KR100550943B1 - Method for eliminating fluorescence radiated from cyanine or porphyrin dyes, coating composition of color compensation film, color compensation film and filter by using the same composition - Google Patents

Abstract

The present invention relates to a fluorescence removal method of a cyanine or porphyrin-based pigment and a coating liquid composition for a color correction film using the method, and more particularly to a cyanine used in a color correction filter of a plasma display panel (PDP). Alternatively, in order to reduce the fluorescence of the porphyrin-based pigment, a method of removing the fluorescence of the cyanine and the porphyrin-based pigment by adding an additional pigment having a maximum excitation wavelength and a maximum absorption wavelength at the maximum emission wavelength of the pigment and a color correction film using the method It relates to a coating liquid composition for. According to the present invention, the fluorescence generated in the cyanine and the porphyrin-based pigment can be efficiently blocked.

Plasma Display Panel (PDP), Color Correction, Cyanine, Porphyrin, Fluorescence

Description

Fluorescence removal method of cyanine or porphyrin pigment, coating liquid composition for color correction film, color correction film and filter using this composition USING THE SAME COMPOSITION}             

Figure 1 shows the fluorescence spectrum according to the excitation wavelength of the cyanine pigment TY-171 according to Comparative Example 1 of the present invention,

Figure 2 shows the fluorescence spectrum according to the excitation wavelength of the cyanine pigment HAO-01 according to Comparative Example 1 of the present invention,

Figure 3 shows the fluorescence spectrum according to the excitation wavelength of porphyrin-based pigment TAP-2 according to Comparative Example 1 of the present invention.

The present invention relates to a fluorescence removal method of cyanine and porphyrin dyes and a coating liquid composition for color correction filters using these dyes, and more particularly, to cyanine and porphyrin dyes used for color correction filters in plasma display panels (PDPs). The present invention relates to a method for efficiently reducing fluorescence and a coating liquid composition for color correction filters of PDP using this method.

Plasma displays are easy to be large screens, and are becoming thinner self-luminous display means. In order to use plasma displays in color TVs, it is necessary to widen the color reproduction range of light emitted from the panel. This can be done through improvement of the phosphor, but also through the color correction function of the front filter of the plasma display.

Plasma displays use ultraviolet light emission of the discharge gas, and as the discharge gas, a penning gas mainly mixed with neon (Ne) and a small amount of xenon (Xe) gas is used. Using this ultraviolet ray as the excitation source, the phosphor emits R, G, and B primary colors, thereby realizing color. However, in the plasma display, in addition to the visible light emitted from the phosphor, strong orange visible light is generated from neon, which appears as a plurality of emission peaks in the wavelength region of 580 nm or more. Due to such light emission, color and blue color reproducibility of the display device are deteriorated. This can be solved by removing the light emission of 580 nm or more with a filter. However, since this area corresponds to the red light emission area, the red luminance is reduced. Therefore, rather than removing a wide range of light emission, by removing near 590 nm, which is the maximum emission wavelength by neon, a selective visible light absorbing pigment having a half width is developed to increase the color reproducibility of blue and green and to minimize the decrease in luminance of red. It became.

This selective visible light absorbing pigment is a cyanine-based and porphyrin-based pigments can obtain a desired absorbance in a small amount due to the high absorption coefficient of about 10 ⁵ cm ^-1 M ^-1 , because it has a narrow half-width of several tens of nm It is very suitable as a visible light absorbing dye. However, such cyanine-based or porphyrin-based pigments fluoresce in many cases and thus have a problem of degrading the color reproducibility of the display. Therefore, even in the case of synthesizing a pigment having a high absorption coefficient and a small half width in the desired wavelength band, it is often not used as a problem of fluorescence.

As a result of earnest research to solve the problems of the prior art, the present inventors have found the maximum excitation wavelength band and the maximum emission wavelength band of the fluorescence dye and have a maximum absorption in the wavelength band in the vicinity. The present invention has been made by discovering that the use of a small amount of can reduce the fluorescence of cyanine and porphyrin pigments.

One object of the present invention is to provide a method for reducing the fluorescence of cyanine or porphyrin-based pigments, which are pigments for color correction filters in displays such as plasma displays.

Another object of the present invention to provide a coating liquid composition for a color correction film.                         

Still another object of the present invention is to provide a color correction film and a color correction filter using the coating solution composition.

According to an aspect of the present invention for achieving the above object, by reducing the fluorescence of the pigment by adding a different excitation wavelength of the cyanine or porphyrin-based pigment that is a fluorescence dye or the maximum absorption wavelength at the maximum emission wavelength A method is provided.

According to another aspect of the invention, the cyanine or porphyrin pigment, the maximum excitation wavelength or maximum emission wavelength of the cyanine or porphyrin pigment, that is, a pigment having a maximum absorption in the wavelength band of 450 ~ 550 nm or 600 ~ 700 nm, the In addition to the one pigment is provided a coating liquid composition for a color correction film comprising a dye, an organic solvent and a binder for correcting the color coordinates of the color correction film.

According to another aspect of the present invention, a color correction film and a color correction filter using the coating liquid composition for the color correction filter are provided.

Hereinafter, with reference to the accompanying drawings will be described in detail with respect to the present invention.

In the present invention, as a substance for reducing the fluorescence of cyanine or porphyrin-based pigments, a fluorescence reduction effect can be obtained with a small amount of pigment using a dye that absorbs light of an excitation wavelength band that causes fluorescence and a light emitting wavelength band that emits fluorescence.

Fluorescence spectra of cyanine and porphyrin pigments having maximum absorption in the wavelength range of 580 to 595 nm used for color correction of PDP were measured to find that the maximum excitation wavelength was around 500 nm and the maximum emission wavelength was around 630 nm. Therefore, the dyes used to reduce the fluorescence of cyanine and porphyrin pigments used for PDP color correction have a maximum absorption at 600 to 700 nm, preferably 620 to 650 nm, which is the maximum emission wavelength band of these cyanine and porphyrin pigments. Pigments are suitable. Moreover, the pigment | dye which has a maximum absorption in 450-550 nm which is the maximum excitation wavelength band of these cyanine and a porphyrin type pigment | dye, Preferably 470-520 nm is preferable.

These pigments may be used alone or in combination to match color coordinates, and the amount added may be used by finding a minimum amount of fluorescence that is reduced by using a spectro-fluorometer. However, more than the minimum usage may be used to match a particular color coordinate value. Generally, 50 to 200 weight% of the cyanine and porphyrin pigment which are neon light absorption pigments are used.

The coating solution composition for a color correction film of the present invention is a cyanine or porphyrin-based pigment, a dye having a maximum absorption wavelength at the maximum excitation wavelength and a maximum emission wavelength of the cyanine or porphyrin-based pigment, and additional pigments for matching color coordinates to a combination of the dyes. And suitable organic solvents and binder resins.

The cyanine dye used in the coating liquid composition of the present invention may be represented by the structure of Formula 1, and the porphyrin dye may be represented by the structure of Formula 2.

Wherein X and Z each represent O, S, Se or an amine (RN ^- wherein R represents an alkyl or substituted phenyl group), Y represents an alkyl, alkyl ether or alkyl ester, and R ¹ to R ⁹ represents an alkyl or alkoxy or substituted phenoxy or thiophenoxy or halogen, each of which is C _1-4 , or a cyclic or aromatic cyclic compound constituting a 5- or 6-membered circle with ones in close proximity to each other, A ⁻ is the anion paired F, Cl, Br, halogens, perchlorate (ClO ₄ ^-) of the I, borate (BF ₄ ^-) tetrafluoroborate, antimonate hexafluorophosphate (SbF ₆ ^-), para-toluenesulfonyl Nate, camphorsulfonate, and the like.

In the formula, M represents a metal such as Mg, Cu, Zn, Pd, Ni, R ¹ represents halogen or C _1-4 alkyl or C _1-4 alkoxy group, R ² -R ⁶ are each C _1-4 alkyl or C _1-4 alkoxy or phenoxy or substituted phenoxy or C _1-4 alkylsulfide or thiophenoxy or substituted thiophenoxy or phenyl or substituted phenyl or halogen Type.

Commercially available cyanine or porphyrin pigments include HAO-01, manufactured by Hayashibara biochemical, TY-171, manufactured by Asahi Denka, TAP-2, manufactured by Yamada Chemical, and the like. For example.

The pigments having the maximum absorption wavelength and the maximum absorption wavelength at the maximum luminous wavelength of the cyanine or porphyrin-based pigments used in the coating liquid composition of the present invention are 600 to 700 nm, which is the maximum emission wavelength band of these cyanine and porphyrin-based pigments, preferably Dyestuffs having a maximum absorption at 620-650 nm are suitable. Moreover, the pigment | dye which has a maximum absorption in 450-550 nm which is the maximum excitation wavelength band of cyanine and a porphyrin type pigment | dye, Preferably it is 470-520 nm is preferable. These pigments are quinophthalone-based, thioxanthene-based, methine-based, perynone-based, anthraquinone-based, anthrapyridone-based anthrapyridone-based, and quinacridone. (Quinacridone), Phthalocyanine (Phthalocyanine), and the like, for example, M-Dohmen's Lumaplast Red-A2G, Lumaplast Blue-DR, Lumaplast Blue-RR and the like.

Any additional pigment for adjusting the color coordinates to the combination of the pigments may be used as long as it is dissolved in an organic solvent.

The organic solvent used in the coating composition of the present invention is methyl ethyl ketone (MEK), acetone (Cyclohexanone), cyclopentanone (Cyclopentanone), ether compound Dioxolane (Dioxolane), Dioxane, dimethoxyethane and aromatic compounds, toluene, xylene, and the like are suitable.

As the binder used in the coating composition of the present invention, an acrylic binder that is well mixed with cyanine or porphyrin and well mixed with an organic solvent is suitable. Examples thereof include IR-G205 from Japan Catalyst, a polymethylmethacrylate binder, ADKOPTOMER KRM-2826 from Asahi Denka Co., and the like.

According to the coating conditions, a composition for applying to a substrate such as a PET film can be obtained by mixing in a composition having an appropriate viscosity.

The coating liquid composition for color correction film of the present invention is applied to a transparent substrate such as a PET film using an automatic coating machine, a reverse roll coater, a gravure coater, and then dried by hot air to display a PDP or the like. A color correction film can be obtained. In addition, the color correction film may be directly attached to the display panel using an adhesive or attached to the front protective glass to be used as a color correction filter.

Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples. However, the following examples are provided to explain preferred embodiments of the present invention, and the scope of the present invention is not limited by the following examples.

Comparative Example 1. Fluorescence spectrum measurement of cyanine and porphyrin pigment

 Comparing the degree of fluorescence according to the excitation wavelength of the cyanine-based pigment (TY-171 from Asahi denka, HAO-01 from Hayashibara Biochemical) and the porphyrin-based pigment (TAP-2 from Yamada Chemical) In order to measure the fluorescence spectrum by measuring excitation wavelengths of 300, 400, 500 and 600 nm in a solution prepared by dissolving 1 mg of each of the pigments in 10 ml of a 1,3-dioxolane solvent, the fluorescence spectrum was measured (FP of Jasco Co., Ltd.). -6500 spectrofluorometer), the results are shown in Table 1 and FIGS.

1 shows a fluorescence spectrum according to the excitation wavelength of TY-171, a cyanine pigment, Figure 2 shows a fluorescence spectrum according to the excitation wavelength of HAO-01, Figure 3 is an excitation wavelength of the porphyrin pigment TAP-2 It shows a fluorescence spectrum according to. It can be seen from Table 1 and FIGS. 1 to 3 that the maximum excitation wavelength of each pigment is around 500 nm, and the intensity of fluorescence can be seen from the maximum value of the graph.

Example 1 Fluorescence Change of Neon Light Blocking Pigment by Addition of Red Pigment with Maximum Absorption Near Maximum Excitation Wavelength (500 nm) of Fluorescent Pigment

The three pigments TY-171, HAO-01, and TAP-2 and 490 used in Comparative Example 1 to determine the degree of fluorescence reduction by adding a pigment having maximum absorption near the maximum excitation wavelength of the fluorescent dye A commercially available red pigment (Lmapast Red-A2G from M-Dohmen) having a maximum absorption in the vicinity of 1 nm is mixed at 20, 40, 60 and 80% by weight based on the weight of each of the three selective visible light absorbing pigments 1, 3- Each fluorescence spectrum was measured by exciting the solution prepared by dissolving in dioxolane at 500 nm (using Jasco's FP-6500 spectrofluorometer), and the results are shown in Table 2.

Example 2 Fluorescence Change of Neon Light Blocking Pigment with Addition of Blue Pigment with Maximum Absorption at Maximum Emission Wavelength (620-660 nm) of Fluorescent Pigment

The three pigments TY-171, HAO-01, and TAP-2 used in Comparative Example 1 were used to determine the degree of fluorescence reduction by adding a dye having maximum absorption near the maximum emission wavelength of the fluorescent dye. A commercially available blue pigment (Lmaplast Blue-DR from M-Dohmen) having a maximum absorption in the vicinity of 620 to 660 nm is mixed at 20, 40, 60 and 80% by weight based on the weight of each of the three selective visible light absorbing pigments. Each fluorescence spectrum was measured by exciting the solution prepared by dissolving in, 3-dioxolane solvent at 500 nm (using Jasco FP-6500 spectrofluorometer), and the results are shown in Table 3.

      Examples 3 to 6 below are examples of manufacturing a color correction film for reducing the strong orange color of the 580 ~ 595nm visible light region of the PDP. Depending on the characteristics of the display, the transmittance in the 580 to 595 nm region of the color correction film varies, and the desired color coordinate value varies. In Examples 3 to 6 below, a color correction film having a minimum transmittance of 30 to 35% and a color coordinate (x, y, Y) of (0.280 ± 0.003, 0.300 ± 0.003, 66 ± 1) in the 580 to 595 nm region was used. Prepared.

< Example 3>

Cyanine-based selective visible light (580-595 nm) absorbing dye (TY-171) is commercially available blue pigment (Lmaplast Blue-RR from M-Dohmen Co., Ltd.) having a maximum absorption at 0.015% by weight of the total coating liquid composition and 590 to 640 nm. ) 0.015% by weight, additional pigment (M-Dohmen Lumaplast Yellow-GG) 0.005% by weight, violet pigment (M-Dohmen Violet-R) 0.003% by 1,3-dioxolane Or dissolved in 70% by weight of methyl ethyl ketone (MEK), and then mixed with 30% by weight of the acrylic binder (IR-G205) to prepare a coating liquid composition. After coating the coating liquid composition prepared by using an automatic coater (Bar coater) on a PET film, and dried for 5 minutes at 80 ℃ with a hot air dryer to prepare a color correction film having a coating layer thickness of 8 ㎛.

< Example 4>

0.015% by weight of the cyanine-based dye (TY-171) used in Example 3 and 0.007% by weight of a commercially available blue dye (Lmaplast Blue-DR from M-Dohmen Co., Ltd.) having a maximum absorption at 620-660 nm, around 490 nm. 0.007% by weight of commercially available red pigment (Lmapast Red-A2G from M-Dohmen) and 0.001% by weight of additional pigment (M-Dohmen Lumaplast Yellow-GG) having a maximum absorption at a wavelength of 1, Dissolved in 70% by weight of 3-dioxolane or methyl ethyl ketone (MEK), and then mixed with 30% by weight of the acrylic binder (IR-G205) to prepare a coating solution composition. After coating the coating liquid composition prepared by using an automatic coater (Bar coater) on a PET film, and dried for 5 minutes at 80 ℃ with a hot air dryer to prepare a color correction film having a coating layer thickness of 8 ㎛.

< Example 5>

Cyanine-based selective visible light (580 to 595 nm) absorbing dye (HAO-01) 0.022% by weight and commercially available blue pigment having a maximum absorption at 590 to 640 nm (0.022% by weight of Lumaplast Blue-RR from M-Dohmen) and green After dissolving 0.003% by weight of a pigment (M-Dohmen's Lumaplast Green-5B) in 40% by weight of 1,3-dioxolane or methyl ethyl ketone (MEK), an acrylic binder (ADKOPTOMER KRM-2826-1) 60 Mix with weight percent to prepare a coating solution composition. After coating the coating liquid composition prepared by using an automatic coater (Bar coater) on a PET film, and dried for 5 minutes at 80 ℃ with a hot air dryer to prepare a color correction film having a coating layer thickness of 8 ㎛.

< Example 6 >

0.02% by weight of porphyrin-based selective visible light absorbing pigment (TAP-2) and a commercially available blue pigment (M-Dohmen's Lumaplast Blue-DR) having a maximum absorption at 620-660 nm, wavelength of around 490 nm 0.007% by weight of the commercially available red pigment (Lmapast Red-A2G from M-Dohmen) and 0.005% by weight of the violet pigment (M-Dohmen Lumaplast Violet-R) to match the color coordinates After dissolving in 70% by weight of dioxolane or methyl ethyl ketone (MEK), and mixed with 30% by weight of an acrylic binder (IR-G205) to prepare a coating solution composition. The coating liquid composition prepared by using an automatic coater (Bar coater) was applied to a PET film, and then dried at 80 ° C. for 5 minutes with a hot air dryer to prepare a color correction film having a coating layer thickness of 8 μm.

The minimum transmittance in the specific visible light region (580-595 nm) of the color correction film prepared by Examples 3 to 6 was measured using a spectrophotometer of Perkin-Elmer, and the CIE According to the -1930 standard, color coordinate values were calculated using a D ₆₅ light source and a 2 ° viewing angle, and the results are shown in Table 4.

< Example 7>

The pressure-sensitive adhesive film is added to the coated surface of the color correction film prepared in Examples 3 to 6, and it is attached to the tempered glass coated with tin oxide or a thin film of anti-oxidation by lamination. Thereafter, an antireflection film was attached to the opposite side of the tempered glass to prepare a color correction filter for PDP.

Light emission (625-635nm) (arbitrary unit) TY-171 HAO-01 TAP-2  Excitation wavelength (nm) 300 24.6 71 5.7 400 25 110 4.2 500 107.6 207 27 600 8.3 117 8.9

Luminescence (625 to 635 nm) (arbitrary unit) TY-171 HAO-01 TAP-2  Pigment ratio (Red-AG / cyanine or porphyrin pigment) 0.2 84.6 171 22.5 0.4 70.2 142 19.8 0.6 58.5 122 17.1 0.8 49.3 94 14.7

Light emission (625 ~ 635nm) (arbitrary unit) TY-171 HAO-01 TAP-2  Pigment ratio (Blue-DR / cyanine or porphyrin pigment) 0.2 60.7 124 12.7 0.4 13.8 36.1 ≒ 0 0.6 ≒ 0 3.5 ≒ 0 0.8 ≒ 0 ≒ 0 ≒ 0

Minimum transmittance (%) (580 ~ 595 nm) Color coordinate value (CIE-1930 standard, 2 ° viewing angle, D ₆₅ light source) x y Y (%) Example 3 31.9 0.280 0.302 65.9 Example 4 33.3 0.281 0.298 66.6 Example 5 33.7 0.280 0.298 66.2 Example 6 32.3 0.279 0.303 65.9

Through Tables 1 to 4, in order to remove the fluorescence of the cyanine or porphyrin-based pigment, which is a selective visible light absorbing dye, the fluorescence can be effectively reduced by adding a small amount of the dye having the maximum absorption at the maximum excitation wavelength band and the maximum emission wavelength band of the dye. It can be seen that a color correction film having a desired color can be produced.

According to the fluorescence removal method of the selective visible light absorbing dye of the present invention, the fluorescence can be effectively reduced by using a dye having an absorption maximum at the maximum excitation wavelength band and the maximum emission wavelength band of the cyanine or porphyrin pigment. In addition, it is also possible to produce a color correction filter of the plasma display with reduced fluorescence using the coating liquid composition for color correction film using the fluorescence removal method of the present invention.

Claims (10)

In the fluorescence removal method of the selective visible light absorbing dye, a pigment having a maximum absorption wavelength near the maximum excitation wavelength of the selective visible light absorbing dye that fluoresces and a pigment having a maximum absorption wavelength near the maximum emission wavelength of the selective visible light absorbing dye are selected. Fluorescence removal method of the selective visible light absorption pigment | dye characterized by adding 1 or more types. The method of claim 1, wherein the maximum absorption wavelength of the selective visible light absorbing dye is 580 ~ 595 nm fluorescence removal method of the selective visible light absorbing pigment. The method of claim 1 or 2, wherein the selective visible light absorbing dye is a cyanine of the formula (1) or a porphyrin dye of the formula (2) having a maximum excitation wavelength of 450 to 550 nm, a maximum emission wavelength of 600 to 700 nm. Fluorescence treatment of selective visible light absorbing pigments characterized by: [Formula 1]

Wherein X and Z each represent O, S, Se or an amine (RN ^- wherein R represents an alkyl or substituted phenyl group), Y represents an alkyl, alkyl ether or alkyl ester, and R ¹ to R ⁹ represents an alkyl or alkoxy or substituted phenoxy or thiophenoxy or halogen, each of which is C _1-4 , or a cyclic or aromatic cyclic compound which forms a five- or six-membered circle with each other in close proximity, and A- is the anion paired F, Cl, Br, halogens, perchlorate (ClO ₄ ^-) of the I, borate (BF ₄ ^-) tetrafluoroborate, antimonate hexafluorophosphate (SbF ₆ ^-), para-toluenesulfonyl Nate or camphorsulfonate; [Formula 2]

In the formula, M represents a metal of Mg, Cu, Zn, Pd, Ni, R ¹ represents halogen or C _1-4 alkyl or C _1-4 alkoxy group, R ² -R ⁶ are each C _1-4 alkyl or C _1-4 alkoxy or phenoxy or substituted phenoxy or C _1-4 alkylsulfide or thiophenoxy or substituted thiophenoxy or phenyl or substituted phenyl or halogens Indicates. According to claim 1, wherein the pigment having a maximum absorption wavelength in the vicinity of the maximum excitation wavelength of the selective visible light absorbing dye or a pigment having a maximum absorption wavelength in the vicinity of the maximum emission wavelength of the selective visible light absorbing pigment is a quinophthalone system, Composed of Thioxanthene, Methine, Perynone, Anthraquinone, Anthrapyridone, Quinacridone and Phthalocyanine Selective fluorescence removal method of the selective visible light absorbing pigment, characterized in that one species selected from the group. (i) Cyanine of formula (I) or porphyrin dye of formula (II) having a maximum excitation wavelength of 450 to 550 nm and a maximum emission wavelength of 600 to 700 nm: (ii) 450 to 550 nm or 600 to 700 nm wavelength band Pigments with maximum absorption at; (iii) additional pigments for obtaining the desired color coordinates in addition to the (i) pigment and the (ii) pigment; (iv) organic solvents; And (v) coating liquid composition for a color correction film comprising a binder. [Formula 1]

Wherein X and Z each represent O, S, Se or an amine (RN ^- wherein R represents an alkyl or substituted phenyl group), Y represents an alkyl, alkyl ether or alkyl ester, and R ¹ to R ⁹ represents an alkyl or alkoxy or substituted phenoxy or thiophenoxy or halogen, each of which is C _1-4 , or a cyclic or aromatic cyclic compound which forms a five- or six-membered circle with each other in close proximity, and A- is the anion paired F, Cl, Br, halogens, perchlorate (ClO ₄ ^-) of the I, borate (BF ₄ ^-) tetrafluoroborate, antimonate hexafluorophosphate (SbF ₆ ^-), para-toluenesulfonyl Nate or camphorsulfonate; [Formula 2]

In the formula, M represents a metal of Mg, Cu, Zn, Pd, Ni, R ¹ represents halogen or C _1-4 alkyl or C _1-4 alkoxy group, R ² -R ⁶ are each C _1-4 alkyl or C _1-4 alkoxy or phenoxy or substituted phenoxy or C _1-4 alkylsulfide or thiophenoxy or substituted thiophenoxy or phenyl or substituted phenyl or halogens Indicates. The coating liquid composition for a color correction film according to claim 5, wherein the maximum absorption wavelength of the dye (ii) is in the range of 470 to 520 nm or 620 to 650 nm. The coating solution composition for a color correction film according to claim 5 or 6, wherein the content of the dye (ii) is 50 to 200% by weight of the cyanine or porphyrin dye. The coating liquid composition of claim 5 or 6, wherein the organic solvent is selected from the group consisting of ketone compounds, ether compounds, and aromatic compounds, and the binder is an acrylic binder. The color correction film using the coating liquid composition for color correction films of Claim 5 or 6. A color correction filter for display using the color correction film of claim 9.

Images