 10-20%

λ _D 480-490nm

P 20-35%

According to a preferred embodiment, the glass according to the invention comprises glass-forming main components and a colorant mainly consisting of Fe, Ce, Co, Cr and Se according to at least one of the above ranges. Ti may also be added to the composition.

In another preferred form, the glass according to the invention comprises a glass-forming main component and a colorant consisting of Fe, Ce, Co, Cr and Se according to at least one of the above ranges. Ti may also be added to the composition.

It would be desirable if the glasses according to the invention were free of fluorine compounds, or at least said compounds did not constitute more than 0.2% by weight of F relative to the glass. These compounds will actually cause environmentally harmful furnace effluents and will also cause corrosion to the refractory lining the interior of the production furnace.

The colored glass according to the invention preferably forms a glazing of a motor vehicle. For example, the glazing can advantageously be used for side or rear windows or roof glazing or openable sunroofs of vehicles.

The glass according to the invention can be coated. For example, the coating may be a metal oxide layer which will reduce the temperature rise due to solar radiation and reduce the temperature rise in the passenger compartment of a vehicle using the glass as a glazing.

The glasses according to the invention can be produced by conventional methods. As batch material it is possible to use natural materials, recycled glass, slag or a combination of these materials. The colorant does not have to be added in the form indicated, but this manner of supplying the level of added colorant in the form indicated corresponds to conventional practice. In practice, iron is added as red iron oxide, cobalt is added as hydrated sulfates such as CoSO ₄ 7H ₂ O or CoSO ₄ 6H ₂ O, and chromium is added as dichromate such as K ₂ Cr ₂ O ₇ . Cerium is often introduced as oxide or carbonate, and vanadium is added as vanadium oxide or sodium vanadate. When present, selenium can be added in elemental form or in the form of a _selenite such as _Na2SeO3 or _ZnSeO3 .

Other elements are sometimes present as a result of impurities in the batch materials used to prepare the glasses according to the invention; whether these materials are natural materials which are increasingly used, recycled glass or slag, but when these impurities do not give These glasses are still considered to be in accordance with the present invention.

The invention will now be illustrated by the following examples:

Examples 1-143

Table I identifies the basic composition of the glasses by non-limiting indications. It should be understood that with a basic composition having oxides within the weight percent ranges given at the beginning of the description, glasses with the same optical and energetic properties can be obtained.

The glass according to the invention comprises: less than 100 ppm NiO, less than 500 ppm _MnO2 , and unless otherwise stated, less than 3 ppm Se, less than 0.1% _TiO2 and more than 2% MgO.

Table I

Analysis of basic glass SiO₂Al₂O₃CaOMgONa₂OK₂OSO₃ 71.5-71.9% 0.8% 8.8% 4.2% 14.1% 0.1% 0.05-0.45%

The following table gives the concentrations of the individual components, the optical and energetic properties of the glasses of the invention. The concentrations are determined by X-ray fluorescence of the glass and converted into the molecular states shown.

Table II

Example Fe₂O₃(%) Fe²⁺/total iron (%) CeO₂(%) Co(ppm) Cr₂O₃(%) Se(ppm) TLA4(%) TUV4(%) λ_D(nm) TE4(%) P(%) SE 1 0.875 32.73 0.29 150 351 32.9 12.6 483.3 25.9 30.2 1.27 2 0.873 35.42 0.49 146 352 33.0 11.8 483.4 24.9 30.2 1.32 3 0.893 41.52 0.10 152 352 31.4 15.8 482.9 22.4 33.3 1.40 4 0.874 33.58 0.49 147 354 32.8 11.2 483.5 25.5 29.8 1.29 5 0.871 33.28 0.39 145 355 32.7 11.7 483.6 25.7 29.7 1.27 6 0.870 32.72 0.49 147 362 32.7 11.1 483.6 25.8 29.6 1.27 7 0.848 24.12 0.97 142 359 34.9 8.3 484.4 31.4 25.3 1.11 8 0.890 39.35 0.10 152 343 31.7 16.0 482.8 23.1 33.0 1.37 9 0.867 35.19 0.48 146 352 32.4 11.7 483.4 24.8 30.5 1.31 10 0.873 39.08 0.29 141 347 32.4 13.8 483.3 23.5 31.3 1.38 11 0.850 25.65 0.97 138 363 35.2 8.3 484.8 30.5 24.8 1.15 12 0.854 48.24 0.29 143 298 29.6 14.3 482.4 20.4 35.8 1.45 13 0.854 46.99 0.285 148 308 31.8 14.1 483.2 21.5 32.9 1.48 14 0.861 47.85 0.28 168 310 29.7 14.4 482.5 20.6 35.4 1.44 15 0.898 49.89 0.30 148 354 29.9 12.9 483.4 19.6 33.8 1.53 16 0.900 50.25 0.30 155 362 29.3 13.4 482.5 19.3 36.1 1.52 17 0.882 45.50 0.30 149 322 29.3 13.3 482.0 20.6 36.1 1.42 18 0.908 48.94 0.32 151 329 28.6 13.1 482.5 19.1 36.5 1.50 19 0.906 49.05 0.30 160 333 27.5 12.9 482.1 18.7 37.8 1.47 20 0.906 48.24 0.30 164 333 28.5 12.7 482.5 19.3 36.3 1.48 twenty one 0.864 30.81 0.68 145 313 33.8 10.1 483.2 27.4 29.1 1.23 twenty two 0.852 24.58 0.89 144 310 34.9 8.6 483.6 31.3 26.6 1.15 twenty three 0.850 23.97 0.97 141 316 35.3 8.3 483.8 31.9 25.8 1.11

Example Fe₂O₃(%) Fe²⁺/total iron (%) CeO₂(%) Co(ppm) Cr₂O₃(%) Se(ppm) TLA4(%) TUV4(%) λ_D(nm) TE4(%) P(%) SE twenty four 0.847 43.34 0.30 139 341 30.5 14.2 482.3 22.2 34.9 1.37 25 0.800 44.00 0.30 140 400 30.3 15.4 482.6 22.6 34.6 1.34 26 0.750 45.00 0.30 145 450 29.5 16.8 482.7 22.7 35.3 1.30 27 0.700 45.00 0.50 145 500 29.7 15.6 483.0 23.9 34.7 1.24 28 0.650 47.00 0.50 150 500 28.9 16.9 482.5 23.5 36.5 1.22 29 0.700 45.00 0.40 155 400 28.8 16.7 481.6 23.7 38.0 1.22 30 0.600 45.00 0.70 160 380 29.5 15.4 480.8 26.4 39.4 1.12 31 0.550 45.00 0.70 155 550 29.8 16.9 482.4 27.0 36.2 1.10 32 0.700 45.00 0.50 150 450 29.3 15.6 482.3 23.8 36.3 1.23 33 0.500 50.00 0.90 155 590 28.2 15.8 482.6 25.0 37.6 1.13 34 0.600 40.00 0.90 150 50 35.7 12.2 478.0 32.4 38.7 1.10 35 0.850 40.00 0.90 140 50 33.4 6.3 479.6 26.4 36.3 1.26 36 0.600 50.00 0.90 150 0 32.1 12.1 478.0 26.1 43.0 1.23 37 0.850 40.00 0.90 140 0 33.8 6.1 479.1 26.7 37.0 1.26 38 0.875 50.00 0.90 100 50 36.1 5.4 481.7 21.8 32.1 1.66 39 0.850 55.00 0.90 70 50 39.8 5.7 483.1 21.1 28.3 1.88 40 0.875 60.00 0.90 50 300 39.0 5.5 487.7 17.0 23.2 2.29 41 0.850 50.00 0.90 30 0 49.2 5.3 485.5 27.2 19.6 1.81 42 0.847 40.00 0.30 139 340 31.8 14.2 482.3 24.4 33.7 1.30 43 0.850 44.00 0.30 140 500 28.8 14.5 483.9 20.8 33.2 1.39 44 0.850 45.00 0.30 150 200 29.9 13.8 483.9 21.5 33.2 1.39 45 0.850 45.00 0.30 170 100 28.9 13.6 479.3 21.5 44.3 1.34 46 0.850 40.00 0.30 190 50 29.5 13.5 478.3 24.5 46.9 1.20 47 0.850 45.00 0.30 200 0 27.0 13.4 478.0 21.2 51.2 1.28 48 0.850 45.00 0.30 250 380 19.6 14.2 480.1 17.5 54.9 1.12 49 0.600 25.00 0.95 350 20 24.9 11.4 475.4 36.8 69.9 0.68 50 0.875 45.00 0.90 76 600 32.4 6.9 489.8 21.3 19.8 1.52 51 0.850 50.00 0.11 105 600 29.0 17.0 486.2 17.1 28.4 1.69 52 0.850 50.00 0.90 120 500 27.8 7.3 485.1 17.9 30.3 1.55 53 0.700 55.00 0.90 160 0 28.6 9.7 478.6 20.3 46.2 1.41 54 0.850 30.00 0.90 165 500 31.6 7.2 483.5 29.7 31.1 1.07 55 0.850 45.00 0.90 180 380 25.3 7.0 481.9 20.1 40.8 1.26 56 1.000 40.00 0.30 139 340 29.3 10.6 482.9 20.4 33.4 1.44

Example Fe₂O₃(%) Fe²⁺/total iron (%) CeO₂(%) Co(ppm) Cr₂O₃(%) Se(ppm) TLA4(%) TUV4(%) λ_D(nm) TE4(%) P(%) SE 57 0.950 44.00 0.30 140 500 27.2 12.1 484.3 18.1 39.1 1.50 58 0.970 45.00 0.30 150 200 28.0 11.0 481.1 18.4 39.1 1.52 59 1.000 45.00 0.30 170 100 17.6 10.1 479.9 17.6 44.0 1.51 60 1.000 40.00 0.30 190 50 27.1 10.0 479.0 20.5 46.6 1.32 61 0.970 45.00 0.30 200 0 25.1 10.6 478.5 18.0 50.9 1.39 62 0.850 45.00 0.10 160 380 27.8 16.6 481.9 16.6 39.2 1.39 63 0.850 45.00 0.10 140 550 28.2 17.0 484.2 20.0 33.4 1.44 64 0.850 45.00 0.95 140 700 26.3 7.1 486.5 19.5 29.5 1.35 65 0.900 40.00 0.95 140 800 26.7 6.1 488.2 20.9 26.5 1.28 66 0.875 45.00 0.90 150 950 23.1 7.7 488.8 23.1 17.0 1.35 67 0.900 40.00 0.50 237 600 20.0 11.1 482.1 18.7 47.2 1.07 68 0.700 35.00 0.90 5 30 50.0 9.7 485.3 37.8 10.7 1.32 69 0.700 30.00 0.20 34 30 50.0 18.1 481.1 39.7 15.8 1.26 70 0.510 55.00 0.10 165 500 28.0 24.9 481.6 21.6 42.7 1.29 71 0.850 45.00 0.90 280 380 16.4 7.0 479.9 17.1 58.9 0.96 72 0.970 45.00 0.90 200 600 19.9 4.7 483.6 15.1 41.3 1.32 73 0.990 45.00 0.90 220 600 17.8 4.2 483.1 13.9 44.9 1.27 74 0.850 30.00 0.20 48 455 42.9 15.6 490.9 32.8 12.9 1.31 75 0.850 20.00 0.90 200 380 33.4 6.94 481.0 35.8 35.4 0.93 76 0.850 25.00 0.20 180 380 33.8 15.4 481.1 32.6 35.4 1.04 77 0.850 20.00 0.30 180 380 35.6 14.1 481.1 35.9 33.3 0.99 78 0.850 50.00 0.20 140 300 28.1 15.3 481.9 17.9 38.2 1.57 79 0.850 50.00 0.40 150 380 26.5 15.3 482.4 17.3 38.5 1.53 80 0.820 30.00 0.40 100 380 39.2 13.7 482.4 32.7 38.5 1.20 81 0.800 33.00 0.40 80 200 41.6 13.8 482.4 32.9 38.5 1.27 82 0.750 35.00 0.40 50 180 44.4 14.9 482.4 33.9 38.5 1.31 83 0.850 32.00 0.20 40 150 45.3 14.9 482.4 33.5 38.5 1.35 84 0.650 40.00 0.20 20 50 48.0 19.4 482.4 34.7 38.5 1.38 85 0.800 32.00 0.40 15 20 49.2 13.4 482.4 36.5 38.5 1.35 86 0.847 43.34 0.30 139 341 30.5 14.2 482.3 22.2 34.9 1.37 87 0.850 44.00 0.30 140 340 10 27.8 14.1 482.8 20.3 28.3 1.37 88 0.900 45.00 0.30 145 450 30 20.3 13.2 487.6 14.8 14.4 1.38 89 0.850 45.00 0.50 175 500 30 15.3 12.4 485.0 14.0 18.9 1.09

Example Fe₂O₃(%) Fe²⁺/total iron (%) CeO₂(%) Co(ppm) Cr₂O₃(%) Se(ppm) TLA4(%) TUV4(%) λ_D(nm) TE4(%) P(%) SE 90 1.000 50.00 0.50 190 500 15.0 9.0 482.4 9.8 44.1 1.53 91 1.000 50.00 0.40 156 400 30 15.1 9.7 485.8 8.5 18.4 1.77 92 0.850 45.00 0.70 145 300 20 24.2 9.3 483.2 18.6 22.2 1.30 93 0.900 45.00 0.50 130 0 20 28.6 9.7 479.6 19.8 23.8 1.44 94 0.890 40.00 0.70 100 0 30 33.6 7.3 483.3 24.1 8.8 1.39 95 0.880 50.00 0.90 120 35 25 27.0 5.4 481.6 17.2 18.7 1.57 96 0.900 40.00 0.90 130 0 28 28.4 4.9 479.9 22.4 15.4 1.27 97 0.847 43.34 0.30 139 341 30.5 14.2 482.3 22.2 34.9 1.37 98 0.850 44.00 0.30 140 340 4 29.1 14.1 482.4 21.1 32.5 1.38 99 0.900 45.00 0.20 145 450 7 25.6 14.4 483.8 17.7 30.5 1.44 100 0.850 45.00 0.50 163 500 15 20.8 12.3 484.0 16.8 27.0 1.24 101 1.000 50.00 0.50 180 400 3 16.9 8.7 482.1 10.6 41.4 1.59 102 1.000 50.00 0.40 156 400 6 20.5 9.7 483.2 11.7 35.0 1.75 103 0.850 45.00 0.70 145 300 14 25.6 9.3 482.7 19.4 26.4 1.32 104 0.900 45.00 0.50 130 0 13 30.2 9.7 479.6 20.7 28.7 1.46 105 0.890 40.00 0.90 100 0 15 36.8 4.9 481.7 26.2 18.7 1.40 106 0.880 50.00 0.80 100 550 11 29.7 7.6 489.8 17.2 18.7 1.72 107 0.900 40.00 0.30 130 500 15 27.9 13.2 486.9 20.7 19.5 1.35 108 0.900 40.00 0.30 130 450 15 28.3 13.1 486.1 21.0 20.1 1.35 109 0.900 40.00 0.30 130 400 15 28.7 13.0 485.3 21.3 20.7 1.35 110 0.900 42.00 0.30 130 350 15 28.3 12.9 484.4 20.2 22.0 1.40 111 0.950 45.00 0.40 130 500 27.6 10.9 484.8 17.9 31.4 1.55 112 0.850 44.00 0.40 110 500 31.4 13.3 485.3 21.7 27.6 1.45 113 0.850 50.00 0.40 120 450 28.6 13.2 484.2 17.8 32.2 1.60 114 0.800 50.00 0.30 100 500 30.8 15.7 485.3 19.3 28.3 1.59 115 0.825 40.00 0.80 100 550 33.6 9.1 487.1 25.4 22.9 1.32 116 0.800 45.00 1.00 160 300 28.5 6.8 481.6 22.6 38.1 1.26 117 0.850 45.00 1.00 140 380 28.8 5.8 483.2 21.4 33.4 1.35 118 0.850 45.00 1.00 125 370 30.2 5.8 483.7 21.9 30.8 1.38 119 0.850 45.00 0.95 115 400 30.9 6.4 484.4 22.0 28.8 1.41 120 0.855 25.00 0.95 110 450 38.7 6.4 486.1 34.8 20.1 1.11 121 0.875 45.00 0.50 115 450 30.5 11.4 484.7 20.6 29.2 1.48 122 0.950 50.00 0.40 105 490 28.0 10.9 485.7 15.4 28.9 1.82

Example Fe₂O₃(%) Fe²⁺/total iron (%) CeO₂(%) Co(ppm) Cr₂O₃(%) Se(ppm) TLA4(%) TUV4(%) λ_D(nm) TE4(%) P(%) SE 123 0.850 59.00 0.40 120 500 24.6 13.3 484.5 11.6 34.8 2.12 124 0.700 64.00 0.40 80 400 29.5 16.6 484.4 14.1 30.9 2.09 125 0.850 65.00 0.50 75 400 27.0 11.9 485.4 9.7 30.0 2.78 126 0.850 60.00 0.40 80 380 28.8 13.1 485.0 12.9 29.6 2.24 127 0.850 42.00 0.30 120 500 31.4 14.5 484.8 22.7 28.9 1.39 128 0.850 43.00 0.30 130 600 29.3 14.7 485.4 21.1 29.8 1.39 129 0.855 40.00 0.30 140 650 29.1 14.7 485.6 22.4 29.9 1.30 130 0.825 45.00 0.30 115 500 31.1 15.1 484.8 21.5 29.1 1.44 131 0.800 45.00 0.30 105 490 32.4 15.6 485.1 22.5 27.5 1.44 132 0.850 45.00 1.00 100 0 35.4 4.9 480.4 35.4 31.2 1.43 133 0.830 45.00 1.35 120 300 31.3 1.9 483.4 23.3 30.0 1.34 134 0.810 47.00 0.10 105 460 31.9 17.7 484.5 21.0 29.1 1.52 135 0.828 41.92 0.29 148 379 31.8 15.3 483.0 23.1 32.8 1.38 136 0.800 40.00 0.90 105 100 37.0 7.5 480.9 28.5 29.3 1.30 137 0.850 45.00 0.30 185 850 21.7 15.2 485.4 16.7 37.1 1.29 138 0.850 46.00 0.30 180 800 22.1 15.1 485.1 16.5 37.2 1.34 139 0.850 45.00 0.80 175 750 22.9 9.0 485.3 18.0 35.4 1.27 140 0.875 47.00 0.10 175 750 22.3 16.9 484.8 15.5 37.8 1.44 141 0.845 35.00 0.80 200 700 25.1 9.0 484.0 24.2 36.9 1.04 142 0.856 40.00 0.30 187 750 24.0 12.5 484.7 20.5 36.4 1.16 143 0.845 35.00 0.80 115 200 36.6 7.9 481.9 29.7 28.2 1.23

Claims (41)

1. Colored soda-lime glass comprising glass-forming principal components and a colorant comprising: - iron, expressed in terms of the weight of the oxide _Fe2O3 relative to the total weight of the glass, i.e. the total iron content is greater than or _equal to 0.5% and less than or equal to 1.0%; - ferrous iron, expressed in terms of Fe ²⁺ atomic weight relative to the total weight of iron atoms present in the glass, i.e. the Fe ²⁺ /total Fe ratio is in the range of 20-65%, - cerium, in an amount greater than or equal to 0.1%, expressed in weight of _CeO2 relative to the total weight of the glass; - Titanium in an amount greater than or equal to 0% and less than 0.2% expressed by weight of _TiO2 relative to the total weight of the glass; - chromium, with a chromium content of at least ₅ ppm expressed as _Cr2O3 by weight relative to the total weight of the glass; And the glass has the following properties: - light transmission TLA4 in the range of 15-55%, which is measured for light source A and calculated relative to a thickness of 4 mm; - a total transmission TUV4 of ultraviolet rays less than or equal to 30% measured for a thickness of 4 mm; - the transmitted dominant wavelength λ _D is less than or equal to 491 nm, Wherein said main component of forming glass comprises by weight percentage relative to the total weight of glass: SiO ₂ 60-75% _Na2O 10-20% CaO 0-16% K ₂ O 0-10% MgO 0-10% Al ₂ O ₃ 0-5% BaO 0-2% BaO+CaO+MgO 10-20% K ₂ O+Na ₂ O 10-20%. _{B2O3 0-5} %. 2. The colored soda-lime glass according to claim 1, characterized in that the total iron content is less than or equal to 0.90%. 3. The colored soda-lime glass according to claim 2, characterized in that the total iron content is less than or equal to 0.89%. 4. Colored soda lime glass according to claim 1, characterized in that the total iron content is at least 0.7%. 5. Colored soda lime glass according to claim 4, characterized in that the total iron content is at least 0.75%. 6. Colored soda-lime glass according to claim 1, characterized in that the colorant comprises cerium in an amount greater than 0.15% expressed as a weight of _CeO2 relative to the total weight of the glass. 7. Colored soda lime glass according to claim 6, characterized in that the content of cerium is greater than 0.25%. 8. Colored soda-lime glass according to claim 1, characterized in that the colorant comprises cerium in an amount greater than 0.10% expressed as a weight of _CeO2 relative to the total weight of the glass. 9. Colored soda lime glass according to claim 8, characterized in that the content of cerium is less than or equal to 0.50%. 10. Colored soda-lime glass according to claim 1, characterized in that the colorant comprises titanium in a content of less than 0.15% expressed as the weight of _TiO2 relative to the total weight of the glass. 11. Colored soda-lime glass according to claim 10, characterized in that the titanium content is less than 0.10%. 12. Colored soda-lime glass according to claim 1, characterized in that the colorant comprises cobalt in an amount greater than 75 ppm expressed as the weight of Co relative to the total weight of the glass. 13. Colored soda lime glass according to claim 12, characterized in that the cobalt content is greater than 100 ppm. 14. Colored soda-lime glass according to claim 1, characterized in that the colorant comprises cobalt in a content expressed in weight of Co relative to the total weight of the glass of less than or equal to 350 ppm. 15. Colored soda lime glass according to claim 14, characterized in that the cobalt content is less than or equal to 250 ppm. 16. The colored soda lime glass according to claim 1, characterized in that the chromium content is greater than or equal to 50 ppm. 17. Colored soda lime glass according to claim 16, characterized in that the chromium content is greater than or equal to 100 ppm. 18. Colored soda-lime glass according to claim 1, characterized in that the colorant comprises chromium in an amount of less than ₁₀₀₀ ppm expressed as a weight of _Cr2O3 relative to the total weight of the glass. 19. Colored soda lime glass according to claim 18, characterized in that the chromium content is less than or equal to 500 ppm. 20. Colored soda-lime glass according to claim 1, characterized in that the colorant comprises vanadium in a content of less than ₁₀₀₀ ppm expressed in weight of _V2O5 relative to the total weight of the glass. 21. Colored soda lime glass according to claim 20, characterized in that the vanadium content is less than 500 ppm. 22. Colored soda-lime glass according to claim 1, characterized in that the colorant contains selenium in an amount of less than 30 ppm expressed as the weight of Se relative to the total weight of the glass. 23. Colored soda lime glass according to claim 22, characterized in that the selenium content is less than 20 ppm. 24. The colored soda-lime glass according to any one of claims 16-19, comprising a glass-forming main ingredient and a colorant consisting essentially of iron, cerium, titanium, cobalt and chromium. 25. The colored soda-lime glass according to any one of claims 16-19, comprising a glass-forming main ingredient and a colorant consisting of iron, cerium, titanium, cobalt and chromium. 26. Colored soda-lime glass according to any one of claims 1-3, characterized in that the colorant comprises ferrous iron expressed as Fe2 ⁺ weight relative to the total weight of iron atoms present in the glass The content is in the range of 35-55%. 27. The colored soda-lime glass according to claim 26, characterized in that the content of ferrous iron expressed by weight of Fe2 ⁺ is between 40-50%. 28. The colored soda-lime glass as claimed in claim 1, characterized in that its energy transmission TE4 measured on the basis of the moon distribution and calculated with a thickness of 4 mm is below 45%. 29. Colored soda lime glass according to claim 28, characterized in that its TE4 is below 35%. 30. Colored soda lime glass according to claim 29, characterized in that its TE4 is below 25%. 31. The colored soda lime glass as claimed in claim 1, characterized in that its light transmission TLA4 is in the range of 20-45%. 32. Colored soda lime glass according to claim 31, characterized in that its TLA4 is in the range of 25-35%. 33. Colored soda lime glass according to claim 1, characterized in that its selectivity SE4 is greater than 1.0. 34. Colored soda lime glass according to claim 33, characterized in that its selectivity SE4 is greater than 1.1. 35. The colored soda-lime glass as claimed in claim 1, characterized in that its total transmission TUV4 of ultraviolet rays, measured for a thickness of 4 mm, is less than or equal to 25%. 36. Colored soda lime glass according to claim 35, characterized in that its TUV4 is less than or equal to 20%. 37. Colored soda-lime glass according to one of claims 1 to 3, characterized in that its transmitted excitation purity is greater than 10%. 38. Colored soda lime glass according to claim 37, characterized in that its transmitted excitation purity is greater than 15%. 39. The colored soda-lime glass according to any one of claims 1-3, characterized in that its transmission dominant wavelength λ _D is less than or equal to 489 nanometers. 40. The colored soda-lime glass according to claim 39, characterized in that its transmission dominant wavelength is less than or equal to 487 nanometers. 41. The colored soda-lime glass as claimed in one of claims 1 to 3, characterized in that it is covered with a metal oxide layer.