JP2002146240A - Surface treating film-forming solution, its manufacturing method, surface treating film and display equipment - Google Patents

Abstract

PROBLEM TO BE SOLVED: To prepare a surface treating film-forming solution capable of forming a surface treating film having high film strength and transparency, and the film being suitable for high contrast and highly fine display, and to provide a manufacturing method of the solution, a surface treating film therefrom and a display equipment. SOLUTION: The surface treating film-forming solution is manufactured by comprising an organic dyestuff and an inorganic binder, or in addition to these, further a conductive fine particle, and the organic dyestuff being selected from among a quinacridone based dyestuff, an azomethine based dyestuff and a phthalocyanine based dyestuff, and comprising a secondary particle which is formed by agglomerating plural primary particles having a particle diameter of <=0.2 μm. The surface treating film 15 is formed by coating the surface treating film-forming solution by a spin coating method on the front face of a panel 8 of a plane type cathode ray tube.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel surface treatment film forming solution, a surface treatment film thereof, and a display device. The present invention relates to a surface treatment film and a display device.

[0002]

2. Description of the Related Art A cathode ray tube is a typical display device. With the increasing image quality of television,
CRTs in which a wavelength selective absorption film (optical filter) is formed on the front surface of a face plate have been manufactured.

The filter selectively absorbs external light of a specific wavelength by this filter, thereby preventing reflection of the external light and absorbing 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 filter is an organic dye / glass gel composite film produced by using a sol-gel method (JP-A-1-320742, JP-A-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 around 560-590 nm, which is the highest in human luminous sensitivity, and efficiently absorb the sidebands of green and red light emitters to improve color purity and improve contrast. Because it is effective to give. As a solution for forming these films, there are a solution in which a dye is dissolved in a solution and a solution in which pigment-based particles are dispersed.

Japanese Patent Application Laid-Open No. 7-503742 discloses a sol-bound colorant cluster and a method for producing the same, but does not disclose miniaturization of an organic pigment at all. or,
JP-A-57-30765 discloses that an organic pigment is wet-milled with a glass bead mill having a diameter of 4.0 to 5.0 mm. However, this publication does not disclose forming a film having higher transparency.

[0006]

Although these dye-based rhodamine dyes and pigment-based dyes are very effective in improving contrast, they have the following drawbacks. That is, in the wavelength selective absorption film as described above, since the dye having an absorption at 560-590 nm strongly develops a purple-red color, the panel surface of the display device is colored with a strong unique color, and the commercial value is reduced. I will. Therefore, it is necessary to dope a complementary color dye to cancel this color. Usually, there are few dyes having an ideal complementary color relationship, and it is necessary to dope a large number of various dyes in order to produce the complementary color.

In order to form a film containing these plural kinds of dyes and pigments, it is necessary to prepare a uniformly dissolved solution or a uniformly dispersed solution in a film forming solution. In these solutions, it is necessary to select the type of dye or pigment to be used in order to increase the contrast of the film and make the film achromatic. In addition, it is necessary to prepare a film forming solution for preparing this film. When the organic dye to be used is a dye, it is easy to mix a plurality of types because of high solubility in a solution. However, in the case of a dye, there is a disadvantage that light resistance is extremely poor. On the other hand, in the case of pigments, the light resistance is very excellent. However, it is necessary to make the particle size of the organic pigment used extremely small in order to ensure the transparency of the film. However, there has been a limit to the atomization of these organic pigments in the past. In addition, there is a problem that dispersion is difficult when the particles are atomized. In addition, an inorganic binder is required to adhere these pigments to the film, but if the inorganic binder is contained in the dispersion of the pigment, dispersion becomes worse, and when the film is formed, haze increases and transparency increases. There was a problem that it was difficult to secure the space.

SUMMARY OF THE INVENTION An object of the present invention is to provide a surface treatment film forming solution for forming a surface treatment film which has high film strength and transparency and is suitable for high contrast and high definition display, a method for producing the same, a surface treatment film therefor, and display. It is to provide a device. Also,
Another object of the present invention is to provide a surface treatment film forming solution for forming a conductive film, a method for producing the same, a surface treatment film thereof, and a display device.

[0009]

The present invention provides an organic dye and an inorganic binder selected from quinacridone dyes, azomethine dyes and phthalocyanine dyes, and further contains conductive fine particles, wherein the organic dye is The surface treatment film forming solution is characterized by comprising secondary particles formed by aggregating a plurality of primary particles, wherein the primary particles have a particle size of 0.2 μm or less, preferably 0.1 μm or less.

The present invention also provides an organic dye and an inorganic binder selected from a quinacridone dye, an azomethine dye and a phthalocyanine dye, and further contains conductive fine particles, and the organic dye has a particle size of 0. 0.2 μm or less, preferably 0.1 μm or less. The thickness of the film is 0.1-1.0
μm, preferably 0.2 to 0.6 μm.

Further, the present invention relates to a display device having a surface treatment film on a substrate surface as a screen, wherein the surface treatment film comprises an organic dye and an inorganic dye selected from a quinacridone dye, an azomethine dye and a phthalocyanine dye. It is characterized in that it contains a binder and further contains conductive fine particles, and the particle size of the organic dye is 0.2 μm or less, preferably 0.1 μm or less.

That is, the particle size of the organic dye is set to 0.2 μm or less by obtaining finer particles by finely dividing the organic dye using a bead mill made of ceramics. It is more preferably 0.1 μm or less. Therefore, in the film in which the divided primary particles are formed, the size of the divided particle size is the particle size of the organic dye. Then, when forming this film, it has an inorganic binder and a solvent as a dispersion medium, and is performed using a mixed solution thereof, so that in the solution, the organic dye exists as secondary particles larger than the primary particles due to aggregation of the primary particles. . The size of the secondary particles can be selected according to the size of the primary particles of the organic dye, the size of the inorganic binder, the composition of the dispersion medium, and the like.

The pigment component contained in the surface-treated film contains a quinacridone dye, an azomethine dye and a phthalocyanine dye so as to improve the color purity without hindering the emission spectrum of the illuminant, The contrast can be increased. In addition, the combination of the addition of the three color dyes makes the film achromatic,
Coloring unique to organic dyes on the panel surface can be avoided.

The pigment particles contained in the surface treatment film are as follows:
Particles having a particle size of not more than 0.2 μm and having a particle size of not less than 0.2 μm are not suitable as a pigment for a wavelength selective absorption film because the haze in the film is increased and the transparency of the film is reduced. In particular, 0.1 μm
The following is preferred.

Further, an inorganic binder is required to deposit the organic pigment on the substrate. However, SiO ₂ sol is most suitable for improving the film strength and cost, and has a low molecular weight.
2,000 to 15,000 are most suitable because they can be added without destroying the pigment dispersion. In the case of a SiO ₂ sol having a molecular weight of 2,000 or less, since the interaction between the pigment particle surface and the SiO ₂ sol is large, the dispersant on the pigment particle surface is detached from the surface, the dispersion is disturbed, and the pigment particles precipitate or become very Due to the growth of large secondary particles, transparency of the film is not ensured during film formation. When the molecular weight of the SiO ₂ sol is 15,000 or more, the dispersibility can be ensured, but the adhesion to the glass surface as a base material during film formation becomes poor, and the strength of the film becomes insufficient.

Further, by adding conductive particles to these solutions, it is possible to impart conductivity to the surface-treated film produced using this solution, so that new added value can be given. . That is, an antistatic effect and an effect of removing leakage electromagnetic waves can be provided. As the conductive particles that can be contained in the solution, ATO, ITO, Ag,
Pd, Pt, Au and the like are preferred. By preparing a solution using ultrafine particles that do not affect the transparency of the film, the transparency and conductivity of the film can be ensured.

According to the present invention, a mixed solution containing an organic dye and a dispersion medium of the organic dye is loaded into a bead mill together with a bead, and the bead mill is rotated at a high speed so that the particle diameter of the organic dye is 0.2 μm or less. , And preferably a pulverization treatment so as to have a concentration of 0.1 or less.

Further, the present invention provides a method of mixing the above-mentioned pulverized mixed solution and an inorganic binder by ultrasonic vibration, and further adding conductive fine particles to these and mixing them by ultrasonic vibration. A method for producing a solution for forming a surface treatment film, characterized in that:

[0019]

BEST MODE FOR CARRYING OUT THE INVENTION

Example 1 A solution of quinacridone (QN), phthalocyanine green (PcG), and azomethine yellow (Y) in 10 wt% each of isopropyl alcohol (IPA) was prepared. The solution was passed through a horizontal bead mill (ZrO ₂ vessel, using ZrO ₂ beads having a diameter of 0.3 mm) at a rotation speed of 2000 rpm for 60 minutes to make the pigment fine. When the primary particles of this solution were observed with a transmission electron microscope, the particle size was about 0.05 μm for quinacridone (QN) and phthalocyanine green (Pc
G) was about 0.02 μm, and azomethine yellow (Y) was about 0.1 μm. And these primary particles are in solution
It is formed as secondary particles formed by aggregating a plurality of particles into one particle.

This ultrafine pigment solution was mixed in the following concentration and method. First, each of the finely divided pigments, quinacridone (QN) 0.2 wt%, phthalocyanine green (PcG) 0.12 wt%, azomethine yellow (Y) 0.07 wt%
A), and a polymer dispersant is added to the solution so as to have a concentration of 20% of the solid content of the pigment. Similarly, a vertical bead mill (ZrO
₂ vessels, 0.3φZrO ₂ beads used), 200 rpm
The mixture was stirred and mixed at 0 rpm for 30 minutes.

Next, an SiO ₂ sol (molecular weight: 4000) containing ethanol as a main solvent was added to the above IPA solution so as to be 2.0 wt%, and the mixed solution was ultrasonically dispersed for 20 minutes. Thus, a solution for forming a surface treatment film was prepared.

Using this solution, a film was formed on a glass substrate by spin coating, and the optical characteristics of the film formed by heat treatment at 160 ° C. were evaluated. The luminous transmittance was 69.95%, and the L, The a * and b * values were L = 86093, a * = 0.43, and b * =-3.24, and were achromatic colors. The haze value of the film was as low as 0.3%, and the film was highly transparent. The BCP (Brightness Contorast Performannce) value, which is an index of contrast,
When the reflection luminance reduction rate ΔRf and the luminance reduction rate are ΔB,
BCP = ΔB / √ΔRf), a very high value of 1.08. The pencil hardness of the film was as high as 9H. The mechanical pencil test also withstands a scratch test with a load of 2 kg.

According to the present embodiment, in the solution for forming the wavelength selective absorption film of the display device, the type of pigment particles to be contained, the ultra-fine atomization, and the molecular weight of the SiO ₂ sol are optimized to achieve the optical performance. A surface-treated film having good characteristics and film strength was obtained. In addition, the display device having the surface treatment film has improved contrast and high definition.

In a similar manner, the molecular weight of the SiO ₂ sol is increased to 2000 and
Films were prepared using 15,000 films, and all had good film characteristics. On the other hand, when the molecular weight was 850 or 19,000, the dispersion of the pigment was broken, the transparency of the film was insufficient, or the strength of the film was low, and the film was poor in practical use. Further, a film obtained from a solution prepared using a pigment particle diameter of 0.15 to 0.2 μm has a haze value of 8.5% for the film.
Although the film was rather high and the particle size exceeded 0.2 μm, the haze value of the film was much higher and the film had low transparency.

[0025]

Example 2 A mixed solution was prepared by adding 1% by weight of ITO (In ₂ O ₃ (Sn)) ultrafine particles, which are conductive particles, to the whole solution in the film forming solution obtained in Example 1. Then, using this solution, a film having a thickness of about 0.2 μm was formed by spin coating in the same manner as in Example 1. Its surface resistance is 8x10 ⁶
A film having an antistatic performance as low as Ω / □ was obtained. Further, in the solution for forming the wavelength selective absorption film of the display device, the type of pigment particles to be contained, ultra-fine atomization, and Si
By optimizing the molecular weight of the O ₂ sol, a surface-treated film having good optical properties and film strength was obtained.

Similarly, ATO (SnO ₂ (Sb)), Ag, Pd,
A similar film having a low surface resistance was obtained by using a colloid-dispersed ultrafine particle such as Pt or Au, and a film having conductivity was obtained.

In the same manner, the molecular weight of the SiO ₂ sol was increased to 2000 and
Films were prepared using 15,000 films, and all had good film characteristics. On the other hand, when the molecular weight was 850 or 19,000, the dispersion of the pigment was broken, the transparency of the film was insufficient, or the strength of the film was low, and the film was poor in practical use. Further, a film obtained from a solution prepared using a pigment particle diameter of 0.15 to 0.2 μm has a haze value of 8.5% for the film.
Although the film was rather high and the particle size exceeded 0.2 μm, the haze value of the film was much higher and the film had low transparency.

[0028]

Embodiment 3 FIG. 1 shows a half of a cross-sectional view of a flat type cathode-ray tube according to the present invention. This embodiment is similar to the first embodiment.
Using each of the solutions obtained in Steps 2 and 3, a surface-treated 15 film produced by applying the solution by spin coating and heat-treating it at a predetermined temperature was formed as a wavelength selective absorption film on the front surface of the panel 8 of the flat-type CRT. Things. As shown in the figure, an electron gun 1, an antenna getter 2, an interior graphite layer 3, an inner shield 4, a funnel 5, a frame 6, a box 7, a panel 8, a green 9, a blue 10, and a red phosphor 13, It has a black matrix AX 12 and an Al film 14. FIG. 2 is an enlarged view of A in FIG.

According to the above-described embodiment, the wavelength selective absorption film of the CRT uses a specific pigment and particles obtained by ultrafine atomization thereof, and has a specific molecular weight of the SiO ₂ sol.
A surface treatment film 15 having good optical characteristics and film strength and further having antistatic properties can be obtained. As a result, the display device has an improved contrast and a high-definition display device.

[0030]

As described above, according to the present invention, in a solution for forming a wavelength selective absorption film of a display device, a specific kind of pigment particles to be contained and ultrafine atomization thereof are provided.
By optimizing the molecular weight of SiO ₂ sol, optical properties,
A surface-treated film having good film strength is obtained. In addition, the display device having the surface treatment film has improved contrast,
High definition can be obtained.

[Brief description of the drawings]

FIG. 1 is a partial cross-sectional view of a cathode ray tube according to the present invention.

FIG. 2 is an enlarged view of A in FIG. 1;

[Explanation of symbols]

1. Electron gun, 2. Antenna getter, 3. Interior graphite layer,
4: inner shield, 5: funnel, 6: frame, 7: mask, 8: panel, 9: green, 10: blue, 11
... red, 13 ... phosphor, 12 ... black mat Aix,
14 ... Al, 15 ... Surface treated film.

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Junji Sakai 7-1-1, Omika-cho, Hitachi City, Ibaraki Prefecture Inside the Hitachi Research Laboratory, Hitachi, Ltd. (72) Inventor Daigoro Kamoto Omika-cho, Hitachi City, Ibaraki Prefecture Hitachi 1-1, Hitachi Ltd. (72) Inventor Tadayoshi Fujieda 4-3-1-1, Higashicho, Hitachi City, Ibaraki Prefecture Hitachi Chemical Co., Ltd., Yamazaki Plant (72) Inventor Yoshiyuki Horibe Ibaraki Prefecture Hitachi Chemical Industry Co., Ltd. Yamazaki Office, 4-3-1-1, Higashicho, Hitachi City (72) Inventor Hiroshi Yamazaki 4-1-1, Higashicho, Hitachi City, Ibaraki Prefecture Hitachi Chemical Co., Ltd. Yamazaki Office F-term (reference) 4G059 AA07 AB19 AC08 AC12 FA01 FA27 FA28 FB09 4J038 AA011 HA441 JA34 JB27 KA08 KA20 LA07 NA20 5C028 AA04 AA07 AA10 5C032 AA02 DD02 DE01 DE03 DG01 DG02

Claims (14)

[Claims] 1. An organic dye comprising an organic dye and an inorganic binder, wherein the organic dye comprises secondary particles formed by aggregating a plurality of primary particles, and the primary particles have a particle size of 0.2 μm or less. Characteristic surface treatment film forming solution. 2. An organic dye comprising an organic dye, an inorganic binder and conductive fine particles, wherein the organic dye comprises secondary particles formed by aggregating a plurality of primary particles, and the primary particles have a particle size of 0.2.
A solution for forming a surface treatment film, which is not more than μm. 3. The surface treatment film forming solution according to claim 1, wherein the organic dye is selected from a quinacridone dye, an azomethine dye and a phthalocyanine dye. 4. The solution for forming a surface treatment film according to claim 1, wherein the inorganic binder comprises a silica sol having an average molecular weight of 2,000 to 15,000. 5. The surface treatment film forming solution according to claim 2, wherein the conductive fine particles are at least one of ATO, ITO, Ag, Pd, Pt and Au. 6. A mixed solution containing an organic dye and a dispersion medium of the organic dye is loaded together with beads into a bead mill, and the bead mill is rotated at a high speed so that the particle size of the organic dye is 0.2%.
A method for producing a solution for forming a surface treatment film, wherein the solution is pulverized so as to have a particle size of not more than μm. 7. A mixed solution containing an organic dye and a dispersion medium of the organic dye is loaded together with beads into a bead mill, the bead mill is rotated at a high speed, the organic dye is pulverized, and the pulverized mixed solution is mixed. And mixing the inorganic binder with an inorganic binder by ultrasonic vibration. 8. A mixed solution containing an organic dye and a dispersion medium of the organic dye is loaded into a bead mill together with beads, the bead mill is rotated at a high speed, the organic dye is pulverized, and the pulverized mixed solution is mixed. A method for producing a solution for forming a surface treatment film, comprising mixing an inorganic binder and conductive fine particles by ultrasonic vibration. 9. A surface treatment film for a display device, comprising an organic dye and an inorganic binder, wherein the organic dye has a particle size of 0.2 μm or less. 10. A surface treatment film for a display device, comprising an organic dye, an inorganic binder and conductive fine particles, wherein the organic dye has a particle size of 0.2 μm or less. 11. A surface-treated film according to claim 9, wherein said organic dye is selected from a quinacridone dye, an azomethine dye and a phthalocyanine dye. 12. The surface treatment film for a display device according to claim 10, wherein the conductive fine particles are at least one of ATO, ITO, Ag, Pd, Pt, and Au. 13. A display device having a surface treatment film on the surface of a substrate serving as a screen, wherein said surface treatment film contains an organic dye and an inorganic binder, and has a particle diameter of 0.2 μm.
m or less. 14. A display device having a surface treatment film on the surface of a substrate serving as a screen, wherein the surface treatment film comprises an organic dye,
A display device comprising an inorganic binder and conductive fine particles, wherein the particle size of the organic dye is 0.2 μm or less.