JP3210921B2 - Green concealed glass - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

FIELD OF THE INVENTION This invention relates to low luminous transmittance which is highly desirable for use as a glazing for the privacy of vehicles such as side windows 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%.
It has a luminous transmittance of ４０40%. As used herein, the term "green" has a dominant wavelength of about 480-565 nm,
Meaning includes glass, which can be characterized as green-blue, green-yellow, or green-grey. 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. Some glasses use cobalt, selenium, and optionally nickel along with iron to further suppress infrared and ultraviolet light and color, and are disclosed in Jones, U.S. Pat. Cheng) et al., US Pat. No. 5,278,108, Baker.
No. 5,308,805, and Gulotta et al., US Pat. No. 5,393,583, and European Patent Application EP 0705800.
Along with this colorant combination, there are other glasses containing chromium, as described in Pons U.S. Pat. No. 4,104,076.
US Patent No. 4,3 of Dela Ruye
No. 39,541; U.S. Pat. No. 5,023,210 to Krumwiede et al .; and Combes.
s) et al., US Pat. No. 5,352,640, European Patent Application EP 0 536 049, French Patent 2,331,
527 and Canadian Patent 2,148,954. Still other glasses are, for example, WO 96 /
It may include additional materials as described in 00194, which teaches the inclusion of fluorine, zirconium, zinc, cerium, titanium, and copper in the glass composition and includes alkaline earth oxides. It requires that the total 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]

[Means for Solving the Problems]

The present invention, SiO ₂ about 66-75 wt%, Na ₂ O from about 10-20 wt% CaO about 5 to 15 wt% MgO 0 to about 5 wt% Al ₂ O ₃ 0~ about 5 wt% K ₂ O 0 And about 5% by weight of the base glass, and about 1.5-3.5% by weight of total iron Fe about 0.386-0.875% by weight of CoO about 220-400 ppm of Se about 27-54 ppm of Cr ₂ O ₃ about 250～375Ppm, 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 to .49% by weight, from 5.02 to 14.68 % Luminous transmittance (LTA)
And 1.07 to 8.00% of total solar ultraviolet transmittance (TS
UV) and a total solar infrared transmission (TSIR) of 0.89 to 9.29%. The present invention also 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 about 480-565.
nm, preferably a dominant wavelength in the range of about 495-560 nm and a color characterized by a stimulating purity of about 20% or less, preferably about 10% or less, more preferably about 7% or less.
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% TiO
₂ consisting essentially of a solar radiation absorbing colorant moiety.

[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.

In the present invention, the basic glass is made of iron,
Infrared in the form of selenium, selenium, chromium and possibly titanium
Add line and UV absorbing material and colorant. here
As noted, iron is Fe_TwoO_ThreeAnd FeO,
Cobalt is expressed as CoO and selenium is expressed as element Se.
Chromium is Cr_TwoO_ThreeWhere titanium is TiO _Two
Expressed as The glass composition described here may contain a small amount
Materials, such as melting and fining aids, tramps
p) It is recognized that it may contain materials or impurities.
Should be. Further, as one aspect of the present invention,
As discussed in more detail, the performance of glass against sunlight
A small amount of additional material in the glass to improve
It should be recognized that it is acceptable.

[0010] Iron oxide in glass compositions has several functions.
Fulfill. Ferric oxide, Fe_TwoO_ThreeIs a strong UV absorber
And acts as a yellow colorant on the glass. Oxidation first
Iron and FeO are strong infrared absorbers and blue colorants
Work as Of all iron present in the glass described here
The amount is determined according to standard analytical methods._TwoO_ThreeWhich is expressed as
All iron is actually Fe_TwoO_ThreeMeans that it is in the form of
It does not mean. Similarly, the amount of iron in the ferrous state is
But it is actually FeO in the glass as
May not be present. Glass composition described here
In order to reflect the relative amounts of ferrous and ferric in the material,
The term "redox" refers to iron in the ferrous state (FeO).
Is expressed as total iron (Fe_TwoO_ThreeDivided by the amount of
Means something. In addition, unless otherwise stated,
The term “total iron” in the description refers to Fe _TwoO_ThreeAll represented as
Means iron and the term “FeO” is expressed as FeO
Means ferrous 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 shaping equipment used to make the glass compositions of the present invention include US Patent No. 4,381,934 to Kunkle et al., Pecorar.
o) etc., as described in U.S. Pat. No. 4,792,536, and Cerutti et al., U.S. Pat. No. 4,886,539, which are well known in the art. Including, but not limited to, conventional continuous melting operations or multi-stage melting operations. 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. 2 is a computer model composition obtained from a color and spectral performance computer model of glass developed by PPG 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 m
m (0.160 in), based on Table 2
Are based on a reference thickness of 3.91 mm (0.154 in). For purposes of comparison, U.S. Pat.
The spectral properties of the examples were approximately determined at various thicknesses using the formulation described in 792,536. 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 available from Parry Moon air mass
Calculated using 2.0 solar direct data and integrated using the Trapezoidal Rule as 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 0.1 ppm.
It contained 02% by weight of TiO ₂ . Caret B
1.417 wt% total iron, 0.362 wt% FeO,
It contained 211.25 ppm CoO, 25 ppm Se, and 7.5 ppm Cr ₂ O ₃ . Caret C
0.93 wt% total iron, 0.24 wt% FeO, 6p
It contained pm of Cr ₂ O ₃ and 0.02% by weight of TiO ₂ . When preparing the melt, the components were weighed and mixed. Next, put the material in a 4-inch platinum crucible,
(2600 ° F.) for 30 minutes, then 1454 ° C.
(2650 ° F.) for 1 hour. Next, the molten glass is placed in water to frit, dried, and dried.
n, then heated again at 1454 ° C. (2650 ° F.) 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 can be determined by using a Perkin-Elmer Lambda 9UV prior to strengthening the glass or subjecting it to long-term ultraviolet radiation that affects the spectral properties of the glass.
Determined on annealed samples using a / VIS / NIR spectrophotometer.

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
Se, about 15-800 ppm of Cr ₂ O ₃ , and 0.0
2 comprising about 1 wt% of TiO _2. In another aspect, the glasses comprise from about 1 to less than 1.4% by weight total iron, about 0.
2-0.60% by weight FeO, more than 200 ppm,
Up to about 500 ppm CoO, about 5-70 ppm S
e, more than 200 ppm up to about 800 ppm Cr ₂
O _3, and from 0 to about 1 wt% of TiO _2. The redox ratio of these glasses is about 0.20 to 0.40, preferably about 0.22 to 0.35, more preferably about 0.23
０．２0.28 is maintained. 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 Cr ₂ O ₃ , and 0 to about 1% by weight, preferably about 0.
02 to 0.5% by weight of the total composition of TiO _2. Those glass compositions that fall within this luminous transmittance range are less than about 30%,
Preferably it has a TSUV of no more than 12%, no more than about 35%, preferably no more than about 20%, and no more than about 30%, preferably no more than about 20%.

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 of Cr ₂ O ₃ and about 0.02-0.5% by weight of T
iO ₂ included. Those glass compositions falling within this luminous transmittance range have a TSUV of about 35% or less, preferably 20% or less, and a TUV of about 40% or less, preferably about 15% or less.
It has a SIR and a TSET of about 45% or less, preferably 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 . Those glass compositions falling within this luminous transmittance range have a TSUV of about 35% or less, a TSI of about 40% or less.
R, 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 to 0.
5 wt%, preferably of TiO ₂ from 0.194 to 0.355 wt%. These glasses have a luminous transmission (LTA) of 25-40%, a total solar ultraviolet transmission (TSUV) of about 25% or less, a total solar infrared transmission (TSIR) of about 20% or less, and about 30%. It has the following total solar energy transmission (TSET):

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,
Strengthening and solarization of the glass compositions described herein increase LTA, and increase TSUV, TSIR, and TSE.
It is believed to decrease T. 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 and absorbs both ultraviolet and infrared in different valence states. Cr ₂ O _{3 in} the range of about 25-800 ppm as described above
It 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.

Continuation of front page (72) Inventor Robert B. 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 (1)

(57) [Claims] 1. A SiO ₂ about 66-75 wt%, Na ₂ O from about 10-20 wt% CaO about 5 to 15 wt% MgO 0 to about 5 wt% Al ₂ O ₃ 0~ about 5 wt% K ₂ O a base glass portion comprising the 0 to about 5 wt%, total iron about 1.5 to 3.5 wt% FeO from about 0.386 to 0.875 wt% CoO about 220～400Ppm Se about 27~54ppm Cr ₂ O ₃ about 250～375Ppm, and a green infrared ultraviolet absorbing glass article having a composition consisting of essentially composed solar radiation absorbing colorant portion from the TiO ₂ from 0 to 0.49 wt%, 5.02 to 14. Luminous transmittance of 68% (LTA)
And 1.07 to 8.00% of total solar ultraviolet transmittance (TS
UV) and a total solar infrared transmission (TSIR) of 0.89 to 9.29%.