KR20010039727A - Selectively light-absorptive material, coating composition containing the same and filter manufactured using the coating composition - Google Patents

Abstract

PURPOSE: A light selective absorption material for color display panel, a coating material which includes the same, and a filter manufactured by the coating material are provided to improve the color purity and the contrast by shielding reflection light of display panel and emission light corresponding to the middle color of ternary color. CONSTITUTION: R1, R2, R3, R4, R5, R6, R7,and R8 is displaced with one to three of ring compound that is selected independently on each other from group that is composed of hydrogen, nondisplaced phenyl, alkyl group of carbon number 1 to carbon number 8, alkoc group of carbon number 1 to carbon number 8, nitro group, halogen atom, hallide, alkylamino group carbon number 1 to carbon number 8, aminoalkyl group carbon number 1 to carbon number 8, and phenyl group having displacement group selected out of siano group, or that is selected from aromatic ring compound group of chemical equation 2a-g melting and adhering two displacement base to be adjacent each other and to be selected out of displacement base of R1,R2,R3,R4,R5,R6,R7,and R8. The rest of displacement base is selected from independently on each other from group that is composed of hydrogen, alkyl group of carbon number 1 to carbon number 8, alkoc group of carbon number 1 to carbon number 8, allyl group, halogen atom, hallide, siano group, nitro group.

Description

Selective light-absorptive material, coating composition containing the same and filter manufactured using the coating composition}

The present invention relates to a light selective light absorber for a color display device that can improve color purity and contrast of a color display device, a coating agent comprising the same, and a filter made of the coating material.

Color display devices are widely used in products such as televisions, computers, and video game machines. Cathode ray tube (CRT), which most of them employ, is a display device using a vacuum tube, and uses the principle that electron kinetic energy of electron gun is converted into light energy by colliding with light emitting body of screen. In this case, since the wavelength range of the generated light is mainly visible light, it is used in a display device such as a general television or a computer monitor. The CRT can represent various different colors while using only the three primary colors of red (R), green (G), and blue (B).

However, as shown in FIGS. 1 and 2, the emission spectrum emitted from the color display device has a problem that red, green, and blue ambient light are emitted in a large amount depending on the characteristics of the phosphor, thereby lowering color purity or limiting the implementation range of colors. have. 1 shows a typical emission spectrum of a CRT, where the green emission spectrum is very wide and tends to be slightly yellowish. Therefore, in the CRT, red and blue light emission have sufficiently achieved color purity, but in the case of green, a color biased to yellow is expressed.

In addition, the surface reflection of the ambient light in the display device tires the viewer's eyes, and there is a problem that the contrast of the display device is not realized in the bright external light.

Reflected light appearing in the display device is the addition of the external light reflected from the glass surface used as the screen and the light reflected from the luminous material inside the screen has been studied in the art to reduce this. For example, US Pat. No. 4,989,953 discloses an attempt to reduce reflected light. However, this patent only reduces the glare of monochrome monitors.

One attempt to reduce reflected light for a color display device is by using a neutral density (ND) filter or an attenuator. The ND filter is a method of improving contrast by transmitting only a portion of light regardless of wavelength, and can be formed by making a colloidal suspension of silver or graphite grains on an appropriate medium and attaching it to a monitor surface. Although widely used in the production of, there is a problem that reduces the brightness of the screen.

Another method to reduce the reflected light of the color display is to combine an ND filter and an antireflection coating, which reduces the reflection of external light from the illuminator and the reflected light on the display surface. The disadvantage is that it does not reduce the luminance and improve the color purity.

As a method of minimizing luminance reduction while simultaneously improving color purity and contrast, a method of transmitting light of three primary colors emitted from a display device and blocking light of the remaining areas has been proposed. Unlike the ND filter, this method allows the light emitted from the display device to be sufficiently transmitted while sufficiently reducing external light, thereby minimizing the decrease in luminance compared to the effect of increasing contrast, and simultaneously blocking the display of colors other than the three primary colors emitted from the display device. There is an advantage that the implementation of the color can be greatly extended by improving the color purity of the device.

As such examples, US Pat. Nos. 4,288,250, 4,520,115, and 4,245,242 have applied colored glass containing metal oxides, including neodium oxide, as the front material for cathode ray tubes or used as filters. This method transmits the light emitted from the display device and restricts the transmission of light between the three primary colors, which are other areas, to prevent the display device from lowering the brightness of the display device and to reduce the reflectance of the external light and improve the color purity. Not only is the manufacturing process of the colored glass complicated, but the manufacturing cost is high and it is disadvantageous.

In addition, Japanese Patent Publication No. 44-5091, Japanese Patent Publication No. 59-217705, Hei 4-106150, Hei 6-88007 and Hei 10-120860 are colored plastics in which neodium oxide or organic neodium compound is dispersed or dissolved in plastic. In order to improve the characteristics of the color display device using the, they had a disadvantage in that the characteristics gradually deteriorated due to the difficulty of dispersion or dissolution and yellowing of the plastic material.

In addition, Japanese Patent Laid-Open No. Hei 2-210480 and U.S. Patent No. 5,200,667 propose a color display device filter mainly composed of a pigment and a plastic resin material. However, the dye has a broad light absorption width and a small light selectivity to improve color purity. Although the US Patent No. 5,834,122 proposes a band pass filter for a display device having improved light selectivity by combining a color-selective dye, the absorbing dye between green and red or between blue and green is durable. There is a problem that it is difficult to be practical due to this lack.

Meanwhile, PDP (plasma display panel), which is increasingly used as another type of display device, encapsulates and seals an inert gas such as helium, neon, argon, xenon or a mixture thereof in a partition surrounded by glass or the like. After this, a high voltage is applied to ionize the gas to form a plasma, and the ultraviolet rays emitted therein excite the phosphor to emit light. PDPs can be secured with a wide viewing angle, are easier to be enlarged than other display devices, and are considered to have the most suitable characteristics as high-quality televisions of the PDP in the future as thin-type light emitting display devices.

However, plasma display devices are currently being developed by many display device manufacturers, but have a disadvantage in that the luminance is low, the surface reflection of the phosphor is high, and the color purity does not reach the cathode ray tube due to the orange light emitted from the encapsulated gas helium.

FIG. 2 shows the emission spectrum of the plasma display panel. The emission spectrum of green has a tendency toward the shorter wavelength, and the blue tendency toward the longer wavelength when compared with the emission spectrum of the CRT of FIG. In addition, the red color has a strong emission peak near 590 nm, which is due to the inclusion gas neon. Therefore, it is difficult to implement red, and blue and somewhat greenish colors can be seen.

Considering the various uses and potential uses of CRTs and PDPs, the development of devices or mechanisms that reduce reflection on the display surface and improve overall color purity and contrast without serious loss of screen brightness and clarity is urgently needed.

Therefore, the present inventors have solved the above problems and continue to study to improve the color purity and contrast by absorbing the reflected light of the color display device, between blue and ultraviolet, between blue and green, between green and red and between red and ultraviolet The present invention was found to be able to improve the color purity and contrast of a color display device by applying a light absorber capable of absorbing light to a color display filter.

Accordingly, an object of the present invention is to provide a light selective light absorber for a color display device which can improve the color purity and contrast of the color display device with the reflected light of the color display device and the emission light corresponding to the intermediate color of the three primary colors.

Another object of the present invention is to provide a photoselective absorbent coating comprising the photoselective light absorber.

Another technical problem to be achieved by the present invention is to provide a light selective absorbent filter comprising the light selective light absorber.

1 shows a typical emission spectrum of a cathode ray tube,

2 shows the emission spectrum of the plasma display panel,

Figure 3 shows the absorption spectrum of the octaphenyl tetraaza porphyrin absorbent prepared in Synthesis Example 1 of the present invention,

Figure 4 shows the absorption spectrum of the tribenzyl tetraaza porphyrin absorbent prepared in Synthesis Example 2 of the present invention,

5 shows an absorption spectrum of the ruthenium octaphenyltetraazapophyrin absorber prepared in Synthesis Example 3 of the present invention,

Figure 6 shows the absorption spectrum of the copper tetramethyltetraazapopyrine light absorber prepared in Synthesis Example 4 of the present invention,

Figure 7 shows the absorption spectrum of the nickel tetrabutyl tetraaza porphyrin absorbent prepared in Synthesis Example 5 of the present invention,

FIG. 8 shows a comparison of transmission spectra before and after light exposure of the glass substrates colored with the light selective absorbent coating agents of Example 1 and Comparative Example 1 of the present invention;

9 shows color coordinates of three primary colors measured after mounting the glass substrates colored with the photoselective absorbent coating agents of Examples 2, 5, 8 and Comparative Example 2 of the present invention on a cathode ray tube,

FIG. 10 illustrates color coordinates of three primary colors measured after the glass substrates colored with the photoselective absorbent coating agents of Examples 2, 5, 8, and 2 of the present invention are mounted on a plasma display panel.

FIG. 11 shows the emission spectra of the plasma display panels before and after the glass substrates colored with the photoselective absorbent coating of Example 1 were mounted on the plasma display panel.

FIG. 12 shows the emission spectra of the plasma display panels before and after the glass substrates colored with the photoselective absorbent coating of Example 4 were mounted on the plasma display panel.

FIG. 13 shows the emission spectra of the plasma display panels before and after the glass substrates colored with the photoselective absorbent coating of Example 7 were mounted on the plasma display panel.

Fig. 14 shows the transmission spectra of the colored glass substrates obtained in Examples 10, 11 and Comparative Example 2 of the present invention.

In order to achieve the first technical problem, the present invention provides a photoselective light absorber for a color display device, comprising a tetraazapophyrin derivative of formula (1).

<Formula 1>

Wherein R1, R2, R3, R4, R5, R6, R7 and R8 are each independently hydrogen; Unsubstituted phenyl group; An alkyl group having 1 to 8 carbon atoms; An alkoxy group having 1 to 8 carbon atoms; Nitro group; Halogen atom; Halides; Cyano group; Alkylamino groups having 1 to 8 carbon atoms; Aminoalkyl groups having 1 to 8 carbon atoms; A phenyl group having a substituent selected from an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, a nitro group, a halogen atom, a halide, an alkylamino group having 1 to 8 carbon atoms, an aminoalkyl group having 1 to 8 carbon atoms, and a cyano group; A ring of 1-3 selected from the group of aromatic ring compounds of formula 2a-g, wherein two substituents adjacent to each other selected from the group or selected from the substituents of R1, R2, R3, R4, R5, R6, R7 and R8 are fused together Compound, and the remaining substituents are independently of each other hydrogen; An alkyl group having 1 to 8 carbon atoms; An alkoxy group having 1 to 8 carbon atoms; Allyl groups; Halogen atom; Halides; Cyano group; Nitro group; selected from the group consisting of.

<Formula 2a>

<Formula 2b>

<Formula 2c>

<Formula 2d>

<Formula 2e>

<Formula 2f>

Wherein R ', R ", R"', and R "" are independently of each other hydrogen; an alkyl group having 1 to 8 carbon atoms; An alkoxy group having 1 to 8 carbon atoms; Allyl group; Halogen atom; Cyano group; Nitro group; selected from the group consisting of

X is a halogen atom or an alkyl sulfonate having 1 to 8 carbon atoms,

Y is an alkyl group or allyl group having 1 to 8 carbon atoms,

The dotted line portion shows the portion bonded to the pyrrole group of the formula (1).

In addition, the first technical problem of the present invention is made by a photo-selective light absorber for a color display device comprising a tetraazapopyrine derivative of formula (3).

Wherein R1, R2, R3, R4, R5, R6, R7 and R8 are each independently hydrogen; Unsubstituted phenyl group; An alkyl group having 1 to 8 carbon atoms; An alkoxy group having 1 to 8 carbon atoms; Nitro group; Halogen atom; Halides; Cyano group; Alkylamino groups having 1 to 8 carbon atoms; Aminoalkyl groups having 1 to 8 carbon atoms; A phenyl group having a substituent selected from an alkoxy group having 1 to 8 carbon atoms, an alkyl group having 1 to 8 carbon atoms, a nitro group, a halogen atom, a halide, an alkylamino group having 1 to 8 carbon atoms, an aminoalkyl group having 1 to 8 carbon atoms, and a cyano group; A ring of 1-3 selected from the group of aromatic ring compounds of formula 2a-g, wherein two substituents adjacent to each other selected from the group or selected from the substituents of R1, R2, R3, R4, R5, R6, R7 and R8 are fused together Compound, and the remaining substituents are independently of each other hydrogen; An alkyl group having 1 to 8 carbon atoms; An alkoxy group having 1 to 8 carbon atoms; Allyl group; Halogen atom; Halides; Cyano group; Nitro group; selected from the group consisting of

M is a metal ion having a number of 2 oxides and complexes with a tetraazapophyrin ring or a metal ion having a number of oxides 2 and a complex with a tetraazapophylline ring and having a ligand capable of forming a coordinating bond with the metal ion. ,

<Formula 2a>

<Formula 2b>

<Formula 2c>

<Formula 2d>

<Formula 2e>

<Formula 2f>

Wherein R ', R ", R"', R "" are independently of each other hydrogen; An alkyl group having 1 to 8 carbon atoms; An alkoxy group having 1 to 8 carbon atoms; Allyl group; Halogen atom; Cyano group; Nitro group; selected from the group consisting of

X is a halogen atom or an alkyl sulfonate having 1 to 8 carbon atoms,

Y is an alkyl group or allyl group having 1 to 8 carbon atoms,

The dotted line portion shows the portion bonded to the pyrrole group of formula (3).

The second technical problem of the present invention is achieved by the photo-selective absorbent coating for color display device, characterized in that it comprises the above-described photo-selective light absorber, a plastic resin and an organic solvent.

A third technical problem of the present invention is achieved by a light selective absorbing filter for a color display device, comprising a light selective light absorber and a plastic resin.

In order to improve the color purity and contrast of the color display device, a light absorber capable of absorbing light is required between blue and ultraviolet rays, between blue and green, between green and red, and between red and infrared rays, especially between blue and green. Among red, green light absorbers having the following characteristics are most ideal.

(1) light absorber between blue and green

Maximum absorption wavelength: 460 to 500 nm, absorption band width: 20 to 30 nm

(2) light absorber between green and red

Maximum absorption wavelength: 550 to 600 nm, absorption band width: 50 to 70 nm

Tetraazapophyrin derivatives according to the present invention have a strong primary absorption band in the region of 530 to 620 nm, secondary absorption bands in the region of 620 to 700 nm, and an absorption band width of about 30 in the absorption region of these two regions. It is about 50nm, the tetraazapopyrine derivative of the formula (3) has a strong primary absorption band in the width of about 30 to 50nm, in the region of 570 to 610nm. As described above, the tetraazapophyrin derivatives of Chemical Formulas 1 and 3 according to the present invention absorb the light between red and green and have excellent light selective absorbance required by the optical filter for color display devices.

As described above, the tetraazapophyrin derivatives of Chemical Formulas 1 and 3 absorb light between red and green, thereby greatly improving color purity and contrast of the color display device. In addition, the tetraazapophyrin derivatives of the formulas (1) and (2) exhibit excellent heat resistance and light resistance, and thus can be used for a long time in image display devices such as cathode ray tubes and plasma display panels.

In R1, R2, R3, R4, R5, R6, R7 and R8 of the tetraazapophyrin derivative of the formula (1) or 3, specific examples of the alkyl group having 1 to 8 carbon atoms include methyl group, ethyl group, propyl group, butyl group, isobutyl Group, tert-butyl group, pentyl group, isopentyl group, neopentyl group, octyl group and the like, and specific examples of the alkoxy group having 1 to 8 carbon atoms include methoxy group, ethoxy group, propoxy group, butoxy group and pentoxy group And specific examples of halogen atoms include fluorine, chlorine, iodine or bromine, and specific examples of halides include chloromethyl group, bromomethyl group, iodomethyl group, fluoromethyl group, and the like. Specific examples include methylamino group, ethylamino group and the like, and specific examples of the aminoalkyl group having 1 to 8 carbon atoms include aminomethyl group and aminoethyl group.

In the tetraazapophyrin derivative, two substituents adjacent to each other selected from the substituents of R1, R2, R3, R4, R5, R6, R7, and R8 are fused to each other and represented by 2 to 3 ring compounds of Formula 2a. It is preferable that at least one of R ', R ", R"', and R "" in the ring compound of is an alkyl group having 2 to 6 carbon atoms or an alkoxy group having 2 to 6 carbon atoms.

<Formula 2a>

Further, in the tetraazapophyrin derivative, R1, R2, R3, R4, R5, R6, R7 and R8 are each a phenyl group; Or 1 to 5 carbon atoms selected from the group consisting of an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, a nitro group, a halogen atom, an alkylamine group having 1 to 8 carbon atoms, an aminoalkyl group having 1 to 8 carbon atoms, and a cyano group It is preferable that it is a phenyl group which has a substituent.

The tetraazapophyrin derivative of the formula (1) is particularly preferably selected from compounds of the following structural formula.

In addition, in the tetraazapophyrin derivative of formula (3), M is Ni, Mg, Mn, Co, Cu, Ru or V or Mn or Ru coordinated with one or more ligands selected from ammonia, water and halogen atoms. In particular, the tetraazapophyrin derivative of the formula (3) is preferably selected from the compounds represented by the following structural formula.

The photoselective light absorber according to the present invention may be prepared by dissolving in an organic solvent together with a plastic resin and preparing a coating agent. The content of the photoselective light absorber in this coating agent is from 0.05 to 1% by weight based on the coating solids. At this time, if the content of the light-selective light absorber is less than 0.05% by weight, it is not preferable because the implementation of the required light absorption properties are insufficient, and if the content of the light-selective light absorber exceeds 1% by weight, the physical properties of the coating agent are lowered.

In the light selective absorbent coating agent of the present invention, it is preferable to use a transparent plastic resin such as poly (methyl methacrylate), polyvinyl alcohol, polycarbonate, ethylene vinyl acetate and polyvinyl butyral as the plastic resin. The content is preferably 5 to 40% by weight based on the total weight of the organic solvent. If the content of the transparent plastic resin is less than 5% by weight it is difficult to secure the thickness for implementing the required physical properties, if the content exceeds 40% by weight is not preferable because the coating properties are lowered.

As the organic solvent, toluene, xylene, propyl alcohol, isopropyl alcohol, methylcellulose solution, ethylcellulose solution, dimethylformamide and the like can be used.

In the photoselective absorbent coating of the present invention, azo dyes, cyanine dyes, diphenylmethane dyes, triphenylmethane dyes, phthalocyanine dyes, and xanthene dyes are used to control the transmittance of each wavelength region of the color display device or to realize whiteness. , Diphenylene dyes, dyes such as indigo or porphyrin can be further added. At this time, the content of the dye is preferably 0.05 to 3% by weight based on the total weight of the total solid content of the coating agent. If the content of the dye is less than 0.05% by weight is insufficient implementation of the required light absorption characteristics, if the content of more than 3% by weight is not preferable because the physical properties of the coating agent is lowered.

In the coating agent of the present invention, it is preferable to further add an infrared ray blocking agent to block infrared rays (especially near infrared rays) reflected from a color display device, in particular, a plasma display panel. Such infrared ray blocking agents are represented by the following Chemical Formulas 4, 5 and 6 The compound which becomes, etc. can be used.

In Formula 4, R9 is an alkyl group having 1 to 6 carbon atoms, Q is ClO ₄ , Ab ₂ F ₆ , BF ₃ , toluenesulfonate or benzenesulfonate.

In Formula 5, M 'is Ni, Pd or Pt, R10 is hydrogen or an alkyl or alkoxy group having 1 to 10 carbon atoms; Phenyl substituted with halogen or alkylamine; Or a phenyl group.

In Formula 6, M ″ is Fe, Ni, Cu, Co, or Pt, R11 is hydrogen; an alkyl or alkoxy group having 1 to 10 carbon atoms; halogen; or a nitro group, and A ⁺ is a tetraalkylammonium cation ( In this case, the alkyl group has 1 to 6 carbon atoms.

In addition, a stabilizer may be further added to the light selective absorbent coating agent of the present invention to improve light resistance. Stabilizers that can be used include radical reaction inhibitors that prevent the fading of pigments that can be used conventionally.

The photo-selective absorbent coating of the present invention may be used by coating the glass, plastic or plastic film to be mounted on the display device, or by directly coating the surface of the display device, and such coating may be performed using conventional methods. It may be performed by, for example, spin coating or roll coating. The photo-selective absorbent coating agent of the present invention is preferably coated with a thickness of 1 to 20㎛. If the coating film thickness of the photoselective absorbent coating agent is less than 1 μm, the desired absorption characteristics are insufficient. If the thickness is greater than 20 μm, the coating properties are deteriorated.

The photoselective absorbent filter of the present invention is completed by coating and drying the above-described photoselective absorbent coating agent. Therefore, since the solvent contained in the coating is removed during the drying process, the photoselective absorption filter includes a tetraazapophyrin derivative represented by Chemical Formula 1 or 3 and a plastic resin.

Hereinafter, the present invention will be described with reference to the following synthesis examples and examples, but the present invention is not limited to the following synthesis examples and examples.

Synthesis Example 1: Octaphenyltetraazapopyrin Compound

According to a method known in J. Am. Soc., 929 (1937), octaphenyltetraazapyrroline wherein tetraazapophyrin R1, R2, R3, R4, R5, R6, R7 and R8 is a phenyl group Synthesized together.

100 parts by weight of iodine, 50 parts by weight of phenylacetonitrile and 1500 parts by weight of ethyl ether were mixed and dissolved in a three-necked round bottom flask, followed by a solution of 300 parts by weight of methanol dissolved in 18 parts by weight of sodium (cooled with ice water). Was added slowly over 30 dispersions.

Upon completion of the reaction, water, diluted thiosulfate solution, water and sodium sulfate solution were added sequentially to the reaction mixture. Subsequently, the solvent was removed from the resultant, and the resulting yellow solid was evaporated under reduced pressure to obtain diphenylmaleinitrile (yield: 50%).

When 5 parts by weight of the diphenylmaleimnitrile and 0.5 parts by weight of magnesium were reacted at 275 ° C. for 10 minutes, violet crystals were formed. Here the metal residue was removed with dilute acetic acid solution, sodium carbonate solution was added to warm to 50 ° C., and the unreacted nitrile compound was hydrolyzed. The magnesium octaphenylpopyazine thus obtained was washed with a sufficient amount of hot water and dried.

The magnesium octaphenyl-pyrazine compound was added to a dilute hydrochloric acid solution, and heated sufficiently to remove magnesium ions, and then recrystallized by dissolving with benzene to obtain octaphenyltetraazapyrroline, the target compound. The absorption spectrum of this octaphenyl tetraaza porphyrin is as shown in FIG.

Synthesis Example 2 Tribenzyltetraazapopyrin Compound

According to a method known from J. Am. Soc., 112, 9641 (1990), tetraazapophyrin R2 is a t-butyl group and R1, R3, R4, R5, R6, R7 and R8 are hydrogen Tribenzyltetraazapopyrin compounds were synthesized as follows.

Into a three-necked round bottom flask, 30 g of 1-chloronaphthalene, 10 g of t-butylphthalonitrile, and 10 g of phenyldibromoborane were added thereto, followed by heating and melting at 260 ° C. for about 10 minutes to react with tributylated sub-phthalocyanine. Was obtained (yield: 50%).

One equivalent of the tributylated subphthalocyanine compound and one equivalent of diiminoisoindolin were dissolved in a mixed solvent of dimethyl sulfoxide and 1-chloronaphthalene (2: 1 by volume), and then, these were reacted at 80 to 90 ° C. for 24 hours. Reacted. The reaction product was evaporated under reduced pressure to remove the solvent, and chromatography was carried out to obtain a tribenzyl tetraazapyrroline compound as a powdery light blue target product. The absorption spectrum of this tribenzyltetraazapopyrin is as shown in FIG.

Synthesis Example 3 Ruthenium Octaphenyl Tetraazaporphyrin Compound

According to a method known in J. Am. Soc., 929 (1937), tetraazapophyrin compounds wherein R 1, R 2, R 3, R 4, R 5, R 6, R 7 and R 8 are all hydrogen were synthesized as follows. .

100 parts by weight of iodine, 50 parts by weight of phenylacetonitrile and 1500 parts by weight of ethyl ether were mixed and dissolved in a three-necked round bottom flask, followed by a solution of 300 parts by weight of methanol dissolved in 18 parts by weight of sodium (cooled with ice water). Was added slowly for 30 minutes.

Upon completion of the reaction, water, diluted thiosulfate solution, water and sodium sulfate solution were added sequentially to the reaction mixture. Subsequently, the solvent was removed from the resultant, and the resulting yellow solid was evaporated under reduced pressure to obtain diphenylmaleimnitrile (yield: 50%).

5 parts by weight of the obtained diphenylmaleimnitrile compound and 0.5 parts by weight of pentaamine dinitrogenruthenium dichloride ([Ru (NH ₃ ) ₅ (N ₂ )] Cl ₂ ) were reacted at 275 ° C. for 30 minutes to obtain purple crystals. Got it. Here, the metal residue was removed with a dilute acetic acid solution, a sodium carbonate solution was added thereto, warmed to 50 ° C, and the unreacted nitrile compound was hydrolyzed. The ruthenium octaphenyltetraazapopyrin thus obtained was washed with a sufficient amount of hot water and dried. The absorbance spectrum of the obtained ruthenium octaphenyltetraazapopyrin is as shown in FIG.

Synthesis Example 4 Copper Tetramethyltetraazapopyrin Compound

Copper tetramethyltetraazaphosphine was synthesized according to the method known from J. Am. Soc., 4839 (1952) as follows.

60 parts by weight of metal-free tetramethyltetraazapophyrin and 1.5 parts by weight of anhydrous copper were refluxed for 3 hours in a solvent of 25 parts by weight of o-dichlorobenzene. After the reaction was completed, the reaction mixture was filtered in cold state. Subsequently, the resultant was extracted with chloroform, and then pure copper tetramethyltetraazaporphyrin was obtained through crystallization (yield: 33%). At this time, the absorption spectrum of the copper tetramethyltetraazapopyrin is as shown in FIG.

Synthesis Example 5 Nickel Tetrabutyltetraazapopyrin Compound

According to a method known from J. Am. Soc., 4839 (1952), nickel tetrabutylteazapophyrin was synthesized as follows.

50 parts by weight of metal-free tetrabutyltetraazapophyrin and 1.5 parts by weight of anhydrous nickel chloride were refluxed for 1.5 hours in a solvent of 25 parts by weight of o-dichlorobenzene. Upon completion of the reaction, the reaction mixture was filtered while hot. The solid was washed with hot water and ethanol and then extracted with chlorobenzene. Subsequently, the resultant product was crystallized to obtain pure nickel tetrabutylteazapophyrin. The absorption spectrum of this nickel tetrabutyl tetraaza porphyrin is as shown in FIG.

Synthesis Example 6 Cobalt Tetrabutylteazapophyrin Compound

According to a method known from J. Am. Soc., 4839 (1952), cobalt tetrabutylteazapophyrin was synthesized as follows.

50 parts by weight of metal-free tetrabutylteazapophyrin and 1.5 parts by weight of anhydrous cobalt chloride were refluxed for 1.5 hours in a solvent of 25 parts by weight of o-dichlorobenzene. Upon completion of the reaction, the reaction mixture was filtered while hot. The solid was washed with hot water and ethanol and then extracted with chlorobenzene. Subsequently, the resultant product was crystallized to obtain pure cobalt tetrabutylteazapophyrin.

Synthesis Example 7 Vanadium Oxide Octaphenyl Tetraazaporphyrin

According to a method known from J. Am. Soc., 4839 (1952), vanadium oxide octaphenyltetraazapiphyrin was synthesized as follows.

50 parts by weight of the metal free octaphenylteazapophyrin and 1.5 parts by weight of anhydrous vanadium oxide were refluxed in a solvent of 25 parts by weight of o-dichlorobenzene for 1.5 hours. Upon completion of the reaction, the reaction mixture was filtered while hot. The solid was washed with hot water and ethanol and then extracted with chlorobenzene. Subsequently, the resultant product was crystallized to obtain pure vanadium oxide octaphenyltetraazapopyrine.

Synthesis Example 8. Manganese octaphenylteazapopyrine

According to a method known from J. Am. Soc., 4839 (1952), manganese octaphenylazatetraazapopyrin was synthesized as follows.

50 parts by weight of the metal-free octaphenylteazapophyrin and 1.5 parts by weight of anhydrous manganese were refluxed in a solvent of 25 parts by weight of o-dichlorobenzene for 1.5 hours. Upon completion of the reaction, the reaction mixture was refluxed in the hot state. The solid was washed with hot water and ethanol and then extracted with chlorobenzene. Subsequently, pure manganese octaphenyltetraazapopyrine was obtained through crystallization of the resultant product.

Compounds of the following structural formulas were synthesized by following a procedure analogous to that described in the synthesis examples.

Example 1.

Step 1: Preparation of Photo Selective Absorbent Coating for Display

100 ml of methyl ethyl ketone (MEK) was added to the reactor, and 30 g of polymethyl methacrylate was added thereto to dissolve while warming. Thereafter, 10 mg of octaphenyltetraazaporphyrin prepared in Synthesis Example 1 was added to the mixture, followed by dissolution. Then, 12 mg of acridine orange (Acridine Orange, Aldrich Chemical) was slowly added to 5 ml of isopropyl alcohol. A photoselective absorbent coating for a display device was prepared.

Step 2: manufacture the filter for the display

The coating prepared in Step 1 was spin coated on a transparent glass substrate, and then dried at 90 ° C. for 10 minutes to form a colored glass substrate having a colored layer having a thickness of about 6 μm. The colored glass substrate was mounted on a cathode ray tube and a plasma display panel, and the color coordinates, contrast ratio, and luminance ratio of three primary colors were measured and shown in Table 1 below.

In addition, in order to evaluate the stability to the light of the manufactured colored glass substrate, after the antireflective polyethylene terephthalate film was bonded to the colored glass substrate, it was exposed for 3 hours at 2 kW xenon hamp before and after exposure The transmittance of was measured using a spectrophotometer. FIG. 8 shows a comparison of transmittances before and after light exposure of a glass substrate colored with the light selective absorbent coating agent for a color display device according to Example 1. FIG. FIG. 11 shows the emission spectra of the plasma display panels before and after the glass substrates colored with the photoselective absorbent coating of Example 1 were mounted on the plasma display panel.

Example 2

Step 1: Preparation of Photo Selective Absorbent Coating for Display

100 ml of methyl ethyl ketone (MEK) was added to the reactor, and 30 g of polymethyl methacrylate was added thereto to dissolve while warming. Thereafter, 8 mg of octaphenyltetraazapophyrin prepared in Synthesis Example 1 and 150 mg of IRG022 (Japanese chemical) were dissolved in the mixture. Subsequently, 10 mg of acridine orange dissolved in 5 ml of isophthalic acid was slowly added to the mixture to prepare a light selective absorbent coating agent for a display device.

Step 2: manufacture the filter for the display

The coating agent prepared in Step 1 was carried out in the same manner as in Step 2 of Example 1 to form a colored glass substrate having a colored layer having a thickness of about 6 μm. The colored glass substrate was mounted on a cathode ray tube and a plasma display panel to measure color coordinates, contrast ratio, and luminance ratio of three primary colors, and the results are shown in FIGS. 9-10 and Table 1 below.

Example 3

Step 1. Photoselective absorbent coating for display device

A photo-selective absorbent coating for a display device was manufactured by following the same procedure as in Step 1 of Example 2, except that 100 mg of Q-1 (Japan Photosensitive Pigment Co., Ltd.) was used instead of IRG022.

Step 2. Optical Filter for Display

The photoselective absorbent coating obtained in Step 1 was carried out in the same manner as in Step 2 of Example 1 to form a colored glass substrate having a colored layer having a thickness of about 6 μm. The colored glass substrate was mounted on a cathode ray tube and a plasma display panel to measure color coordinates, contrast ratio and luminance ratio of three primary colors, and the results are shown in Table 1 below.

Example 4

Step 1: Preparation of Photo Selective Absorbent Coating for Display

100 ml of methyl ethyl ketone (MEK) was added to the reactor, and 30 g of polymethyl methacrylate was added thereto to dissolve while warming. Thereafter, 10 mg of tribenzyltetraazaporphyrin prepared in Synthesis Example 2 was added to the mixture to dissolve it. Subsequently, 12 mg of acridine orange dissolved in 5 ml of isopropyl alcohol was slowly added to the mixture to prepare a light selective absorbent coating agent for a display device.

Step 2: manufacture the filter for the display

The coating agent prepared in Step 1 was carried out in the same manner as in Step 2 of Example 1 to form a colored glass substrate having a colored layer having a thickness of about 6 μm. The emission spectra of the PDPs before and after the colored glass substrates were mounted on the plasma display panel were measured, and the results are shown in FIG. 12. In addition, the colored glass substrate was mounted on a cathode ray tube and a plasma display panel to measure color coordinates, contrast ratio, and luminance ratio of three primary colors, and are shown in Table 1 below.

Example 5

Step 1: Preparation of Photo Selective Absorbent Coating for Display

100 ml of methyl ethyl ketone (MEK) was added to the reactor, and 30 g of polymethyl methacrylate was added thereto to dissolve while warming. Thereafter, 8 mg of tribenzyltetraazaporphyrin prepared in Synthesis Example 2 and 150 mg of IRG022 (Japanese chemical) were dissolved in the mixture. Subsequently, 10 mg of acridine orange dissolved in 5 ml of isophthalic acid was slowly added to the mixture to prepare a light selective absorbent coating agent for a display device.

Step 2: manufacture the filter for the display

The coating agent prepared in Step 1 was carried out in the same manner as in Step 2 of Example 1 to form a colored glass substrate having a colored layer having a thickness of about 6 μm. The colored glass substrate was mounted on a cathode ray tube and a plasma display panel to measure color coordinates, contrast ratio, and luminance ratio of three primary colors, and the results are shown in FIGS. 9-10 and Table 1 below.

Example 6

Step 1: Preparation of Photo Selective Absorbent Coating for Display

A photo-selective absorbent coating for a display device was manufactured by the same method as Step 1 of Example 5, except that 100 mg of Q-1 was used instead of IRG022.

Step 2: manufacture the filter for the display

The coating agent prepared in Step 1 was carried out in the same manner as in Step 2 of Example 1 to form a colored glass substrate having a colored layer having a thickness of about 6 μm. The colored glass substrate was mounted on a cathode ray tube and a plasma display panel to measure color coordinates, contrast ratio and luminance ratio of three primary colors, and the results are shown in Table 1 below.

Example 7

Step 1: Preparation of Photo Selective Absorbent Coating for Display

75 ml of toluene was added to the reactor, and 25 g of polymethylmethacrylate was dissolved while warming up. Thereafter, 30 mg of ruthenium octaphenyl tetraazapophyrin prepared in Synthesis Example 3 was added to the mixture to dissolve to prepare a photoselective absorbent coating agent for a display device.

Step 2: manufacture the filter for the display

The coating agent prepared in Step 1 was carried out in the same manner as in Step 2 of Example 1 to form a colored glass substrate having a colored layer having a thickness of about 6 μm. The colored glass substrate was mounted on a cathode ray tube and a plasma display panel, and the color coordinates, contrast ratio, and luminance ratio of the three primary colors were measured, and the results are shown in Table 1 below. The emission spectra were measured and the results are shown in FIG. 13.

Example 8

Step 1: Preparation of Photo Selective Absorbent Coating for Display

75 ml of toluene was added to the reactor, and 25 g of polymethylmethacrylate was dissolved while warming up. Thereafter, 30 mg of ruthenium octaphenyltetraazaporphyrin prepared in Synthesis Example 3 and 150 mg of IRG022 were added to the mixture to dissolve it. Subsequently, 5 mg of acridine orange dissolved in 5 ml of isopropyl alcohol was added to the mixture to prepare a light selective absorbent coating agent for a display device.

Step 2: manufacture the filter for the display

The coating agent prepared in Step 1 was carried out in the same manner as in Step 2 of Example 1 to form a colored glass substrate having a colored layer having a thickness of about 6 μm. The colored glass substrate was mounted on a cathode ray tube and a plasma display panel, and the color coordinates of the three primary colors and the contrast and luminance ratios before and after the colored glass substrate was mounted on the plasma display panel were measured. 1 is shown.

Example 9

Step 1: Preparation of Photo Selective Absorbent Coating for Display

A photo-selective absorbent coating for a display device was manufactured by the same method as Step 1 of Example 8, except that 100 mg of Q-1 was used instead of IRG022.

Step 2: manufacture the filter for the display

The coating agent prepared in Step 1 was carried out in the same manner as in Step 2 of Example 1 to form a colored glass substrate having a colored layer having a thickness of about 6 μm.

This colored glass substrate was mounted on the cathode ray tube and the plasma display panel, and the color coordinates of the three primary colors, the contrast ratio before and after mounting, and the luminance ratio were measured and shown in Table 1 below.

Example 10

Step 1: Preparation of Photo Selective Absorbent Coating for Display

75 ml of toluene was added to the reactor, and 25 g of polymethylmethacrylate was dissolved while warming up. Thereafter, 30 mg of copper tetramethyltetraazaporphyrin prepared in Synthesis Example 4 and 150 mg of IRG022 were added and dissolved in the mixture. Subsequently, 5 mg of acridine orange dissolved in 5 ml of isopropyl alcohol was added to the mixture to prepare a light selective absorbent coating agent for a display device.

Step 2: manufacture the filter for the display

The coating agent prepared in Step 1 was carried out in the same manner as in Step 2 of Example 1 to form a colored glass substrate having a colored layer having a thickness of about 6 μm.

The colored glass substrate was mounted on a cathode ray tube and a plasma display panel, and the color coordinates of three primary colors, contrast ratios before and after mounting, and luminance ratios were measured. The results are shown in Table 1 below. The results are shown in FIG.

Example 11

Step 1: Preparation of Photo Selective Absorbent Coating for Display

75 ml of toluene was added to the reactor, and 25 g of polymethylmethacrylate was dissolved while warming up. Thereafter, 30 mg of nickel tetramethyltetraazaporphyrin and 150 mg of IRG022 prepared in Synthesis Example 5 were added and dissolved in the mixture. Subsequently, 5 mg of acridine orange dissolved in 5 ml of isopropyl alcohol was added to the mixture to prepare a light selective absorbent coating agent for a display device.

Step 2: manufacture the filter for the display

The coating agent prepared in Step 1 was carried out in the same manner as in Step 2 of Example 1 to form a colored glass substrate having a colored layer having a thickness of about 6 μm. The colored glass substrate was mounted on a cathode ray tube and a plasma display panel, and the color coordinates, contrast ratio, and luminance ratio of the three primary colors were measured, and the results are shown in Table 1 below. 14 is shown.

Comparative Example 1

20 g of polyvinyl alcohol is dissolved in 100 ml of water, where 12 mg of fluorescein amine isomer I (Aldrich Chemical) and 10 mg of phloxine B (Aldrich Chemical), 5 mg of sulfohodiamine 101 (Sulforhodiamine) 101, Aldrich Chemical Co., Ltd. and 13.5 mg of Luxol Fast Blue (Aldrich Chemical Co., Ltd.) were dissolved, and the solution was spin-coated on a transparent glass substrate and dried at 50 ° C. for 1 hour to color about 8 μm thick. A layer was formed. The colored glass substrate thus obtained was evaluated in the same manner as in Example 1, and the characteristics of the display device were evaluated.

In addition, in order to evaluate the stability to the light of the colored glass substrate, it was treated in the same manner as in Example 1 and the change in transmittance before and after light exposure was measured and shown in FIG. 8.

Referring to FIG. 8, it was confirmed that due to the photolysis of the pigment blocking the green emission and the red emission spectrum, the change in the transmittance was severely shown in the corresponding region.

Comparative Example 2

A coating agent was prepared according to the same method as Example 11 except for using 8 mg of Eastwell 590 (Eastwell Co., Ltd.) instead of nickel tetramethyltetraazapopyrine, and coloring treated with this coating agent. A glass substrate was obtained. The obtained colored glass substrate was mounted on CRT and PDP in the same manner as in Example 2, and the color coordinates, contrast ratios before and after mounting, and luminance ratios were measured, and are shown in FIGS. 9, 10, and Table 1, and were separately obtained using a spectrophotometer. The transmission spectrum is shown in FIG.

In Table 1, Cr and Er are values representing contrast ratios and luminance ratios before and after mounting a colored glass substrate on a CRT or PDP.

Referring to Table 1, a color display device having a glass substrate colored with a coating agent containing a photoselective light absorber of the present invention is a color coordinate device than a color display apparatus having a glass substrate colored with a coating agent containing a conventional light absorber. And it was confirmed that the contrast was improved.

When the coating agent including the light selective light absorbing agent according to the present invention is applied to a color display device, color purity and contrast of the color display device may be improved by blocking reflected light of the display device and emission light corresponding to an intermediate color of three primary colors.

Claims (14)

Photo-selective light absorber for a color display device comprising a tetraazapopyrine derivative of formula: <Formula 1> Wherein R1, R2, R3, R4, R5, R6, R7 and R8 are each independently hydrogen; Unsubstituted phenyl group; An alkyl group having 1 to 8 carbon atoms; An alkoxy group having 1 to 8 carbon atoms; Nitro group; Halogen atom; Halides; Cyano group; Alkylamino groups having 1 to 8 carbon atoms; Aminoalkyl groups having 1 to 8 carbon atoms; A phenyl group having a substituent selected from an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, a nitro group, a halogen atom, a halide, an alkylamino group having 1 to 8 carbon atoms, an aminoalkyl group having 1 to 8 carbon atoms, and a cyano group; A ring of 1-3 selected from the group of aromatic ring compounds of formula 2a-g, wherein two substituents adjacent to each other selected from the group or selected from the substituents of R1, R2, R3, R4, R5, R6, R7 and R8 are fused together Compound, and the remaining substituents are independently of each other hydrogen; An alkyl group having 1 to 8 carbon atoms; An alkoxy group having 1 to 8 carbon atoms; Allyl groups; Halogen atom; Halides; Cyano group; Nitro group; selected from the group consisting of. <Formula 2a> <Formula 2b> <Formula 2c> <Formula 2d> <Formula 2e> <Formula 2f> Wherein R ', R ", R"', and R "" are independently of each other hydrogen; an alkyl group having 1 to 8 carbon atoms; An alkoxy group having 1 to 8 carbon atoms; Allyl group; Halogen atom; Cyano group; Nitro group; selected from the group consisting of X is a halogen atom or an alkyl sulfonate having 1 to 8 carbon atoms, Y is an alkyl group or allyl group having 1 to 8 carbon atoms, The dotted line portion shows the portion bonded to the pyrrole group of the formula (1). A photoselective light absorber for a color display device comprising the tetraazapophyrin derivative of formula (3): <Formula 3> Wherein R1, R2, R3, R4, R5, R6, R7 and R8 are each independently hydrogen; Unsubstituted phenyl group; An alkyl group having 1 to 8 carbon atoms; An alkoxy group having 1 to 8 carbon atoms; Nitro group; Halogen atom; Halides; Cyano group; Alkylamino groups having 1 to 8 carbon atoms; Aminoalkyl groups having 1 to 8 carbon atoms; A phenyl group having a substituent selected from an alkoxy group having 1 to 8 carbon atoms, an alkyl group having 1 to 8 carbon atoms, a nitro group, a halogen atom, a halide, an alkylamino group having 1 to 8 carbon atoms, an aminoalkyl group having 1 to 8 carbon atoms, and a cyano group; A ring of 1-3 selected from the group of aromatic ring compounds of formula 2a-g, wherein two substituents adjacent to each other selected from the group or selected from the substituents of R1, R2, R3, R4, R5, R6, R7 and R8 are fused together Compound, and the remaining substituents are independently of each other hydrogen; An alkyl group having 1 to 8 carbon atoms; An alkoxy group having 1 to 8 carbon atoms; Allyl group; Halogen atom; Halides; Cyano group; Nitro group; selected from the group consisting of M is a metal ion having a number of 2 oxides and complexes with a tetraazapophyrin ring or a metal ion having a number of oxides 2 and a complex with a tetraazapophylline ring and having a ligand capable of forming a coordinating bond with the metal ion. , <Formula 2a> <Formula 2b> <Formula 2c> <Formula 2d> <Formula 2e> <Formula 2f> Wherein R ', R ", R"', R "" are independently of each other hydrogen; An alkyl group having 1 to 8 carbon atoms; An alkoxy group having 1 to 8 carbon atoms; Allyl group; Halogen atom; Cyano group; Nitro group; selected from the group consisting of X is a halogen atom or an alkyl sulfonate having 1 to 8 carbon atoms, Y is an alkyl or allyl group having 1 to 8 carbon atoms, The dotted line portion shows the portion bonded to the pyrrole group of the formula (1). The cyclic compound of claim 2, wherein in the tetraazapophyrin derivative, two substituents adjacent to each other selected from the substituents of R1, R2, R3, R4, R5, R6, R7, and R8 are fused together. 2 to 3, At least one of R ', R ", R"', and R "" in the ring compound of Formula 2a is an alkyl group having 2 to 6 carbon atoms or an alkoxy group having 2 to 6 carbon atoms. The tetraazapophyrin derivative according to claim 1 or 2, wherein R1, R2, R3, R4, R5, R6, R7 and R8 each represent a phenyl group; Or 1 to 5 carbon atoms selected from the group consisting of an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, a nitro group, a halogen atom, an alkylamine group having 1 to 8 carbon atoms, an aminoalkyl group having 1 to 8 carbon atoms, and a cyano group It is a phenyl group which has a substituent; The optical selective light absorber characterized by the above-mentioned. The photoselective light absorber of claim 1, wherein the tetraazapophyrin derivative of Chemical Formula 1 is selected from compounds of the following structural formulas. The photoselective light absorber according to claim 2, wherein M is Ni, Mg, Mn, Co, Cu, Ru or V, or Mn or Ru coordinated with at least one ligand selected from ammonia, water and halogen atoms. . The photoselective light absorber of claim 2, wherein the tetraazapophyrin derivative of Chemical Formula 3 is selected from compounds of the following structural formulas. 8. The light selective absorbent coating for color display device according to any one of claims 1 to 7, comprising a light selective light absorber, a plastic resin, and an organic solvent. The optical selection device of claim 8, wherein the plastic resin is at least one selected from the group consisting of poly (methyl methacrylate), polyvinyl alcohol, polycarbonate, ethylene vinyl acetate, and polyvinyl butyral. Absorbent coatings. The optical selection device of claim 8, wherein the organic solvent is at least one selected from the group consisting of toluene, xylene, propyl alcohol, isopropyl alcohol, methyl cellussolve, ethyl cellussolve, and dimethylformamide. Absorbent coatings. 9. The light selective absorbent coating for color display device according to claim 8, further comprising an infrared ray blocking agent. The light selective absorbent coating for color display device according to claim 8, further comprising a dye. 8. The light selective absorbing filter for color display device according to any one of claims 1 to 7, comprising a light selective absorbing agent and a plastic resin. 15. The light selection device of claim 13, wherein the plastic resin is at least one selected from the group consisting of poly (methyl methacrylate), polyvinyl alcohol, polycarbonate, ethylene vinyl acetate, and polyvinyl butyral. Absorbent filter.