JP2001066420A - Surface treated film for display device and display device using same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a high contrast and high definition surface treated film by incorporating organic dyes selected from a quinacridone dye, a disazo yellow dye, an azomethine dye and a phthalocyanine dye. SOLUTION: Organic dyes selected from a quinacridone dye, a disazo yellow dye, an azomethin dye and a phthalocyanine dye are incorporated into a surface treated film for a display device. When these dyes are used, the film can be made achromatic by magenta, green and yellow dyes because the quinacridone magenta dye has the absorption peak in the range of 500-600 nm and the phthalocyanine green dye having absorption in the range of 650-670 nm and the disazo yellow dye having flat absorption in the range of 380-450 nm assume complementary colors to magenta. A wavelength selective absorption film having good contrast characteristics is obtained.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] 1. Field of the Invention [0002] The present invention relates to a surface treatment film which contributes to high contrast and a display device provided with the same on a display surface.

[0002]

2. Description of the Related Art A cathode ray tube is a typical display device. As the image quality of televisions has increased, cathode ray tubes in which a wavelength selective absorption film (optical filter) is formed on the front surface of a face plate have been produced.

In this method, external light having a specific wavelength is selectively absorbed by the optical filter to prevent reflection of the external light and to absorb a side band of a phosphor emission spectrum which is a cause of deterioration of color purity. The purpose is to increase color purity and improve contrast. Usually, this optical filter is an organic dye / glass gel composite film prepared by using a sol-gel method (Japanese Patent Application Laid-Open Nos. 1-320742 and 4-14738).

Further, as an organic dye used for the optical filter, a rhodamine-based organic dye is used because it is easily dissolved in a solution. Many of these rhodamine-based organic dyes have absorption near 560 to 590 nm, which is the highest in human luminous sensitivity, and efficiently absorb side bands of green and red light emitters to improve color purity and improve contrast. Because it is effective for raising.

[0005]

The above-mentioned rhodamine dyes have an excellent effect of improving the contrast of a display device, but have the following drawbacks.

That is, in the wavelength selective absorption film as described above, the dye having an absorption at 560 to 590 nm develops a strong red-violet color, so that the panel surface of the display device is colored with a strong and unique color, and the commercial value is high. Will drop. Therefore, in order to cancel this color, it is necessary to dope a dye that is a complementary color. Normally, there are few dyes having an ideal complementary color relationship, and it is necessary to dope various dyes in order to produce the complementary color.

[0007] Further, in such a device, since the absorptions of a large number of dyes overlap in the visible light region, there is a problem that the light of the emission wavelength of the R, B, and G light emitters is also absorbed, and the color purity and contrast are reduced. .

Further, there is a disadvantage that the doping of several kinds of dyes increases the dye concentration in the film and lowers the film strength. Furthermore, since the rhodamine-based pigment is a dye, there is a problem that light resistance is poor.

[0009] Therefore, a good combination of dyes has not been found as a surface treatment film for a display device. For this reason, there has been no surface treatment film for a display device that has both a wavelength-selective absorption film with good performance and anti-reflection and antistatic performance.

An object of the present invention is to solve the above-mentioned drawbacks and to provide a high-contrast and high-definition surface treatment film and a display device using the same.

Another object of the present invention is to provide a display device having a reflection-preventing effect and a wavelength-selective absorption effect.

[0012]

Means for Solving the Problems [1] A surface treatment film for a display device comprising an organic dye selected from quinacridone dyes, disazo yellow dyes, azomethine dyes, and phthalocyanine dyes.

[2] A surface treatment film for a display device, comprising at least three kinds of organic dyes of a quinacridone dye, a disazo yellow dye (or an azomethine dye), and a phthalocyanine dye.

[3] The surface-treated film formed on the display substrate of the display device contains, in the surface-treated film, an organic dye selected from a quinacridone dye, a disazo yellow dye, an azomethine dye, and a phthalocyanine dye. A display device characterized by the above-mentioned.

[4] The surface-treated film formed on the display substrate of the display device has at least three of a quinacridone dye, a disazo yellow dye (or an azomethine dye), and a phthalocyanine dye in the surface-treated film. A display device comprising a kind of organic dye.

[5] The display device as described above, wherein the surface treatment film contains conductive fine particles.

[6] The conductive fine particles are made of Antimony T
in Oxide (ATO), Indium Tin Oxide (IT
O) The display device described above, which is at least one selected from Ag, Pd, Pt, and Au.

[7] The display device, wherein the surface treatment film has a low refractive index film having a lower refractive index than that of the surface treatment film as an upper layer.

[8] The display device, wherein the low refractive index film is SiO ₂ .

[0020]

[9] The display device, wherein the surface treatment film has a conductive film as an upper layer.

[0021]

BEST MODE FOR CARRYING OUT THE INVENTION Since a rhodamine or quinacridone organic dye develops a purple-red color, it is necessary to dope a complementary green dye to cancel this color.

However, ordinary green color elements are not enough to render the red-violet color elements achromatic. This is because the absorption spectrum of the green dye is different from the spectrum of the rhodamine-based or quinacridone-based red-violet absorption spectrum, which is complementary to the absorption spectrum of the red-violet color.

For this reason, usually, a method is employed in which rhodamine-based or quinacridone-based red-purple is achromatically mixed by mixing yellow and blue. However, no satisfactory combination of pigment dyes exhibiting the wavelength-selective absorption effect has been found so far, and there is no one having good performance.

Further, since the blue dye and the yellow dye have absorption in the light emitting regions of the R luminous body and the B luminous body, these luminescences are absorbed to lower the color purity contrast. Furthermore, this results in insufficient film strength due to an increase in the contained pigment.

The present inventors have studied the absorption spectra of various red-purple pigments, green pigments and yellow pigments.
It has been found that a combination of a quinacridone dye, a phthalocyanine dye, a disazo yellow dye or an azomethine dye can sufficiently achromatize the film color.

It has been found that the use of this dye makes it possible to make the film achromatic with the three components of a reddish purple dye, a green dye and yellow yellow.

This is because the quinacridone-based organic dye has a red-violet transmission performance having an absorption peak at 550 to 600 nm, whereas the phthalocyanine-based green dye has an absorption peak of 650 to 67 nm.
Absorption at 0 nm, and disazo yellow-based yellow
This is because it has a flat absorption in the range of 80 to 450 nm, so that it becomes a complementary color of a red-violet dye and can be efficiently achromatic.

Since the three-component film has relatively weak absorption in the light emitting region of the R and B light emitters, the color purity is improved and the contrast is improved. In addition, this makes it possible to achieve achromatic coloration of the film with a minimum of three types without using many types of organic dyes, and to improve the strength of the film because the amount of dye contained in the film may be small.

Further, since the quinacridone dye, the disazo yellow dye, the azomethine dye and the phthalocyanine dye are all organic pigments, their light resistance is very good as compared with a film using a conventional rhodamine organic dye.

Examples of the quinacridone pigments include CI Pigment Violet 19 and CI Pigment Red 20.
The basic skeleton of quinacridone, such as 7, 209, 202, 207, 206, having various substituents is effective.

Examples of disazo yellow dyes include Pigment Yellow 11, 12, 13, 14, 16, 17, 5
A disazo yellow skeleton such as 5, 81, 83, 93, 94 having various substituents is effective.

Examples of the phthalocyanine dye include Cu phthalocyanine green (CI Pigment Green 7, 3).
Dyes having various halogen substitutions in the phthalocyanine skeleton such as 6) are effective.

As azomethine dyes, CI Pigment Yellow 129, 83 and the like can be typically used.

If the basic skeletons of these dyes are the same, they are not limited to the above-mentioned dyes.

Further, when conductive fine particles are contained in the film containing the above-mentioned dye, antistatic performance can be imparted. Further, when a silica-based low refractive index film is formed on the film containing the conductive fine particles and the newly synthesized dye, a reflection antistatic effect utilizing light interference can be imparted.

In addition, the reflective antistatic performance can be further improved by using a three-layer structure. In the case of a two-layer structure, since the conductive layer is doped with an insulating organic dye, the conductivity of this layer is deteriorated, and the antistatic performance is reduced.

With a three-layer structure, the roles of wavelength selective absorption performance, antistatic performance, and antireflection performance can be shared, and both can be achieved without impairing the respective performances. In particular, if metal-based conductive particles are used for the conductive layer, the surface resistance can be significantly reduced, and a surface treatment film that can cope with the problem of leakage electromagnetic waves can be obtained.

Hereinafter, the present invention will be described specifically with reference to examples.

Example 1 2.0 parts by weight of silica (SiO ₂ ), 0.2 parts by weight of quinacridone (QN), 0.12 parts by weight of phthalocyanine green (PcG), 0.07 parts by weight of disazo yellow (Y) A solution containing 30 parts by weight of methanol, 50 parts by weight of water, 5 parts by weight of butanol, and 14.6 parts by weight of a polymer-based dispersant + hydrochloric acid + ketone-based solvent was mill-dispersed by a ball mill containing zirconia beads for 13 hours.

The solution thus obtained was spin-coated on the face plate of a cathode ray tube at 160 rpm, and then heat-treated at 160 ° C. for 20 minutes. The transmittance curve of this film is shown in FIG. In the figure, reference numeral 1 denotes a transmittance curve of the film of this example.

At 578 nm, an absorption peak based on quinacridone, an absorption peak based on a phthalocyanine dye near 650 nm, and an absorption based on a disazo yellow dye appear at 380 to 490 nm. Luminous transmittance of the film 1 is 69.95%, and L, a *, b * representing color
Are L = 86093, a * = 0.43, b * = − 3.
24, which was an achromatic color.

The BCP value (Brightness Contorast Performance: BCP: BCP = ΔB / √ΔRf, where BCP is the rate of decrease in reflected luminance and ΔB is the rate of decrease in luminance) as an index of contrast is 1. .08
And very high values.

A conventional three-color organic dye film (red dye rhodamine, blue phosphor B50P, yellow phosphor DY50) prepared as a comparative object has L = 87.08, a *.
= 4.50, b * =-3.50, and the color was relatively good, but the BCP value was 1.04 and the contrast was poor.

Further, when the strength of the film was examined by an eraser test (load of 1 kg), the film of the present invention survived the sliding test 150 to 200 times, whereas the conventional three-component film was 10 times.
The film strength was as low as about 0 times.

Light resistance (365 nm, 4 mW / cm)
² , tracking the change in transmittance ΔT). After 100 hours, the dye-based film had a ΔT change of 50% or more, while the film of the present invention had a ΔT of about 2%, indicating that the light resistance was extremely good. I understood.

Example 2 The conductive fine particles ATO (Sn
O ₂ (Sb)) 1.28 parts by weight, silica (SiO ₂ ) 1.0 parts by weight, quinacridone (QN) 0.2 parts by weight, phthalocyanine green (PcG) 0.12 parts by weight, disazo yellow (Y) 0 A solution containing 0.07 parts by weight, 30 parts by weight of methanol, 50 parts by weight of water, 5 parts by weight of butanol, and 13 parts by weight of the balance (polymeric dispersant, hydrochloric acid, ketone solvent) was added to a ball mill containing zirconia beads. Mill dispersed for hours.

This solution was spin-coated at 160 rpm on the surface of a cathode ray tube face plate, and then heat-treated at 160 ° C. for 20 minutes. On top of this film is a SiO ₂ sol 1.0
0% by weight was spin-coated at 160 rpm on a CRT faceplate by the same method,
Heat treatment was performed at 0 ° C. for 20 minutes. FIG. 2 shows a cross-sectional structure of the surface treatment film thus manufactured. In the figure, 3 is an organic dye layer, 4 is an ATO particle, and 5 is a low refractive index SiO ₂ layer.

Since the organic dye layer 3 containing the ATO particles 4 has a high refractive index, when such a film is laminated, antireflection performance is exhibited by the interference effect of light. Also, ATO particles 4
Is conductive, and thus exhibits antistatic performance. The surface resistance of this film was 8 × 10 ⁹ Ω / □ and the surface reflection was 1.5%.

The transmittance performance and surface color of the film were L = 7.
The color was relatively good at 9.84, a * = 2.26, b * =-1.74, the BCP value was as high as 1.09, and the contrast was also good. This film had an antireflection function and an antistatic function, and also had a good wavelength selective absorption function.

As conductive fine particles, instead of ATO, IT
When O (In ₂ O ₃ (Sn)) is used, the surface resistance is 5 × 10 ⁶
Ω / □ and surface reflection of 1.2% were obtained.

Example 3 2.0 parts by weight of silica (SiO ₂ ), 0.2 parts by weight of quinacridone (QN), 0.12 parts by weight of phthalocyanine green (PcG), 0.07 parts by weight of disazo yellow (Y) A solution containing 30 parts by weight of methanol, 50 parts by weight of water, 5 parts by weight of butanol, and 13 parts by weight of the remainder (polymeric dispersant, hydrochloric acid, ketone solvent) was mill-dispersed by a ball mill containing zirconia beads for 13 hours.

This solution was spin-coated on the face plate of a cathode ray tube at 160 rpm, and then heat-treated at 160 ° C. for 20 minutes. 1.00% by weight of an Ag ultrafine particle dispersion sol was spin-coated on the upper surface of this film at 160 rpm on a CRT faceplate surface by the same method,
Next, 0.90% by weight of SiO ₂ sol was applied to the upper layer of this film on the face plate of the cathode ray tube by the same method.
Spin coated at 0 rpm and then heat treated at 160 ° C. for 20 minutes.

FIG. 3 shows a cross-sectional structure of this film. In the figure, 6
Denotes an organic dye layer, 7 denotes a metal (Ag) conductive layer, and 8 denotes a low refractive index SiO ₂ layer.

The surface resistance of this film was 8 × 10 ² Ω / □,
The surface reflection was 0.89%. The transmittance curve of this membrane is shown as curve 2 in FIG. The lowest transmittance is 40% (575
nm).

Since the surface resistance of this film is very low, it is possible to remove leakage electromagnetic waves around the cathode ray tube only by this film. The transmittance performance and surface color of the film were L = 67.08,
The color was relatively good with a * = 2.69 and b * = − 3.29, the BCP value was high at 1.10, and the contrast was also good. Regarding the metal-based antistatic film, not only Ag but also a film of Au, Pt, Pd or the like, or a film of these alloys, a surface treatment film having similar performance was obtained.

Example 4 In this example, an azomethine pigment was used in place of the yellow pigment disazo yellow of Example 1.

2.0 parts by weight of silica (SiO ₂ ), 0.2 parts by weight of quinacridone (QN), 0.12 parts by weight of phthalocyanine green (PcG), azomethine yellow (Y ₂ )
A solution containing 0.075 parts by weight, 30 parts by weight of methanol, 50 parts by weight of water, 5 parts by weight of butanol, and 14.55 parts by weight of a polymer-based dispersant + hydrochloric acid + ketone-based solvent was subjected to a ball mill containing zirconia beads. Mill dispersed for hours.

The solution thus obtained was spin-coated on the face plate of a cathode ray tube at 160 rpm, and then heat-treated at 160 ° C. for 20 minutes. The transmittance curve of this film was almost the same as the transmittance curve obtained in Example 1 of FIG.

The luminous transmittance of this film is 69.70%, and L =
86090, a * = 0.41 and b * = − 3.25, which were achromatic colors. Also, B, which is an index of contrast,
The CP value showed a very high value of 1.09.

Further, both the strength and the light fastness of the film were equivalent to those obtained by blending the disazo yellow of Example 1.

As described in Examples 2 and 3,
A conductive film was obtained by adding the conductive particles ATO and ITO.

When an SiO ₂ film was laminated on this upper layer, an antireflection effect was obtained, and the conductivity and antireflection performance of the film were similar to those of the film using disazo yellow.

[0063]

According to the present invention, the wavelength selective absorption film of the display device uses three kinds of organic dyes, red, green, and yellow, and a quinacridone dye as the red dye. By using a phthalocyanine green dye as the complementary green color and disazo yellow or azomethine yellow as the yellow color, it was possible to efficiently achieve the achromatic coloration of the surface color of the film. Therefore, a wavelength selective absorption film having good color purity and good contrast characteristics can be obtained.

Further, by laminating or containing the conductive fine particle layer, an antistatic function and an antireflection function can be imparted.

[Brief description of the drawings]

FIG. 1 is a graph of a transmittance curve of a wavelength selective absorption film.

FIG. 2 is a schematic cross-sectional view of a reflection / prevention wavelength selective absorption film manufactured in this example.

FIG. 3 is a schematic cross-sectional view of a reflection / prevention / wavelength selective absorption film having a three-layer structure manufactured in this example.

[Explanation of symbols]

1... Transmittance curve of the film of the present embodiment, 2.
Transmittance curve of the film formed by laminating a low refractive index film, 3 ... organic dye layer, 4 ... ATO particles, 5 ... low refractive index SiO ₂ layer, 6 ... organic dye layer, 7 ... metallic (Ag) conductive layer, 8 ... Low refractive index S
iO ₂ layer.

 ──────────────────────────────────────────────────続 き Continuing from the front page (72) Inventor Daigoro Kamoto 7-1-1, Omika-cho, Hitachi City, Ibaraki Prefecture Inside the Hitachi Research Laboratory, Hitachi, Ltd. No. 1-1, Hitachi, Ltd.Hitachi, Ltd.Hitachi Research Laboratories (72) Inventor Norikazu Uchiyama 3300 Hayano, Mobara-shi, Chiba Pref. (72) Inventor Toshio Tojo 3681 Hayano, Mobara-shi, Chiba F-term (reference) in Hitachi Device Engineering Co., Ltd. 2H048 CA04 CA14 CA19 CA24 5C032 AA02 DD02 DE01 DE03 DF03 DG01 DG02 DG04 5G435 AA01 AA02 AA04 AA16 FF02 GG11 GG32 HH03 HH12 KK07

Claims (9)

[Claims] 1. A surface treatment film for a display device comprising an organic dye selected from a quinacridone dye, a disazo yellow dye, an azomethine dye, and a phthalocyanine dye. 2. A surface treatment film for a display device comprising at least three kinds of organic dyes of a quinacridone dye, a disazo yellow dye (or an azomethine dye), and a phthalocyanine dye. 3. A surface treatment film formed on a display substrate of a display device, wherein the surface treatment film contains an organic dye selected from a quinacridone dye, a disazo yellow dye, an azomethine dye, and a phthalocyanine dye. A display device characterized by the above-mentioned. 4. A surface treatment film formed on a display substrate of a display device, wherein the surface treatment film contains at least three kinds of quinacridone dyes, disazo yellow dyes (or azomethine dyes), and phthalocyanine dyes. A display device comprising: an organic dye. 5. The display device according to claim 3, wherein the surface treatment film includes conductive fine particles. 6. The method according to claim 1, wherein said conductive fine particles are made of Antimo Tin Tin Ox.
6. The display device according to claim 5, wherein the display device is at least one selected from ide, Indium TinOxide, Ag, Pd, Pt, and Au. 7. The display device according to claim 3, wherein the surface treatment film has a low refractive index film having a lower refractive index than the surface treatment film as an upper layer. 8. The display device according to claim 7, wherein the low refractive index film is made of SiO ₂ . 9. The display device according to claim 3, wherein the surface treatment film has a conductive film as an upper layer.