JP3170225B2 - Green concealed glass - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

FIELD OF THE INVENTION The present invention relates to low luminous transmittance which is highly desirable for use as a privacy glazing in vehicles such as side and rear windows of box cars. ), A soda-lime-silica glass colored in green.
In particular, the glass is less than 60%, preferably about 10-4.
It has a luminous transmittance of 0%. As used herein, the term "green" has a dominant wavelength of about 480 to 565 nm and includes glass that can be characterized as green-blue, green-yellow, or green-grey in color. Further, the glasses of the present invention exhibit lower infrared and ultraviolet transmission as compared to typical green glass commonly used for automobiles. This glass can also be compatible with the flat glass manufacturing method. This application is related to US patent application Ser. 60 / 021,034.

[0002]

2. Description of the Prior Art Various dark colored infrared ultraviolet absorbing glass compositions are known in the art. The predominant colorant in typical dark tinted automotive blinds is iron, which is usually present in both Fe ₂ O ₃ and FeO. Certain glasses use cobalt, selenium, and optionally nickel along with iron to further suppress infrared and ultraviolet light and color, and are disclosed by Jones in U.S. Pat. Cheng) et al., US Patent No. 5,278,108, Baker
(Baker) et al., US Pat. No. 5,308,805.
No. 5,393,583 to Gulotta et al. And European Patent Application EP 0705.
800. Along with this colorant combination,
There are other glasses that contain chromium, see U.S. Pat. No. 4,104,076 to Pons, Dela Luye.
Ruye), U.S. Pat. No. 4,339,541; Krumwiede et al., U.S. Pat.
No. 3,210, and U.S. Pat. No. 5,352,640 to Combes et al., European Patent Application EP 05
36049, French Patent No. 2,331,527 and Canadian Patent No. 2,148,954. Still other glasses are for example WO 96/00194
May include additional materials as described in
It teaches the inclusion of fluorine, zirconium, zinc, cerium, titanium, and copper in the glass composition, requiring that the total alkaline earth oxide be less than 10% by weight of the glass.

[0003]

When producing infrared and ultraviolet absorbing glass, the relative amounts of iron and other additives are closely monitored and the operating range is adjusted to provide the desired color and spectral properties. Must be controlled within. To complement the green glass typically used in automobiles, which exhibits excellent sunlight performance and is compatible with commercial flat glass manufacturing methods, a dark colored green glass that can be used as a blindfold glazing in vehicles is provided. It would be desirable to have.

[0004]

SUMMARY OF THE INVENTION The present invention provides a green infrared ultraviolet absorbing glass article having a luminous transmittance of up to 60%. The composition of this glass article uses a standard soda-lime-silica glass base composition and also uses iron, cobalt, selenium, and chromium, and optionally titanium as infrared and ultraviolet absorbing materials and colorants. The glass of the present invention has a thickness of about 480-565 nm, preferably about 495-565 nm.
It has a color characterized by a dominant wavelength in the range of 560 nm and an excitation purity of less than about 20%, preferably less than about 10%, more preferably less than about 7%. Glass compositions are given different levels of spectral performance depending on the particular application and the desired luminous transmittance.

In one embodiment of the present invention, the glass composition of the green-infrared-ultraviolet-absorbing soda-lime-silica glass article is about 0.60-4% by weight total iron, about 0.13-0.
9 wt% of FeO, CoO about 40~500ppm, Se about 5～70Ppm, about 15~800ppm Cr ₂
O _3, and includes a solar radiation absorbing colorant portion consisting essentially of TiO ₂ of about 0.02 to 1 wt%. In another aspect of the invention, the glass composition of the article is between about 1 and
Less than 1.4 wt% total iron, about 0.2-0.6 wt% F
eO, C greater than 200 ppm and up to about 500 ppm
oO, about 5-70 ppm Se, more than 200 to about 80
0 ppm Cr ₂ O ₃ , and 0 to about 1 wt% Ti
From O ₂ containing essentially consisting solar radiation absorbing colorant portion.

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION The main components of the base glass of the present invention, that is, the glass which does not contain a substance which absorbs infrared rays or ultraviolet rays and / or a coloring agent, which are the object of the present invention, are characterized by the following. Commercial soda, lime and silica glass.

[0007]

[0008] All "wt%" values used herein are based on the total wt% of the final glass composition.

According to the invention, the base glass is added with infrared and ultraviolet absorbing substances and coloring agents in the form of iron, cobalt, selenium, chromium and optionally titanium. As described herein, iron is represented as Fe ₂ O ₃ and FeO, cobalt is represented as CoO, selenium is represented as element Se, chromium is represented as Cr ₂ O ₃ , titanium is T
iO expressed as _2. The glass compositions described herein may contain small amounts of other materials, such as melting and fining aids, playing cards (t
It should be appreciated that materials may contain ramps or impurities. Furthermore, it should be appreciated that in one aspect of the present invention, as discussed in more detail below, small amounts of additional materials may be included in the glass to improve the performance of the glass against sunlight. .

[0010] The iron oxide in the glass composition performs several functions. Ferric oxide, Fe ₂ O _3, is a strong UV absorber and acts as a yellow colorant on glass. Ferrous oxide, FeO, is a strong infrared absorber and acts as a blue colorant. The amount of total iron present in the glasses described here is expressed as Fe ₂ O ₃ according to standard analytical methods, which does not mean that all iron is actually in the form of Fe ₂ O _3. Absent. Similarly, the amount of iron in the ferrous state is expressed as F
Although reported as eO, it need not actually be present in the glass as FeO. In order to reflect the relative amounts of ferrous and ferric in the glass compositions described herein, the term "redox" refers to the ferrous state of iron (FeO
) Divided by the amount of total iron (expressed as Fe ₂ O ₃ ). Furthermore, unless stated otherwise, the term "total iron" in this specification mean total iron expressed as Fe ₂ O _3, the term "FeO" refers to the ferrous state, expressed as FeO Means iron.

Se is an ultraviolet and infrared absorbing colorant that imparts a pink or brown color to soda / lime / silica glass. Although Se also absorbs some infrared light, its use tends to reduce redox. CoO
Acts as a blue colorant and does not exhibit any appreciable ultraviolet or infrared absorbing properties. Cr ₂ O ₃ gives the glass a green color and helps to adjust the color of the final glass. It is believed that chromium can also provide some UV absorption. TiO ₂ is an ultraviolet absorber that acts as a colorant to give the glass composition a yellow color. In order to obtain the desired green blind glass with the desired spectral properties, a suitable balance between the contents of iron, i.e. ferric oxide and ferrous oxide, chromium, selenium, cobalt and possibly titanium. is necessary.

The glass of the present invention can be melted and clarified in a commercial large-scale continuous melting operation and formed into flat glass sheets of various thicknesses by the float process, in which the molten glass is Supported on a pool of molten metal, usually tin, the glass is banded and cooled. The formation of glass on molten tin has been found to result in the transfer of a measurable amount of tin oxide into the surface portion of the glass that was in contact with the tin. Typically, a piece of float glass has an SnO ₂ concentration of at least 0.05 to 2 wt.% Under the glass surface was in contact with the tin, in the first 25 microns. Typical background concentrations of SnO ₂ can be as high as 30 ppm.

[0013] The melting and forming equipment used to make the glass compositions of the present invention include US Patent No. 4,381,934 to Kunkle et al., Pecolaro.
oraro) et al., U.S. Patent No. 4,792,536;
And U.S. Patent No. 4,88 to Cerutti et al.
As described in US Pat. No. 6,539, this includes, but is not limited to, conventional continuous heating or multi-stage melting operations well known in the art. If necessary, the glass may be homogenized using a stirrer during the melting and / or forming stages of the glass manufacturing operation to produce the glass with the highest optical quality.

Tables 1, 2 and 3 show examples of glass compositions using the principles of the present invention. The examples in Tables 1 and 2 show that P
FIG. 1 is a computer model composition obtained by a color and spectral performance computer model of glass developed by PG Industries, Inc. The examples in Table 3 are actual laboratory melts in the laboratory.
The spectral characteristics shown in Tables 1 and 3 are 4.06 mm
(0.160 in), and those shown in Table 2 are based on a reference thickness of 3.91 mm (0.154 in). For comparison purposes, U.S. Pat.
The spectral properties of the examples were approximately determined at various thicknesses using the formulation described in U.S. Pat. No. 92,536. The tables show iron, cobalt, selenium,
Only the chromium and titanium parts are listed. Regarding the transmittance data given in those tables, the luminous transmittance (LT
A) shows a 2 ° viewing direction over a wavelength range of 380-770 nm and C.I. I. E. FIG. Measured using standard illumination "A", the color of the glass with respect to dominant wavelength and stimulus purity was determined by
I. E. FIG. ASTM E308- using standard lighting "C"
The measurement was performed in the observation direction 2 ° according to the procedure specified in No. 90. Total solar UV transmittance (TSUV) is 300-40
Measured over a wavelength range of 0 nm, the total solar infrared transmission (TSIR) was measured over a wavelength range of 720-2000 nm, and the total solar energy transmission (TSET) was
Measurements were taken over a wavelength range of 300-2000 nm. T
SUV, TSIR, and TSET transmission data are from Parry Moon air mass 2.
Calculated using zero solar direct data and integrated using the Trapezoidal Rule, as is known in the art.

The optical properties reported in Tables 1 and 2 are based on the assumption that, as is well known in the art, the glass is completely homogenous and has been produced by a conventional float glass process. Based on the absorption coefficient of the glass component, the expected properties of the glass including the base glass composition and colorant as generally described herein.

The information given in Table 3 is based on laboratory melts having approximately the following batch components: Cullet A 125 g Cullet B 22.32 g Cullet C 8.93 g Bengal 0.32 g Cr ₂ O ₃ 0.0461 g TiO ₂ 0.3 to 0.6 g Se 0.0037 to 0.0073 g Graphite 0.015 g

The cullet used in the melt contained various amounts of iron, cobalt, selenium, chromium, and / or titanium. In particular, cullet A contains 0.811 wt% total iron, 0.212 wt% FeO, 101 ppm Co
O, 17 ppm Se, 8 ppm Cr ₂ O ₃ , and 0.02% by weight TiO ₂ . Cullet B
Is 1.417% by weight of total iron, 0.362% by weight of Fe
O, 211.25 ppm CoO, 25 ppm Se,
And 7.5 ppm of Cr ₂ O ₃ . Cullet C is 0.93% by weight of total iron, 0.24% by weight of Fe
O, 6 ppm Cr ₂ O ₃ , and 0.02 wt% Ti
O ₂ was included. When preparing the melt, the components were weighed and mixed. Next, put the material in a 4in platinum crucible,
Heat to 2600 ° F. for 30 minutes, then 1
It is believed that it was heated to 454 ° C. (2650 ° F.) for 1 hour. The molten glass is then fritted in water, dried, and placed in a 2 inch platinum crucible at 1454 ° C. (2650 ° C.).
(° F) again for at least 1 hour. Next, the molten glass was poured out of the crucible, a plate was formed, and annealed. A sample was cut from the plate, polished and analyzed. Chemical analysis of the glass composition was determined using a RIGAKU3370 X-ray fluorescence spectrophotometer. The FeO content was determined using wet chemical methods as is well known in the art. The spectral properties of the glass may be annealed using a Perkin-Elmer Lambda 9 UV / VIS / NIR spectrophotometer before strengthening the glass or subjecting it to long-term ultraviolet radiation which affects the spectral properties of the glass. Was determined for the sample.

The following table represents the base oxides of certain experimental melts described in Table 3, which also fall within the base glass compositions described above.

SiO ₂ 70 to 72 wt% Na ₂ O 12 to 14 wt% CaO 8 to 10 wt% MgO 3 to 4 wt% Al ₂ O ₃ 0.1 to 0.6 wt% K ₂ O 0.01 to 0.15% by weight

Analysis of these melts indicated that the glass was about 0.
081% by weight of MnO ₂ . MnO ₂ is presumed to have entered the glass melt as part of the cullet.

[0021]

[Table 1]

[0022]

[Table 2]

[0023]

[Table 3]

[0024]

[Table 4]

[0025]

[Table 5]

[0026]

[Table 6]

[0027]

[Table 7]

[0028]

[Table 8]

[0029]

[Table 9]

[0030]

[Table 10]

[0031]

[Table 11]

[0032]

[Table 12]

[0033]

[Table 13]

[0034]

[Table 14]

[0035]

[Table 15]

[0036]

[Table 16]

[0037]

[Table 17]

[0038]

[Table 18]

[0039]

[Table 19]

[0040]

[Table 20]

[0041]

[Table 21]

[0042]

[Table 22]

[0043]

[Table 23]

[0044]

[Table 24]

Referring to Tables 1, 2 and 3, the present invention relates to a standard soda-lime-silica glass base composition, as well as iron, cobalt, selenium and chromium, and optionally titanium, with infrared and ultraviolet absorbing materials and coloring. Give the green glass used as an agent. Dominant wavelength (DW) and stimulus purity (Pe)
It will be appreciated that not all of the examples are the same green, as indicated by. In the present invention, the glass is about 480-565 nm, preferably about 495-56 nm.
It is preferred to exhibit a color characterized by having a dominant wavelength in the range of 0 nm and an excitation purity of less than about 20%, preferably less than about 10%, more preferably less than about 7%. It is envisioned that the color of the glass may vary within this dominant wavelength range to provide the desired product. For example, green-blue glass is about 485-515 nm, preferably about 49-515 nm.
Dominant wavelength of 0 to 510 nm and 10% or less, preferably 7
%, While the green-yellow glass has a dominant wavelength of about 535-565 nm, preferably about 540-560 nm and less than 10%,
Preferably, it can be produced as having a stimulating purity of 5% or less.

The green infrared ultraviolet absorbing glass disclosed in the present invention has a luminous transmittance (LTA) of up to 60%. In one particular embodiment, the glasses are about 0.
6-4 wt% total iron, about 0.13-0.9 wt% Fe
O, about 40-500 ppm CoO, about 5-70 ppm
Of Se, about 15-800 ppm of Cr ₂ O ₃ , and 0.1.
02 through about 1 wt% of TiO _2. In another aspect,
The glasses have about 1 to less than 1.4 wt% total iron, about 0.2 to 0.60 wt% FeO, more than 200 ppm, up to about 500 ppm CoO, about 5 to 70 ppm Se, more than 200 ppm. Cr up to about 800 ppm
₂ O _3, and from 0 to about 1 wt% of TiO _2. The redox ratio of these glasses is from about 0.20 to 0.40, preferably from about 0.22 to 0.35, more preferably about 0.2 to 0.40.
It is maintained at 23 to 0.28. These glass compositions have a TSU of about 40% or less, preferably about 35% or less.
V, TSI of about 45% or less, preferably about 40% or less
R, and TS of about 50% or less, preferably about 45% or less
Has ET.

The glass compositions of the present invention can be provided as having various levels of spectral performance, depending on the particular application and desired luminous transmittance. In one embodiment of the present invention, for a green infrared ultraviolet absorbing glass having at least one thickness in the range of 1.8-5.0 mm and an LTA of less than 20%, the glass composition comprises about 1
~ 1.4 wt% total iron, about 0.22-0.5 wt%, preferably about 0.3-0.5 wt% FeO, 20
Greater than 0 to about 450 ppm, preferably 200 p
pm to about 350 ppm CoO, about 10-6
0 ppm, preferably about 35-50 ppm Se, about 2 ppm
50-400 ppm, preferably about 250-350 pp
m of Cr ₂ O _3, and 0 to about 1 wt%, preferably of TiO ₂ to about 0.02 to 0.5 wt%. Those glass compositions falling within this luminous transmittance range have a TSUV of about 30% or less, preferably 12% or less, about 35% or less,
Preferably it has a TSIR of about 20% or less, and a TSET of about 30% or less, preferably about 20% or less.

As another embodiment of the present invention, 1.8 to 5.0 m
For green infrared UV absorbing glasses having an LTA of less than 20 to 60% at at least one thickness in the range of m, the glass compositions comprise less than about 1 to 1.4% by weight total iron, about 0.1 to less than 0.1% by weight. 25-0.4 wt% FeO, 200
more than about 250 ppm to about 250 ppm of CoO,
30 ppm Se, more than 200 ppm about 250 pp
m up to Cr ₂ O _3, and about 0.02-0.5% by weight of TiO _2. Those glass compositions falling within this luminous transmittance range have a TSUV of about 35% or less, preferably 20% or less, a TSIR of about 40% or less, preferably about 15% or less, and about 45% or less, preferably about 45% or less. Has a TSET of about 25% or less.

In another embodiment of the present invention, for a green infrared ultraviolet absorbing glass having a nominal thickness of 4.06 mm and an LTA of 20-60%, the glass composition comprises:
0.7 to about 2% by weight, preferably about 0.8 to 1.5% by weight of total iron, about 0.13 to 0.6% by weight, preferably about 0.14 to 0.43% by weight of FeO , More than 200 ppm to about 300 ppm, preferably more than 200 ppm to about 250 ppm CoO, about 5-70 ppm;
Preferably Se about 8～60Ppm, until most about 300ppm than 200 ppm, preferably Cr ₂ O ₃ up to about more than 200 ppm 250 ppm, and from 0 to about 1 wt%, preferably from about 0.02 to 0.5 wt% TiO ₂
including. Those glass compositions falling within this luminous transmittance range have a TSUV of about 35% or less, a TSUV of about 40% or less.
It has an IR, and a TSET of about 45% or less.

In another embodiment of the present invention, the green infrared ultraviolet absorbing glass composition comprises 0.9-1.3% by weight, preferably 1.083-1.11% by weight of total iron, 0.25-1.5% by weight.
0.40 wt%, preferably 0.306-0.35 wt% FeO, 80-130 ppm, preferably 90-1
28 ppm CoO, 8-15 ppm, preferably 10 ppm
~12ppm of Se, 250~350ppm, preferably of 286~302ppm Cr ₂ O _3, and 0.1
0.5 wt%, preferably of TiO ₂ from 0.194 to 0.355 wt%. These glasses are 25-40%
Luminous transmittance (LTA), total solar ultraviolet transmittance (TSUV) of about 25% or less, total solar infrared transmittance (TSIR) of about 20% or less, and total solar energy transmittance (TSET) of about 30% or less. ).

The spectral properties of these glass compositions described herein are expected to change upon strengthening the glass or prolonged exposure to ultraviolet radiation, commonly referred to as solarization. In particular, the toughening and solarization of the glass compositions described herein increase LTA, TSUV, TSIR, and TSET.
Is believed to decrease. As a result, in one aspect of the present invention, the glass composition has selected spectral properties that do not initially fall within the desired ranges described above, but fall into the desired ranges after tempering and / or solarization. May be.

[0052] The sheet thickness of the glass produced by the float process typically ranges from about 1 mm to 10 mm. For glazing in vehicles, glass sheets having the composition and spectral characteristics described herein preferably have a thickness that falls within the range of 1.8-5 mm (0.071-0.197 in). When using a single piece of glass, for example, to strengthen the glass for side windows or rear windows of automobiles, when using multi-layer glass, anneal the glass and use a thermoplastic adhesive such as polyvinyl butyral. It is expected that they will be stacked together.

It is also contemplated that vanadium can be used as a partial or complete replacement for chromium in the glass compositions of the present invention. In particular, vanadium, represented here as V ₂ O ₅ , gives the glass a yellow-green color,
Absorbs both ultraviolet and infrared light in different valence states. Cr ₂ O in the range of about 25-800 ppm as described above
₃ is believed to be able to completely replace the V ₂ O ₅ of 0.01 to 0.32 wt%.

As previously mentioned, other materials may be added to the glass compositions described herein to further reduce infrared and ultraviolet transmission and / or control the color of the glass. In particular, the addition of the following materials to the soda-lime-silica glass containing iron, cobalt, selenium, chromium and titanium described herein is also considered.

MnO ₂ 0 to 0.5% by weight SnO ₂ 0 to 2% by weight ZnO 0 to 0.5% by weight Mo 0 to 0.015% by weight CeO ₂ 0 to 2% by weight NiO 0 to 0.1% by weight

It is recognized that adjustments must be made to the basic iron, cobalt, selenium, chromium, and / or titanium components in view of the color and / or redox impact of these additional materials. Should be done.

Other modifications known to those skilled in the art may be utilized without departing from the scope of the invention as defined in the claims.

──────────────────────────────────────────────────続 き Continuation of the front page (72) Robert B. Inventor. Haysov Delo Drive, Gibsonia, PA, United States 2403 (72) Inventor Anthony Buoy. Longovardo Great Belt Road 222, Butler, PA, USA. Dee. Number 4 (72) inventor Andrew Karaburesu United States Pennsylvania Wexford, Fountain Hills Drive 2614 (56) Reference Patent flat 10-120431 (JP, A) (58 ) investigated the field (Int.Cl. ^7, DB Name) C03C 1/00-14/00

Claims (2)

(57) [Claims] 1. About 66 to 75% by weight of SiO ₂ About 10 to 20% by weight of Na ₂ O About 5 to 15% by weight of CaO 0 to about 5% by weight of MgO 0 to about 5% by weight of Al ₂ O ₃ K ₂ O 0 and about 5 consist wt% basic glass portion, total iron 0.9 to 1.3 wt% FeO 0.25 to 0.40 _{wt% CoO 80~130ppm Se 8~15ppm Cr 2 O} 3 250~350ppm, and a green infrared ultraviolet absorbing glass article having a composition consisting of essentially composed solar radiation absorbing colorant portion from the TiO ₂ 0.1 to 0.5 wt%, 25% to 40% of luminous transmittance ( LTA).
The above glass article. 2. The total iron concentration is about 1.083 to 1.11% by weight, and the FeO concentration is about 0.306 to 0.35% by weight.
And the CoO concentration is 90 to 128 ppm,
The concentration is about 10-12 ppm and the Cr ₂ O ₃ concentration is 28
6 to 302 ppm, and the TiO ₂ concentration is 0.194 to
0.355% by weight; and the glass has a total solar ultraviolet transmittance (TSUV) of about 25% or less, a total solar infrared transmittance (TSIR) of about 20% or less, and a total solar energy transmittance of about 30% or less. (TSET) having a glass article according to claim 1, wherein.