U.S. patent application number 09/234314 was filed with the patent office on 2002-01-17 for dye combinations for image enhancement filters for color video displays.
Invention is credited to MALINOSKI, GEORGE, SUH, SUK YOUN, TENG, CHIA-CHI.
Application Number | 20020005509 09/234314 |
Document ID | / |
Family ID | 22880858 |
Filed Date | 2002-01-17 |
United States Patent
Application |
20020005509 |
Kind Code |
A1 |
TENG, CHIA-CHI ; et
al. |
January 17, 2002 |
DYE COMBINATIONS FOR IMAGE ENHANCEMENT FILTERS FOR COLOR VIDEO
DISPLAYS
Abstract
A bandpass filter containing specific red dyes alone or in
combination with other dyes selectively transmits predetermined
primary color wavelengths as well as selectively absorbs
wavelengths other than the predetermined primary color wavelength.
The filter is particularly useful for enhancing the contrast of
color plasma displays by absorbing visible light emitted at 590 nm
from the display.
Inventors: |
TENG, CHIA-CHI; (PISCATAWAY,
NJ) ; SUH, SUK YOUN; (WARREN, NJ) ; MALINOSKI,
GEORGE; (FAIR HAVEN, NJ) |
Correspondence
Address: |
OBLON SPIVAK MCCLELLAND MAIER & NEUSTADT PC
FOURTH FLOOR
1755 JEFFERSON DAVIS HIGHWAY
ARLINGTON
VA
22202
US
|
Family ID: |
22880858 |
Appl. No.: |
09/234314 |
Filed: |
January 21, 1999 |
Current U.S.
Class: |
252/582 ;
313/112; 313/485; 359/885; 359/890; 428/212; 428/690 |
Current CPC
Class: |
Y10T 428/31504 20150401;
H01J 11/10 20130101; G02B 5/223 20130101; H01J 2211/444 20130101;
Y10T 428/24942 20150115; H01J 29/898 20130101; H01J 11/44
20130101 |
Class at
Publication: |
252/582 ;
428/690; 428/212; 313/485; 313/112; 359/885; 359/890 |
International
Class: |
G02B 005/22; H01J
001/00; H05B 033/02 |
Claims
What is claimed is:
1. A filter for contrast and color enhancement of a color display,
comprising either a first dye having substantially the absorbance
spectrum as shown in FIG. 1, or a second dye having substantially
the absorbance spectrum as shown in FIG. 2, or a mixture of said
first and second dyes uniformly contained in a carrier matrix.
2. The filter of claim 1, comprising a mixture of said first and
second dyes, said mixture containing about 0.02% to about 0.85% by
weight of said first dye and about 0.01% to about 0.45% by weight
of said second dye, said weights based on said matrix.
3. The filter of claim 1, wherein the filter is a multiple bandpass
filter comprising said first and second dyes, Astrazon Orange dye
and Luxol Fast Blue dye uniformly contained in the matrix.
4. The filter of claim 2, further containing Astrazon Orange in
amounts of about 0.02% to about 2.0% by weight and Luxol Fast Blue
in amounts of about 0.02% to about 2.0% by weight, based on the
matrix.
5. The filter of claim 4, further containing Disperse Yellow 9 dye
uniformly contained in the matrix in amounts of about 0.20% to
about 0.80% by weight based on the matrix.
6. The filter of claims 3, further containing IRA 850 dye uniformly
contained in the matrix.
7. The filter of claim 1 wherein said matrix is a polymer
matrix.
8. The filter of claim 7, wherein the polymer matrix comprises
polyvinyl alcohol, polyvinyl acetate, polymethyl methacrylate,
polyacrylate, polyolefin,, polystyrene, polycarbonate, polyvinyl
butyrate, cycloolefin polymer, cycloolefin copolymer, polyurethane,
polyamide, polyester, polyether, polyketone, or polyesteramide.
9. The filter of claim 1, wherein said first and second dyes have a
light fastness characterized as less than 10-20% degradation under
85 MJ/m.sup.2 exposure of white light and a thermal stability
characterized as less than 10-20% degradation under conditions of
70.degree. C., 70% RH for 72 hours.
10. The filter of claim 3, comprising a first layer formed from a
mixture of said first and second dyes uniformly contained within a
polymer matrix, and a second layer juxtaposed on said first layer
and comprising a mixture of Astrazon Orange dye and Luxol Fast Blue
dye uniformly contained within a polymer matrix.
11. The filter of claim 10, wherein the first layer comprises a
polymethyl methacrylate matrix.
12. The filter of claim 11, wherein the second layer comprises
polyvinyl acetate matrix.
13. The filter of claim 1 wherein said matrix is coated onto a
transparent substrate selected from glass and a polymeric
substrate.
14. The filter of claim 1 wherein said matrix is a free standing
polymeric film.
15. A color display device comprising: A face plate containing an
inner and outer surface, the inner surface comprises a layer of
phosphor and the outer surface comprises a translucent filter; The
filter comprises either a first dye having substantially the
absorbance spectrum as shown in FIG. 1, or a second dye having
substantially the absorbance spectrum as shown in FIG. 2, or a
mixture of said first and second dyes, incorporated in a carrier
matrix.
16. The color display device of claim 15, wherein the filter
further comprises Astrazon Orange dye and Luxol Fast Blue dye
contained uniformly in a carrier matrix.
17. The color display device of claim 16, wherein the filter
further comprises Disperse Yellow 9 dye incorporated in a carrier
matrix.
18. The color display device of claim 1 wherein said carrier matrix
is a polymer.
19. The color display device of claim 18, wherein the polymer
matrix is composed of polyvinyl alcohol, polyvinyl acetate,
polymethyl methacrylate, polyacrylate, polyolefin,, polystyrene,
polycarbonate, polyvinyl butyrate, cycloolefin polymer, cycloolefin
copolymer, polyurethane, polyamide, polyester, polyether,
polyketone, or polyesteramide.
20. The color display device of claim 16, wherein the filter
comprises a first layer comprising a mixture of said first and
second dyes contained in a polymeric matrix and a second layer
comprising Astrazon Orange dye and Luxol Fast Blue dye contained in
a separate polymeric matrix.
21. The color display device of claim 21, wherein the first layer
comprises a polymethyl methacrylate matrix and the second layer
comprises a polyvinyl acetate matrix.
22. The color display device of claim 15 wherein said matrix is
coated onto a transparent substrate selected from glass and
polymeric substance.
23. The color display device of claim 15 wherein said matrix is a
free standing polymeric film.
24. The color display device of claim 15 comprising a plasma
display device.
25. A plasma display device and an image enhancement filter
provided thereon, said filter comprising at least one red dye
capable of absorbing visible light emitted at 590 nm.
26. The plasma display device of claim 25 wherein the filter is
capable of absorbing at least 50% of visible light emitted at 590
nm.
27. The plasma display device of claim 25 wherein said at least one
red dye is contained within a polymeric matrix.
28. The plasma display device of claim 27 wherein the carrier
matrix is coated onto a transparent substrate selected from glass
and polymer substance.
29. The plasma display device of claim 27 wherein said matrix is a
free standing polymeric film.
30. The plasma display device of claim 25, further comprising IRA
850 dye capable of shielding IR radiation emitted form plasma of
the plasma display device.
31. A dye solution comprising a solvent and the dye comprising a
dye having substantially the absorbance spectrum as shown in FIG.
1, a dye having substantially the absorbance spectrum as shown in
FIG. 2, Astrazon Orange, Luxol Fast Blue, Disperse Yellow 9, IRA
850, or mixtures thereof.
32. The dye solution of claim 31, wherein the solvent is water, or
organic solvent or mixtures thereof.
33. The dye solution of claim 32 wherein the organic solvent
comprises isopropyl alcohol, methyl alcohol, methyethyl ketone,
acetone, dimethylfuran or mixtures thereof.
Description
FIELD OF THE INVENTION
[0001] The present invention is directed to filters, including
multiple bandpass filters, for video display devices and similar
articles. Specifically, the present invention is directed to
filters containing specific dye combinations for color video
display devices.
BACKGROUND OF THE INVENTION
[0002] Video display devices are nowadays widely used in articles
such as televisions, computers, video games and the like. Many of
them generally employ a cathode ray tube (CRT) which is a vacuum
tube display device in which the image is created by electrons from
an electron gun striking a phosphor screen that converts the
electron energy into light energy over a wide wavelength range,
usually the visible range for common display devices such as
television and computer monitors. The CRT may be monochromatic
(single color) or a color display device which produces images in
more than one color, typically the three primary colors: red, green
and blue.
[0003] A common problem with video display devices is the light
reflected from the device towards the viewer, which generally
fatigues the viewer's eyes. The reflected light consists of ambient
light reflecting off the surface of the screen (which is typically
a glass surface) as well as ambient light reflecting off the
phosphors behind the screen. Several attempts have been made in the
past to avoid or reduce this reflected light. U.S. Pat. No.
4,989,953, in column 2, line 13 through column 3, line 22,
describes some of these earlier attempts and the problems
associated with them. Most of these attempts, however, have
succeeded in reducing the glare from monochromatic display monitors
only.
[0004] For color displays, earlier attempts to reduce light
reflection included, for example, use of a neutral density filter.
Neutral density filters or attenuators are designed to produce
attenuation that is uniform regardless of the wavelength. See, for
example, Jeff Hecht, "The Laser Guidebook," 2nd edition,
McGraw-Hill, Inc., New York, 1992, page 79. Such filters comprise
colloidal suspensions of silver or graphite particles in a suitable
medium and adhere to the monitor surface. This type of filter
transmits a fraction of the light passing through it, independent
of the wavelengths. In fact, neutral density filters are widely
used in the manufacturing of current color CRT displays for lack of
no better alternative. These filters, however, have the
disadvantage of reducing the brightness of the image.
[0005] Another approach has been to use selective filtration by
using different colored plates to absorb certain wavelengths. They,
however, suffer the disadvantage that one has to use a different
color filter for each phosphor element. combining several filter
materials in order to transmit just the desired red, green and blue
generally results in the absorption of some of the desired
wavelengths due to cascading of the different filter materials.
This reduces the amount of red, green and blue that eventually gets
transmitted.
[0006] Yet another approach involves a combination of a neutral
density filter and an antireflection coating. While this cuts down
the reflected light, it also reduces the brightness of the
image.
[0007] U.S. Pat. No. 5,121,030 discloses absorption filters which
contain a transparent substrate with a plurality of spatially
separated areas that contain selective absorptive dye colorants.
Since this requires spaced areas with different dye components
therein, the construction of the filter is quite complex and
difficult to manufacture in large quantities
[0008] U.S. Pat. No. 4,989,953 referred to above advocates the use
of colored filters for monochromatic displays. Thus, for example, a
magenta colored filter is used for CRTs with green phosphors, and a
blue colored filter is used for amber colored CRTs. However, this
concept is not much useful for color displays because the blue
filter, for example, will block out the red and/or green depending
on the spectral characteristics of the filter. The same problem
exists for the other color filters that U.S. Pat. No. 4,989,953
discloses. If such filters are used for full color displays, the
resulting display color will be severely distorted. For this
reason, U.S. Pat. No. 4,989,953 suggests that a neutral density or
gray colored filter must be used for multi-color or black and white
displays. However, this approach, as stated before, reduces the
brightness of the display. Since neutral density filters absorb a
substantial amount of the desired light, the displays using neutral
density filters must be capable of producing intense light. This
was one of the reasons for developing super bright phosphors for
display applications. Such bright phosphors substantially increase
the cost of the display, however.
[0009] Another kind of visual display device being increasingly
used is characterized as a plasma display panel (PDP). The basic
mechanism of monochrome display operation is relatively simple.
Inert gases, such as helium, neon, argon, xenon or mixtures thereof
are hermetically sealed in a glass envelope and are subjected to a
high voltage which causes the gas to ionize, producing a plasma.
Color operation can also be achieved in a plasma display. Such
operation utilizes ultraviolet light generated by the plasma
discharge, rather than the glow of color of the plasma directly.
Thus, in color operation, phosphors are placed in the vicinity of
the plasma discharge. The plasma-generated UV light hits the
phosphors and generates visible light for the display. Plasma
display panels, also known as gas display panels, have features
such as a wide viewing angle, easy to see display because of self
light emission, and a slim form. These advantages have encouraged
increasing use of gas discharge display panels for high quality
television sets. The exact structure of the PDPs is not a feature
of the present invention, and it is contemplated that the filters
of this invention are useful for any color PDP regardless of the
exact configuration. Those of ordinary skill in the art would be
capable of using the inventive filter with any PDP device.
[0010] Unfortunately, plasma displays currently being developed by
various display manufacturers, still do not have high enough
brightness nor high enough red, green, and blue color transmission.
Therefore, neutral density filters cannot effectively be used for
color and contrast enhancement in plasma display applications since
such filters would further reduce the brightness of the display.
Additionally, since the sub-pixels of the phosphors are in close
proximity to each other, there is a need for a physical barrier to
prevent stimulation of a non-selected phosphor region.
[0011] Thus, in view of the varied uses and potential uses for CRTs
and plasma display panels there is a need in the industry to have
some device or mechanism to efficiently reduce the reflected light
from the display devices as well as increase overall color and
improve contrast and color enhancement without significantly
sacrificing the brightness and resolution of the image.
[0012] It is, therefore, an object of this invention to provide a
filter for color displays to reduce light reflected off such
displays.
[0013] It is an additional object of this invention to provide a
filter containing specific dye sets to enhance the contrast and
color of images from a color display monitor without significantly
sacrificing brightness of the image therefrom.
[0014] It is a further object of this invention to provide a
spectrally tuned multiple bandpass filter for color displays,
specifically matched to the three primary colors, namely red,
green, and blue.
[0015] Other objects and advantages of this invention will be
apparent to those skilled in the art from the accompanying
description and examples.
SUMMARY OF THE INVENTION
[0016] One or more of the foregoing objects are achieved by the
provision in the present invention of a spectrally tuned bandpass
filter which is adherable to a display monitor surface in a variety
of ways and enhances the contrast and color of the image without
significantly affecting the brightness and resolution of the image.
The filter of the present invention also can be free-standing and
placed in front of the display monitor. The filter comprises at
least one specific red dye or a mixture of specific red dyes alone
or in combination with other specific dye mixtures and which is
adapted to substantially selectively transmit predetermined primary
color wavelengths of an electromagnetic spectrum as well as to
selectively absorb wavelengths other than said predetermined
primary color wavelengths. The dyes may be on a suitable
transparent substrate which is then adhered to the monitor surface,
or alternately, the dyes may be directly deposited on the monitor
surface by a suitable process such as, for example, spray coating.
Preferably, the dye or combination of dyes are uniformly mixed
within a transparent polymer matrix.
[0017] The word "spectrally tuned" refers to the substantial
selective transmission (at least 50%) of the predetermined primary
colors; the word "transparent" refers to at least 70% transmission
of light of the electromagnetic spectrum which in the common case
such as television display devices such as CRT, plasma displays and
the like, is the visible light. In such a case, the primary colors
are red, green and blue.
[0018] Additionally, the present inventive bandpass filter allows
one to expand the color gamut by adjusting the spectral bandwidth
of the bandpass windows in the respective wavelengths, thereby
allowing more vivid and realistic colors on CRTs and PDPs. This is
a significant improvement over present visual display
technology.
[0019] The present inventive bandpass filter also shields
electromagnetic induction and IR radiation from PDPs which
interfere with the operation of remote control units.
[0020] Still additionally, if one so desired, one may deposit a
suitable antireflection coating on top of the inventive contrast
and color enhancing filter. In that case, the antireflection
coating should be chosen as not to affect the integrity of the
filter physically, chemically and optically. Suitable
antireflection coatings are described, for example, in U.S. Pat.
No. 5,178,955.
BRIEF DESCRIPTION OF THE DRAWINGS
[0021] FIG. 1 discloses the absorbance spectrum of red dye, ABS
594.
[0022] FIG. 2 discloses the absorbance spectrum of red dye, ABS
574.
[0023] FIG. 3 is the absorbance spectrum of a dye set containing
0.40% ABS 574 and 0.53% ABS 594 in a polymethyl methylacrylate
(PMMA) matrix.
[0024] FIG. 4 is the chromaticity diagram of the dye set containing
0.40% ABS 574 and 0.53% ABS 594 in a PMMA matrix.
[0025] FIG. 5 is the absorbance spectrum of a dye set containing
0.25% ABS 574 and 0.50% ABS 594 in a PMMA matrix.
[0026] FIG. 6 is the chromaticity diagram of the dye set containing
0.25% ABS 574 and 0.50% ABS 594 in a PMMA matrix.
[0027] FIG. 7 is the absorbance spectrum of a dye set containing
0.40% ABS 574 and 0.80% ABS 594 in a PMMA matrix in combination
with 1.0% Astrazon Orange and 1.0% Luxol Fast Blue in a polyvinyl
acetate (PVA) matrix.
[0028] FIG. 8 is the chromaticity diagram of the dye set containing
0.40% ABS 574 and 0.80% ABS 594 in combination with 1.0% Astrazon
Orange and 1.0% Luxol Fast Blue in a PVA matrix.
[0029] FIG. 9 discloses the absorbance spectrum of dye set
containing 0.25% ABS 574 and 0.50% ABS 594 in a PMMA matrix in
combination with Astrazon Orange 1.0% and Luxol Fast Blue 1.0% in a
PVA matrix.
[0030] FIG. 10 is the chromaticity diagram of the dye set
containing 0.25% ABS 574 and 0.50% ABS 594 in combination with
Astrazon Orange 1.0% and Luxol Fast Blue 1.0% in a PVA matrix.
[0031] FIG. 11 is the absorbance spectrum of a dye set containing
0.25% ABS 574 and 0.50% ABS 594 in a 6 micrometer PMMA matrix layer
in combination with a second 6 micrometer PVA matrix layer
containing Astrazon Orange 1.0% and Luxol Fast Blue 1.0%.
[0032] FIG. 12 is a chromaticity diagram of the dye set containing
0.25% ABS 574 and 0.50% ABS 594 in a first 6 micrometer PMMA matrix
layer in combination with a second 6 micrometer PVA matrix layer
containing 1.0% Astrazon Orange and 1.0% Luxol Fast Blue.
[0033] FIG. 13 is the absorbance spectrum of a dye set containing
0.065% Astrazon Orange, 0.024% ABS 574, 0.048% ABS 594, and 0.060%
Luxol Fast Blue in a cellulose acetate matrix.
[0034] FIG. 14 is a chromaticity diagram of the dye set containing
0.065% Astrazon Orange, 0.024% ABS 574, 0.048% ABS 594, and 0.060%
Luxol Fast Blue in a cellulose acetate matrix.
[0035] FIG. 15 is the absorbance spectrum of a dye set containing
0.45% Disperse Yellow 9, 0.45% Astrazon Orange, 0.25% ABS 574,
0.50% ABS 594, and 0.55% Luxol Fast Blue in a polyvinyl butyrate
matrix.
[0036] FIG. 16 is a chromaticity diagram of the dye set containing
0.45% Disperse Yellow 9, 0.45% Astrazon Orange, 0.25% ABS 574,
0.50% ABS 594, and 0.55% Luxol Fast Blue in a polyvinyl butyrate
matrix.
[0037] FIG. 17 is the absorbance spectrum of a dye set containing
0.12% Astrazon Orange, 0.18% ABS 574, 0.32% ABS 594, and 0.38%
Luxol Fast Blue, with an IR radiation shielding component in a PMMA
matrix.
[0038] FIG. 18 is a chromaticity diagram of the dye set containing
0.12% Astrazon Orange, 0.18% ABS 574, 0.32% ABS 594, and 0.38%
Luxol Fast Blue, with an IR radiation shielding component in a PMMA
matrix.
[0039] FIG. 19 is a graph illustrating the intensity of the
phosphors of a PDP with and without a filter of the present
invention.
[0040] FIG. 20 is the absorbance spectrum of dye IRA 850, an
infrared shielding dye, dissolved in MEK and DMF in a PMMA
matrix.
DESCRIPTION OF THE INVENTION
[0041] The present invention discloses a spectrally tuned bandpass
filter (notch filter) including multiple bandpass filter, which
substantially increases the transmission of the primary colors from
the reflected light of a color display device while substantially
absorbing the non-primary colors, and thereby improving the
contrast and color of the image for the viewers. The filter
comprises a specific set of suitable dyes that substantially absorb
the non-primary colors without significant effect on the primary
colors.
[0042] Contrast from a display device screen is generally defined
by the term "contrast ratio". Contrast ratio, C, is commonly
defined by the Equation 1: 1 C = T ( ) S ( ) I p ( ) T 2 ( ) S ( )
I a ( ) R ( ) ( 1 )
[0043] where T is the transmittance of the substrate as a function
of wavelength .lambda., S is human eye spectral sensitivity
function, I.sub.p and I.sub.a are respectively the display source
intensity (e.g., phosphor emission intensity) and the ambient light
source intensity, and R is the Reflection Coefficient for the
display phosphors. As can be seen, C can be increased by making
I.sub.a and/or T(.lambda.) arbitrarily small for a given display
system. However, if a display is viewed in the total darkness
(I.sub.a very small), although one can have very high contrast, it
becomes very difficult to compare two different displays without
using an identical condition. Display industries are therefore
making an attempt to use a standardized ambient light condition in
comparing display performance. Similarly by increasing I.sub.p, one
can improve C. In fact, display industry is working very hard to
increase I.sub.p. Since I.sub.a and I.sub.p are independent of
contrast enhancing devices, normalized intensities functions given
in Equations 2 and 3 are generally defined in order to compare the
performance of contrast enhancing devices: 2 i p = T ( ) S ( ) I p
( ) S ( ) I p ( ) and ( 2 ) i a = T ( ) S ( ) I a ( ) S ( ) I a ( )
( 3 )
[0044] where i.sub.a and i.sub.p are normalized ambient and display
intensities respectively. Normalized contrast (C) and the
figure-of-merits (.eta.) are defined as in Equations 4 and 5
respectively: 3 C _ = i p i a and ( 4 ) = C _ i p = i p 2 i a ( 5
)
[0045] For an ideal neutral density or similar filters, there is no
improvement in the figure-of-merits, i.e., .eta.=1. Thus, they do
not improve the real performance, but provide a trade-off between
display brightness and contrast. In other words, they offer
contrast enhancement at the expense of image brightness. Thus, for
example, for a 50% absorptive neutral density filter, contrast may
be doubled, i.e., {overscore (C)}=2, i.sub.p=0.5 and i.sub.a=0.25.
But there is 50% absorption.
[0046] The figure-of-merit is a contrast between the color contrast
of the image and the brightness of the image. In other words, the
figure-of-merit is a balance between the two variables of color
contrast and brightness of the image. Both good color contrast and
brightness are desired. For example, an .eta.=1.2 means that the
contrast is about 20% greater than the brightness. An .eta.<1
means that the contrast can still be improved in the image.
[0047] The spectrally tuned filters of the present invention
comprise suitable dyes contained uniformly within a carrier matrix
such as a polymer matrix. The filters may be present on a CRT or
PDP monitor with or without an intermediary polymeric substrate.
Alternatively, the filters can be free standing and placed in front
of the CRT or PDP monitor. Suitable dyes are those which
selectively absorb undesired wavelengths without significantly
absorbing the desired wavelengths. The desired wavelengths
correspond to the three primary colors; red, blue and green. Table
1 lists suitable dyes useful in the practice of the invention. Many
of these are commercially available trademarked materials from
various sources. One such source is Aldrich Chemical Company,
Milwaukee, Wis.
1 TABLE 1 List of Suitable Dyes ABS 574 ABS 594 Astrazon Orange G
Brilliant Blue R Luxol Fast Blue MBSN Bromochlorophenol Blue Sodium
salt Bromophenol Blue Sodium salt Bromocresol Purple Sodium salt
2',7'-Dichlorofluorescein Eosin Y Fluorescein Fluorescein amine
isomer 1 Fluorescein amine isomer 11 Fluorexon Bromophenol Blue
Acridine Orange Acridine Orange base .sigma. - Cresolphthalein
.sigma. - Cresolphthalein complexone Cresol Red Fast Blue Mordant
Orange 1 Phloxine B Pyronin B Rhodamine 101 Rhodamine 123 Hydrate
Sulfobromophthalein Sodium Hydrate Sulforhodamine 101 Hydrate
Chlorophenol Red IRA 850
[0048] Useful dyes for general purpose image enhancement
application in the filters of this invention should have the
following characteristics:
[0049] 1. Absorption Characteristics
[0050] a) Absorption peak (.lambda.) falling into one of the
following wavelength regions:
[0051] .lambda.430 nm
[0052] 470 nm.lambda.510 nm
[0053] 550 nm.lambda.610 nm
[0054] .lambda.650 nm
[0055] b) Absorption Bandwidth is within the range of 30-80 nm.
[0056] 2. Stability
[0057] a) Light fastness
[0058] Less than 10-20% degradation under 85 MJ/m.sup.2 exposure of
white light (400 nm to 700 nm).
[0059] b) Thermal stability
[0060] Less than 10-20% degradations under following stress
conditions 70.degree. C., 70% RH and 72 hrs.
[0061] 3. Solubility
[0062] a) Soluble in an environmentally friendly solvent.
[0063] b) Soluble in an optically clear polymer resin matrix
suitable for high quality coating.
[0064] Various combinations of the dyes listed in Table 1 may be
employed to obtain a bandpass filter of this invention. Preferably,
the dye combinations include at least one or more red dyes having
the absorbance spectrums of FIGS. 1 or 2 as well as having the
stability and solubility described above. Combinations of these
particular red dyes with other colored dyes can be made to yield
effective multiple bandpass filters for display devices such as
CRTs and PDPs and the like.
[0065] ABS 594 dye and ABS 574 dye are available from Exiton, Inc.
of Dayton, Ohio, a maker of specialty dyes. These red dyes have the
absorbance spectra illustrated in FIG. 1 and FIG. 2, respectively.
The absorbance spectrum of each dye was prepared by preparing a
0.050% sample of each dye in a methylethyl ketone solution
containing 25% of polymethyl methacrylate. The samples were then
measured on a standard spectrophotometer. The value of optical
density, i.e., absorbance, of the dye is not particularly important
in defining a dye material. The value of optical density or
absorbance is always going to be greater when the concentration of
the test sample is increased. However, the wavelength where the
peak or peaks of the absorbance spectrum occur are unique and
remain constant for a particular dye. The location of the
absorption peak is fixed once the dye and solvent system is
selected. Thus, it is the location of the absorption peak or peaks
which characterizes a dye or dye composition.
[0066] In addition to the location of the absorption peaks, the
bandwidth of the spectrum (absorption peaks) can also be used to
identify a dye. In an optical density versus wavelength plot, the
full width in nm at the half peak height is measured as
bandwidth.
[0067] IRA 850 dye, listed in table 1, which is also available from
Exiton, Inc., has the absorbance spectrum illustrated in FIG. 20.
The absorbance spectrum was prepared by adding a 0.05% sample of
the IRA 850 dye to a solution of about 33% dimethylfuran and a 67%
mixture of polymethyl methacrylate and methylethyl ketone by
weight. The sample was measured on a standard spectrophotometer.
The IRA 850 dye is especially effective in shielding IR radiation
from plasma display panels as shown in Example 8 below. IR
radiation emitted from plasma display panels interferes with the
operation of remote control units thus, compromising the optimum
performance of such electronic equipment.
[0068] The dye compositions (the total weight of all the dyes)
comprise generally from about 0.01% to about 10% by weight of the
dry carrier matrix used to form the filter of this invention.
Preferably, the dyes comprise from about 0.04% to less than about
4.0% by weight of the dry matrix. The following are general and
preferred ranges of particular dyes useful in this invention.
Specific amounts of each dye in particular combinations of dyes are
shown in the Examples and can provide a reference to the effect
each dye has on the overall absorbance spectrum of the filter. Such
examples can suggest other useful dye combinations within the
general and preferred weight ranges shown and even beyond the
combinations shown in the examples to provide an effective color
enhancement filter. Dye ABS 574 comprises from about 0.02% to about
0.45% by weight of the matrix, preferably about 0.10% to about
0.45%. ABS 594 comprises from about 0.04% to about 0.85% by weight
of the matrix, preferably from about 0.04% to about 0.80%.
Combinations of ABS 574 and ABS 594 are particularly useful either
alone or with other dyes. Additionally, Astrazon Orange in amounts
of from about 0.02% to about 2.0% by weight of the matrix,
preferably from about 0.060% to about 1.0%; Luxol Fast Blue in
amounts of from about 0.02% to about 2.0% by weight of the matrix,
preferably from about 0.06% to about 1.0%; Disperse Yellow 9 in
amounts from about 0.20% to about 0.80% by weight of the matrix,
preferably from about 0.40% to about 0.70%; and IRA 850 in amounts
from about 0.50% to about 10.00% by weight of the matrix,
preferably from about 4.00% to about 8.00%, can be used singly or
in combination with the ABS red dyes to yield filters with multiple
pass bands of the primary colors.
[0069] The spectrally tuned filters of the present invention can be
prepared by any suitable method in the art for preparing films and
coated films. A set of suitable dyes (e.g., from Table 1) and resin
system is dissolved in a suitable solvent to a sufficient enough
concentration to result in sufficient absorption of the undesired
wavelengths in the transmitted light when on the monitor.
Sufficient absorption is generally over 20%, preferably over 50%
and typically over 80%. Suitable solvents are those that are
compatible with the solvents chosen for the polymer matrix material
as well as dependent on whether or not the dye/polymer matrix
combination is going to be present on a polymeric substrate before
going on the monitor. Such modifications and techniques will be
obvious to those skilled in the art of coatings. Generally a lower
alcohol, water, and the like solvents are non-corrosive and
compatible with each other. Thus, for example, the dyes may be
dissolved in a lower alcohol to form solution A, the polymer matrix
material may be dissolved in water or alcohol to form solution B
and the two solutions may then be mixed in sufficient quantities.
Polymer matrix materials are those polymers which are compatible
with the other materials mentioned above and also form optically
transparent films. Some examples include polyvinyl alcohol (PVOH),
polyvinyl acetate (PVA), vinyl polymers and polyacrylates such as
polyolefins, polymethyl methacrylate (PMMA), polystyrene,
cycloolefin polymers and copolymers (COC), polycarbonate,
polyurethane, polyamide, polyester, polyether, polyketone,
polyesteramide, polyvinyl butyrate (PVB), and the like. Many of the
polymers may also be crosslinkable by suitable techniques such as,
for example, thermal, radiation cure and the like. After mixing
solutions A and B, one may optionally add additives such as, for
example, viscosity modifiers, surfactants, volatilizers and the
like in order to ease and/or enhance film casting, film drying,
film thickness and the like. Such techniques are well known in the
coatings industry.
[0070] One or more films may be formed from the mixture of dye or
dyes and polymer matrix by any suitable technique such as, for
example, solvent casting, extrusion, spray coating, roller coating,
dip coating, brush coating, spin coating and the like. Such film
forming techniques are well known. Alternately, instead of forming
the film or films from a mixture of dye and polymer, the polymer
matrix may be formed first as a film and then dyed. The film, or
films may then be affixed to the monitor surface by a suitable
method such as, for example, use of adhesives.
[0071] Still alternately, the mixture of dye and polymer matrix may
be spun coated on a suitable substrate as a film or films. The
coated substrate may then be affixed to the monitor surface by a
suitable method such as, for example, use of adhesives. Suitable
substrates are glass as well as polymeric. Suitable polymeric
substrates are optically transparent polymers such as, for example,
polyesters, polyacrylates, polyolefins, polycarbonate and the like.
Among polyesters, polymer films such as polyethylene terephthalate
(PET), polybutylene terephthalate (PBT) are preferred.
[0072] When extruded to form a film the dyes can be incorporated
into the molten polymer matrix during extrusion into a film or the
dye and matrix polymer mixture can first be extruded into pellets
and the pellets melted and extruded into the desired film. The film
may then be affixed to the monitor surface by any suitable method.
Such a method is particularly useful when a polyester such as PET
or PBT is used as the matrix.
[0073] In yet another alternate manner, the dye/polymer mix may be
sprayed directly onto the monitor to form a suitable film. The
invention is flexible enough to accommodate such varied
methods.
[0074] The bandpass filter of the present invention can preferably
be employed on both a CRT screen or a plasma display panel. The
filter of the present invention can be applied to the outer surface
of the face plate of CRTs of televisions, computer screens, and the
like, or the filter can be free-standing and placed before the
screen. The inner surface of the CRT screen contains a color
phosphor. Examples of such CRT screens can be found in U.S. Pat.
No. 4,977,347, to Itou et al., U.S. Pat. No. 4,785,217, to Matsuda
et al., and U.S. Pat. No. 4,563,612, to Deal et al., the
disclosures of which are incorporated in their entirety herein by
reference.
[0075] The bandpass filters of the present invention can also be
employed on plasma display panels. Plasma display panels are
essentially a sandwich of glass sealed at the edges with a low
temperature frit enclosing an inert gas mixture and thin-film
conductive electrodes on the inner surfaces of the glass. Parallel
lines of transparent conductors are placed on one of the inner
surfaces and metal electrodes are on the outer surfaces. The filter
of the present invention is placed on the face of the outer glass
surface, or the filter can be free-standing and placed before the
face of the outer glass surface. Examples of suitable plasma
display panels are U.S. Pat. No. 5,818,168, to Ushifusa et al., and
U.S. Pat. No. 3,601,532, to Blitzer et al., the disclosures of
which are incorporated herein in their entirety by reference.
[0076] The following examples are intended to illustrate the
present invention, but are not intended to limit the scope of the
invention.
EXAMPLE 1
[0077] Plasma displays are faced with two major problems: (1) low
blue intensity, and (2) low red color purity due to an unwanted
intense orange peak around 590 nm in the red phosphor emissions
spectrum. The dye set in the present example was designed to
address these two problems.
[0078] Dyes ABS 594 and ABS 574 having the absorbance spectrums as
shown in FIGS. 1 and 2, respectively, were dissolved in methylethyl
ketone to near saturation. Separately, the material employed for
the polymer matrix, polymethyl methacrylate was dissolved in
methylethyl ketone to about 20 weight %. The dye solution was added
to the polymethyl methacrylate solution. A few drops (about 0.01%
by weight of surfactants Genepole.RTM. and Dynol.RTM. were added.
The film was spun-coated on a 4 mil (100 micron) thick polyethylene
terephalate substrate at about 1,000 rpm for about 30 seconds. The
film was then dried in an oven at about 50.degree. C. for about 30
minutes to achieve a total dry film and substrate thickness of
about 8 microns. The weight of the dyes in relation to the dry
polymer matrix was about 0.040% of ABS 574 and about 0.53% of ABS
594. The filter was mounted on a 5 inch diameter plasma display
panel. The filter was attached to the plasma display panel with the
adhesive PET. The selected dye combination was found to be very
stable optically and compatible with the polymethyl methacrylate
polymeric matrix and formed a liquid coated film on the plasma
display panel.
[0079] As illustrated in FIG. 3, the dye set absorbed the unwanted
emission peak at 590 nm. Since the dye set absorbed between the red
and green primary colors, it was expected that there would be an
impact on both red and green transmittance. Surprisingly, there was
a noticed improvement in blue color. The reason for the improved
blue color enhancement was uncertain. However, it is believed that
all three colors were contaminated by orange emission from neon gas
used in the plasma display panel discharges. The orange emission
originating from the neon gas was not the same as the emission from
the red phosphor, but the emission peaks were very close to each
other. One problem with the dye set was a pinkish rest color.
[0080] FIG. 4 is a chromaticity diagram of color emission of a
plasma display panel with (solid line) and without (dashed line) a
filter. FIG. 4 also shows a spectrum locus (curved temperature
scale) of a blackbody radiation in the CIE standard chromaticity
diagram. The + is the white point or sunlight, the solid dot shows
the ambient light in relation to the transmittance from the
filtered and non-filtered panel. The circle on the spectrum locus
shows the reflected white light in relation to the transmitted
light by the panels.
[0081] Table 2 presents the color coordinates of the plasma display
panel with and without the filter of this example. As shown by the
chromaticity diagram, the dye set has improved transmittance in the
red, green, and blue wavelengths over the plasma display panel
without a filter.
[0082] Since the color coordinates defined in the CIE standard
chromaticity diagram are highly non-linear, contrasting the
difference between two colors by the color coordinates alone is
difficult. Thus, the E-values or .DELTA.E is determined for each
coordinate. The E-value or .DELTA.E is proportional to the human
perception difference between two colors. A .DELTA.E=0 indicates
that human perception can not distinguish between two colors. A
.DELTA.E=about 2 or 3 indicates that a very sensitive observer can
tell the difference between two colors. A .DELTA.E=about 5
indicates that there is an obvious difference between two colors to
a human observer, and a .DELTA.E>15 indicates that an observer
can conclude that a color is completely different from the other
colors to which it is compared.
[0083] The .DELTA.E for the red, green, and blue were about 34.0,
24.6, and 9.5, respectively. Thus, an observer can completely
distinguish the red and green colors of the PDP with the present
filter from the red and green colors of the PDP without the filter.
The observer can at least conclude that there is an obvious
difference between the blue color of the PDP with the filter as
opposed to the PDP without the filter.
[0084] Also, the dye set has an improved color temperature of about
+13,500.degree. K, a relative brightness of about 58.2%, a relative
contrast of about 1.57 and a figure of merit of about 0.9137.
EXAMPLE 2
[0085] The present dye set was essentially identical to the dye set
in Example 1, except that ABS 574 comprised about 0.25% and ABS 594
comprised about 0.50% of the film. The process of preparing the
filter in the present example was identical to that in Example
1.
[0086] The filter of this example showed improvements over the
filter of Example 1. Thus, the filter of this example showed
improvements in the green transmission as illustrated in FIG. 5 and
FIG. 6. The overall brightness was increased from about 58.2% to
about 63.6% and the figure-of-merit increased from about 0.9137 in
Example 1 to about 0.9349, see Table 2. The color temperature
improvement was about +7,500.degree. K in contrast to that of the
panel display screen without a filter, and the present plasma
display panel had a relative contrast of about 1.47.
[0087] The .DELTA.E for the red, green, and blue coordinates was
about 31.7, 20.0, and 6.8, respectively. Thus, an observer can
distinguish the red and green colors of the plasma display panel
with the present filter as completely different from the red and
green of the plasma display panel without the filter. The observer
can conclude that there is at least an obvious difference between
the blue of the plasma display panel with the filter in contrast to
the plasma display panel without the filter. However, the rest
color still remained a problem.
EXAMPLE 3
[0088] The present dye set was prepared in an effort to improve the
rest color from the dye sets of Examples 1 and 2 while maintaining
the relatively high blue transmission.
[0089] The present dye set was prepared in a two-layer filter. The
first layer comprised a polymer matrix of polymethyl methacrylate
having a thickness of about 6 microns. The dye package comprised
about 0.40% ABS 574 and about 0.80% ABS 594 by weight of the film.
The first layer was prepared by the same method as described in
Example 1.
[0090] The second layer was composed of the dye package Astrazon
Orange and Luxol Fast Blue. The dyes were dissolved in a solution
of 50% water, 30% isopropyl alcohol, and 20% methyl alcohol. The
dye solution was added to a polymer matrix of polyvinyl acetate. A
few drops (about 0.01% by weight) of the surfactants Genepole.RTM.
and Dynol.RTM. were added. The second layer was spun-coated on the
6 micron first layer at about 1,000 rpm for about 30 seconds. The
filter was then dried in an oven at about 50.degree. C. for about
30 minutes to achieve a total thickness of about 12 microns. The
weight of the dyes in the dried polyvinyl acetate matrix was about
1.0% Astrazon Orange and about 1.0% Luxol Fast Blue. The filter was
mounted on a plasma display panel having a 5 inch diameter.
[0091] FIG. 7 shows the optical density (absorbance) properties of
the subject dye set. The dye set produced a pleasing, slightly blue
tinted gray rest color. This produced a very high color temperature
on the plasma display panel, i.e., about 8,000.degree. K,
suggesting that the filter can be tailored for the color
temperature of displays.
[0092] FIG. 8 illustrates the CIE standard chromaticity diagram
with the improved light transmittance over a plasma display panel
without a filter. Also, there was an improved color temperature of
about +1,500.degree. K, a relative brightness of about 47.1%,
relative contrast of about 1.99% and a figure-of-merit of about
0.9372. The .DELTA.E of red, green, and blue was about 35.8, 27.0,
and 19.7, respectively. Thus, an observer can completely
distinguish the red, green and blue of the plasma display panel
with the filter over the red, green and blue of the plasma display
panel without the filter. Table 2 again sets forth the color
coordinates of the PDP with and without the filter as well as other
optical properties.
[0093] FIG. 19 illustrates the intensity of the blue, green and red
primary colors of the phosphor of the plasma display panel. The
graph with the dotted graph shows the intensity of the phosphor
without the present filter. The blue phosphor emission spectrum is
at about 450 nm, the green phosphor is at about 515 nm, and the red
phosphor emission is at about 610 nm and about 625 nm with an
orange emission at about 590 nm. The red phosphor emission spectrum
has a low red color purity because of the intense orange peak
around 590 nm.
[0094] The addition of the present filter to the plasma display
panel significantly reduces the intensity of the unwanted orange
peak at about 590 nm as shown by the solid graph in FIG. 19. The
filter of the present invention reduces the intensity of the orange
peak to improve the red color purity of the red phosphor emission
spectrum. Thus, as shown by the graphs of FIG. 19, the filter of
the present invention improves the color contrast and enhancement
of a plasma display panel.
EXAMPLE 4
[0095] The dye set of the present example was made in an attempt to
produce a true gray rest color. The present dye set offers a
neutral appearance under ambient light but with the trade-off of
the ability to improve the color temperature of the plasma display
panel. The filter was a two-layer filter as prepared in Example 3
except that the first layer contained ABS 574 at a weight of about
0.25% and ABS 594 at a weight of about 0.50% of the polymethyl
methacrylate matrix. The components of the second layer were
identical as in Example 4 except the second layer was 12 microns
thick.
[0096] FIG. 9 illustrates the absorbance spectrum of the dye set as
modified from the dye set of Example 3. The chromaticity diagram of
FIG. 10 illustrates the improved transmittance of the dye set in
contrast to a plasma display panel without the present filter.
[0097] The present dye set had a improved color temperature of only
about 400.degree. K in contrast to the improved color temperatures
of the other dye sets. The relative brightness was about 36.7, the
relative contrast was about 2.42, and the figure-of-merit was about
0.89. Thus, to improve the relative contrast, the dye set
sacrificed color temperature, relative brightness, and
figure-of-merit, see Table 2.
[0098] The .DELTA.E of the red, green, and blue transmissions were
about 42.5, 36.3, and 28.7, respectively. Thus, an observer can
completely distinguish the red, green, and blue of the plasma
display panel with the filter over the red, green, and blue of the
plasma display panel without the filter.
EXAMPLE 5
[0099] The present dye set also offered a neutral appearance under
ambient light with the trade-off ability to improve the color
temperature of the plasma display panel. The present dye set was
prepared as the dye set in Example 4, except that the second layer
had a thickness of 12 microns.
[0100] FIG. 11 illustrates the absorbance spectrum of the present
dye set and FIG. 12 illustrates a chromaticity diagram of the
present dye set showing the transmittance of red, green, and blue
light as opposed to a plasma display panel without the filter.
[0101] From Table 2 it can be seen that the present dye set
increased the brightness from about 37% in Example 4 to about 56.9%
and increased transmission in the blue region. Also the
figure-of-merit improved significantly from the dye set of Example
4 from about 0.8 to about 0.96, while slightly compromising the
improvement of green color purity. Color temperature was improved,
about 1,000.degree. K relative to the PDP without a filter. The
relative contrast was about 1.69.
[0102] The .DELTA.E of the red, green, and blue color coordinates
were about 28.8, 19.2, and 15.2 respectively. Thus, an observer can
completely distinguish the red, green, and blue colors of the
plasma display panel with the filter over the plasma display panel
without the filter.
EXAMPLE 6
[0103] The present dye filter was prepared by a casting method as
opposed to the coating method of the previous examples. The present
filter was cast onto the surface of the plasma display panel. The
filter was formed from a cellulose acetate layer about 50 microns
in thickness. The dye set consisted of Astrazon Orange, ABS 574,
ABS 594, and Luxol Fast Blue. All the dyes were added to a solution
of acetone and methanol and mixed with cellulose acetate. A few
drops (about 0.01% by weight) of the surfactants Genepole.RTM. and
Dynol.RTM. were added. The film was then cast on the glass surface
of the plasma display panel by using a commercial scale casting
equipment. The final dry weight of the dyes in relation to the
cellulose acetate matrix was about 0.065% of Astrazon Orange, about
0.024% of ABS 574, about 0.048% of ABS 594, and about 0.060% of
Luxol Fast Blue.
[0104] As shown by the data in Table 2 and FIGS. 13 and 14, the
performance of the present film was rather impressive. The relative
brightness was about 64%, relative contrast about 1.45, and
figure-of-merit of about 0.935. The blue transmission was about
68%. Thus, the present dye set showed high brightness, high blue
transmission, a significant increase of color gamut, a good
figure-of-merit, and an improved color temperature of about
+500.degree. K.
[0105] The .DELTA.E of the red, green, and blue color coordinates
was about 25.7, 12.2, and 13.1, respectively. Thus, an observer can
completely distinguish the red color of the plasma display panel
with the filter over the plasma display panel without the filter,
and at least observe that an obvious difference exists between the
green and blue of the plasma display panel with the filter over the
panel without the filter.
EXAMPLE 7
[0106] The filter of this example was an attempt to reproduce dye
set 3 (Example 3) using a single layer coating.
[0107] The present dye combination of Disperse Yellow 9, Astrazon
Orange, ABS 574, ABS 594, and Luxol Fast Blue was mixed in a
solution of 40% methyl ethylketone and 60% methanol. Additionally,
polyvinyl butyrate (polymer matrix) was dissolved in water to 20
weight %. The dye composition was then added to the solution of
polyvinyl butyrate. The film was spun-coated on a 4 mil (100
microns) thick PET film at about 1,000 rpm for about 30 seconds.
The film was then dried in an oven at about 50.degree. C. for about
30 minutes to achieve a total dry film thickness of about 5
microns. The weight of the dyes in the dry polyvinyl butyrate
matrix was about 0.45% Astrazon Orange, about 0.25% ABS 574, about
0.50% ABS 594, and about 0.55% Luxol Fast Blue. This was mounted on
a plasma display panel (a 5 inch color television monitor).
[0108] Again from Table 2, a significant improvement in color
temperature was observed, i.e., about 800.degree. K. The relative
brightness was about 62% with a high blue transmission of about
69%, yet with an acceptable rest color. The relative contrast was
about 1.51 with a good figure-of-merit of about 0.94%. FIG. 15
illustrates the absorbance spectrum of the subject dye set and FIG.
16 shows the improved transmittance of blue, green, and red colors
in contrast to a plasma display panel without the present
filter.
[0109] The .DELTA.E of the red, green, and blue coordinates was
about 24.6, 16.8, and 12.0, respectively. Thus, an observer can
completely distinguish between the red and green from the plasma
display panel with the filter over the plasma display panel without
the filter, and may conclude that there is at least an obvious
difference between the blue of the panel with the filter over the
panel without the filter.
EXAMPLE 8
[0110] The dye set was composed of about 0.12% by weight of
Astrazon Orange, about 0.18% by weight of ABS 574, about 0.32% by
weight of ABS 574, about 0.32% by weight of ABS 594, and about
0.38% by weight of Luxol Fast Blue in a polymethyl methacrylate
polymer matrix. The solvent employed was a mixture of 80% methyl
ethylketone and 20% dimethylfuran. The dye set was spun-coated into
a 7 micron film on PET.
[0111] It was learned that IR radiation from the plasma emitted by
PDP interferes with the operation of remote control units,
requiring IR shielding in filters. Accordingly, this dye set was
designed to meet this requirement by adding about 7% by weight IRA
850 to the polymer/dye solution.
[0112] The present dye set offered a neutral appearance under
ambient light but with the ability of blocking off near infrared
radiation emitted by the plasma without any compromise in the image
enhancement performance. Also, polymethyl methacrylate resin was
again employed in preparing the filter. Polymethyl methacrylate is
an optically better performer than polyvinyl butyrate.
Additionally, an unexpected improvement in stability was also
observed. While not holding to any particularly theory, the lower
moisture absorption from polymehtyl methacrylate as opposed to
polyvinyl butyrate may explain the improvement in stability.
[0113] FIG. 17 illustrates the absorbance spectrum of the present
dye set. FIG. 18 illustrates the chromaticity diagram showing
improved color contrast in the red, green, and blue wavelengths
over a plasma display panel without the filter. Also, the present
dye set showed an improved color temperature of about
+15,000.degree. K, an improved relative brightness of about 62.2%
with a relative contrast of about 1.523, a good figure-of-merit of
about 0.95, see Table 2, and also an improved blue transmission of
about 73%.
[0114] The .DELTA.E of the red, green, and blue coordinates was
about 28.8, 16.0, and 9.6, respectively. Thus, an observer can
completely distinguish the red and green colors of the plasma
display with the filter over the plasma display panel without the
filter, and can at least conclude that there is an obvious
difference between the blue of the plasma display panel with the
filter over the panel with the filter.
2TABLE 2 Polymeric Image Enhancement Film Comparison of Performance
of Dye Sets on PDP Color Figure Temp Brightness of Red Green Blue
White Ambient .degree. K. Contrast Merit No filter 0.607, 0.353
0.236, 0.684 0.157, 0.107 0.311, 0.334 0.310, 0.317 6500 1 1 1
Example 1 0.622, 0.310 0.194, 0.697 0.149, 0.089 0.263, 0.276
0.246, 0.206 20000 0.582 1.57 0.9137 Example 2 0.621, 0.314 0.200,
0.698 0.149, 0.093 0.266, 0.289 0.250, 0.227 14000 0.636 1.47
0.9349 Example 3 0.627, 0.321 0.227, 0.700 0.159, 0.087 0.295,
0.308 0.295, 0.257 8000 0.471 1.99 0.9372 Example 4 0.633, 0.322
0.235, 0.705 0.165, 0.089 0.310, 0.330 0.318, 0.295 6900 0.367 2.42
0.8881 Example 5 0.623, 0.329 0.228, 0.699 0.159, 0.094 0.298,
0.321 0.297, 0.281 7500 0.569 1.69 0.9616 Example 6 0.622, 0.330
0.227, 0.702 0.160, 0.097 0.296, 0.330 0.304, 0.315 7000 0.640 1.45
0.9350 Example 7 0.622, 0.331 0.230, 0.695 0.157, 0.099 0.298,
0.323 0.308, 0.311 7300 0.620 1.51 0.9400 Example 8 0.619, 0.329
0.222, 0.696 0.154, 0.098 0.286, 0.316 0.283, 0.299 8000 0.622 1.52
0.9500
* * * * *