JP2008239592A - Porphyrin compound and filter for display - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a filter for a display that can exclude unnecessary light present between blue and green generated in various displays and has excellent durability, and a compound to be used for the filter for a display that has excellent solubility to a solvent. <P>SOLUTION: The porphyrin compound having the selective absorption maximum between 440 nm and 510 nm and excellent durability and solubility, and the filter for a display using the porphyrin compound are provided. <P>COPYRIGHT: (C)2009,JPO&amp;INPIT

Description

  The present invention relates to a porphyrin compound and a display filter containing the porphyrin compound. In more detail, it is installed to improve the color purity of luminescent colors such as liquid crystal display (LCD), plasma display panel (PDP), electroluminescence display (ELD), cathode ray tube display (CRT), field emission display, etc. The present invention relates to a display filter.

  In recent years, with the advancement of society, optoelectronics-related parts and devices have made remarkable progress every day. In particular, displays for displaying images have been remarkably popularized and developed for computer monitor devices in addition to conventional television receivers. Along with these developments, market demands for display enlargement, thinning, and high image quality are increasing.

  Recently, full-color display is a matter of course when used as a display device. Image display devices such as liquid crystal display devices (LCDs), plasma display panels (PDPs), electroluminescence displays (ELDs), cathode ray tube display devices (CRTs), and electro-emission displays are so-called “colors”. It is possible to display a color image with a combination of “three primary colors”.

  However, each image display device includes extra light emission that reduces the color purity, which is said to be unnecessary emission, in addition to the emission wavelengths of red, green, and blue due to its emission principle. This unnecessary light emission loses the clearness of the image. On the other hand, if the light of the unnecessary wavelength portion is blocked and the three primary colors of red, green, and blue can be extracted as single colors as much as possible, the sharpness (color purity) of the image can be improved.

  Conventionally, various methods have been studied in order to block unnecessary light emission. In LCDs, color purity is improved by improving color filters, and various studies have been reported on other display devices. Up to now, as attempts to improve color purity, Japanese Patent Application Laid-Open No. 58-153904 (Patent Document 1), Japanese Patent Application Laid-Open No. 59-221943 (Patent Document 2), Japanese Patent Application Laid-Open No. 60-22102 (Patent Document). 3), there are reports in JP-A-60-65050 (Patent Document 4), JP-A-5-316329 (Patent Document 5), etc., but the effect is not sufficient. This report mainly discloses a technique for improving the color purity of red, and there are few descriptions regarding the color purity of green and blue.

  In general, a display device under a bright place causes a decrease in contrast due to external light. Conventionally, an ND filter has been used to reduce the influence of external light as much as possible to improve contrast. However, in this method, necessary light emission emitted from the display device is also cut at the same time, which may be accompanied by a decrease in luminance. If it is possible to transmit only necessary light from the display device while selectively blocking outside light, it is considered that an ideal optical filter can be obtained.

  As a method for improving the color purity and contrast at the same time, there is a method using a filter containing a dye that absorbs light in an unnecessary wavelength region, and various studies have been made so far.

  JP-A-2005-338661 (Patent Document 6) reports a filter that efficiently removes unnecessary light existing between blue and green with a pigment. This publication discloses examples of preferred substituents for porphyrin dyes to be carried on a filter from the viewpoint of ease of production, solubility in solvents, dye stability, and absorption characteristics.

Examples of the method for supporting the dye on the filter include:
(1) To be contained in a transparent substrate such as a polymer molded body,
(2) Coating the transparent substrate surface as a dye-containing resin layer.
(3) To be included in the adhesive material,
In any case, it is important to dissolve the dye in an organic solvent to obtain a uniform dye solution from the viewpoint of reducing defects caused by undissolved dye.

However, as a result of additional tests on conventional porphyrin-based dyes, it was revealed that the solubility in organic solvents is not always sufficient.
JP 58-153904 A JP 59-221943 A JP 60-22102 A JP 60-65050 A JP-A-5-316329 JP 2005-338661 A

  The problem to be solved by the present invention is to eliminate unnecessary light existing between blue and green generated in various display devices and to have excellent durability, and to be used for the display filter. It is to provide a compound excellent in solubility in a solvent.

As a result of intensive studies to solve the above problems, the present inventors have completed the present invention. That is, the present invention
[1] A porphyrin compound represented by the general formula (1),

[Wherein R represents an alkyl group having 12 or less carbon atoms, and M represents a divalent atomic group including two hydrogen atoms, a divalent metal, a trivalent metal, or a divalent group including a tetravalent metal. Represents the atomic group. ]
[2] A display filter comprising a porphyrin compound according to [1] in a base material,
About.

  By using the porphyrin compound according to the present invention, it is possible to produce a display filter capable of reducing unnecessary luminescence and improving “color purity of luminescent color” and “contrast in a bright place”. In particular, the display filter of the present invention has a feature that it can selectively remove unnecessary light between blue and green existing in 440 nm to 510 nm, which has been considered difficult, and has excellent durability. Therefore, it is particularly suitable as a high-performance display filter for consumer use in which durability is important. Furthermore, since the porphyrin compound according to the present invention is excellent in solubility in a solvent, productivity at the time of producing the filter is improved. For this reason, the industrial value of the present invention is great.

  The display filter in the present invention contains at least one porphyrin compound represented by the general formula (1).

[Wherein R represents an alkyl group having 12 or less carbon atoms, and M represents a divalent atomic group including two hydrogen atoms, a divalent metal, a trivalent metal, or a divalent group including a tetravalent metal. Represents the atomic group. ]
Specific examples of the porphyrin compound represented by the general formula (1) used in the present invention are described below.

  R represents an alkyl group having 12 or less carbon atoms.

  As the alkyl group having 12 or less carbon atoms, a branched or cyclic alkyl group having 1 to 12 carbon atoms is preferable from the viewpoint of solubility in a solvent, and a branched or cyclic alkyl group having 4 to 8 carbon atoms is particularly preferable.

  Specific examples of the alkyl group having 12 or less carbon atoms include methyl group, ethyl group, n-propyl group, iso-propyl group, n-butyl group, iso-butyl group, sec-butyl group, t-butyl group, n -Pentyl group, iso-pentyl group, 2-methylbutyl group, 1-methylbutyl group, neo-pentyl group, 1,2-dimethylpropyl group, 1,1-dimethylpropyl group, cyclopentyl group, n-hexyl group, 4- Methylpentyl group, 3-methylpentyl group, 2-methylpentyl group, 1-methylpentyl group, 3,3-dimethylbutyl group, 2,3-dimethylbutyl group, 1,3-dimethylbutyl group, 2,2- Dimethylbutyl group, 1,2-dimethylbutyl group, 1,1-dimethylbutyl group, 3-ethylbutyl group, 2-ethylbutyl group, 1-ethylbutyl group, 1,2,2-trimethylbutyl group, 1,1,2 -Trimethylbutyl group, 1-ethyl-2-methylpropyl group, cyclohexyl group, n-heptyl 2-methylhexyl group, 3-methylhexyl group, 4-methylhexyl group, 5-methylhexyl group, 2,4-dimethylpentyl group, n-octyl group, 2-ethylhexyl group, 2,5-dimethylhexyl group 2,5,5-trimethylpentyl group, 2,4-dimethylhexyl group, 2,2,4-trimethylpentyl group, n-octyl group, 3,5,5-trimethylhexyl group, n-nonyl group, n -Decyl group, 4-ethyloctyl group, 4-ethyl-4,5-dimethylhexyl group, n-undecyl group, n-dodecyl group, 1,3,5,7-tetraethyloctyl group, 4-butyloctyl group, 6,6-diethyloctyl group, n-tridecyl group, 6-methyl-4-butyloctyl group, n-tetradecyl group, n-pentadecyl group, 3,5-dimethylheptyl group, 2,6-dimethylheptyl group, 2 , 4-Dimethylheptyl, 2,2,5,5-tetramethylhexyl, 1-cyclopentyl-2,2-dimethyl Examples include a propyl group and a 1-cyclohexyl-2,2-dimethylpropyl group.

  M represents two hydrogen atoms, a divalent metal, an atomic group containing a trivalent metal, or an atomic group containing a tetravalent metal.

  Specific examples when M is a divalent metal include Cu (II), Zn (II), Fe (II), Co (II), Ni (II), Ru (II), Rh (II), Pd (II), Pt (II), Mn (II), Mg (II), Ti (II), Be (II), Ca (II), Ba (II), Cd (II), Hg (II), Pb (II) and Sn (II) are mentioned.

The atomic group containing a trivalent or tetravalent metal, AlCl, InCl, FeCl, MnCl , SiCl 2, GeCl 2, TiO, VO , and the like.

  The preferable specific example of the porphyrin compound shown by General formula (1) of this invention is shown.

  The porphyrin compound represented by the general formula (1) of the present invention is, for example, halogenated at the 3,4-position of the pyrrole part of meso-tetraphenylporphyrin, and coupled with an acetylene derivative substituted with R according to a known method. It can be easily obtained by ring reaction.

  The display filter of the present invention may be composed of a plurality of members having a multilayer structure as will be described later, but the porphyrin compound represented by the general formula (1) of the present invention is contained in only one member. It is not necessary to be contained, and may be contained in a plurality of members.

  Moreover, you may use together the pigment | dye which has absorption in visible region other than the porphyrin compound shown by General formula (1) of this invention according to the desired optical characteristic.

  The display filter of the present invention is characterized in that it contains the porphyrin compound represented by the general formula (1) of the present invention. Moreover, the member which comprises the filter for displays of this invention can use a conventionally well-known thing without a restriction | limiting. For example, as a member constituting the display filter, a transparent substrate (C), a conductive layer (D), and a functional transparent layer (E) can be mentioned. Furthermore, the toning layer (F) containing a pigment | dye may be contained. Furthermore, an adhesive material layer, an adhesive material layer, an impact relaxation layer, an electrode, etc. can also be mentioned.

  As said conductive layer (D), transparent thin films, such as a metal and a metal oxide, a metal mesh layer, etc. are mentioned. Examples of the functional transparent layer (E) include known functional transparent layers such as an antireflection layer, an antiglare layer, an antifouling layer, a hard coat layer, and an anti-Newton ring layer. Of course, one layer may have two or more of the above functions. In the display filter of the present invention, it is preferable that the porphyrin compound represented by the general formula (1) of the present invention is included in any one of the above-described layers and the like. As said toning layer (F), although it is preferable that the porphyrin compound shown by General formula (1) of this invention is contained, it is not restrict | limited to this.

  Further, when the toning layer (F) contains the porphyrin compound represented by the general formula (1) of the present invention, the display has a configuration in which the porphyrin compound is contained in each of the layers other than the toning layer (F). Of course, a filter is also included in the present invention.

  As a configuration of the display filter of the present invention, for example, when a plasma display filter is taken as an example, as a preferred form thereof,

(I) A filter for plasma display having a transparent substrate (C), a conductive layer (D), and a functional transparent layer (E), wherein the transparent substrate (C), the conductive layer (D), and the functional transparent Of the members constituting each of the layers (E), a filter for a plasma display containing the dye of the present invention in at least one member,

(Ii) A plasma display filter having a transparent substrate (C), a conductive layer (D), a functional transparent layer (E), and a toning layer (F), wherein the toning layer (F) is the present invention. And a plasma display filter containing the above dye.

In this invention, the porphyrin compound shown by General formula (1) is contained in at least any one of the members which comprise the filter for a display, It is characterized by the above-mentioned. The method of supporting the dye on the member is not particularly limited, but when specifically exemplified, the dye is
(1) Included in the transparent substrate (C)
(2) Coating the surface of the transparent substrate (C) as a dye-containing resin layer.
(3) To be included in the adhesive material,
And the like. Any known technique may be used as a method for containing the dye as long as the dye is uniformly distributed.

  The method of (1) above in which the pigment is contained in the transparent substrate (C) is specifically exemplified. For example, when the pigment is mixed with the polymer molded body that is the transparent substrate (C), the polymer molded body is constituted. Processing temperature and filming conditions vary depending on the type of resin (hereinafter referred to as base resin). Usually, pigment is added to the base resin powder or pellets, and 150 to 350 ° C. in consideration of the melting temperature of the resin. And a method of forming a plastic sheet and plastic particles by molding after heating and melting, preferably kneading. An additive such as a plasticizer may be added for the purpose of facilitating molding.

  There is a casting method as another method. In the casting method, a dye is added to and dissolved in a resin solution in which a resin or resin monomer is dissolved in an organic solvent, and a plasticizer, a polymerization initiator, an antioxidant, etc. are added as necessary, and the required surface state The polymer molded body can be obtained by pouring into a metal mold having a solvent and volatilizing / drying of the solvent or volatilization / drying of the polymerization / solvent.

  The added amount of the dye varies depending on the absorption coefficient of the dye, the thickness of the polymer molded body, and the desired transmission characteristics, but usually from 1 ppm (parts per million by mass) of the molded body obtained by molding the base resin. 20 weight percent.

  Specific examples of the method of (2) above in which the pigment is coated on the surface of the transparent substrate (C) as a pigment-containing resin layer include those obtained by dissolving the pigment in a binder resin and an organic solvent, An acrylic emulsion-based water-based paint obtained by dispersing a finely pulverized pigment (particle size 50 nm to 500 nm) in a colored acrylic emulsion paint is a bar coater, blade coater, spin coater, reverse coater, die coater, or Examples thereof include a method of coating and drying on the surface of a polymer molded body or glass as a transparent substrate (C) by a conventionally known coating method such as spraying. The concentration of the dye varies depending on the absorption coefficient of the dye, the thickness of the coating, and the target optical characteristics, but is 0.001 to 30 mass percent with respect to the binder resin. In addition, you may add antioxidant etc. in a coating material. Moreover, you may provide a protective layer in order to protect a coating surface.

  The method of (3) above in which a dye is contained in the adhesive material is specifically exemplified. In the present invention, an adhesive, an adhesive, a pressure-sensitive adhesive, and a pressure-sensitive adhesive are described as a pressure-sensitive adhesive without being distinguished. Adhesive materials include acrylic resins, silicone resins, urethane resins, polyvinyl butyral resins, ethylene-vinyl acetate resins, polyvinyl ether resins, saturated amorphous polyesters, melamine resin sheets, and liquid adhesive materials. Is mentioned. A pigment is added to these adhesive materials to obtain an adhesive material containing a pigment. The addition amount of the dye varies depending on the absorption coefficient of the dye, the thickness of the adhesive material, and the original optical properties, but is usually 1 ppm (parts per million by mass) to 30 mass percent of the base adhesive material.

  Examples of the method for forming the adhesive material layer include a method of directly applying an adhesive material to a substrate, or a method of peeling off one release film of an adhesive material sandwiched between release films and attaching it to a substrate. In the invention, the latter is preferably used. As a method for applying the adhesive material, it is generally applied by a bar coating method, a reverse coating method, a gravure coating method, a roll coating method or the like, but is not limited thereto. In the present invention, the bar coat method is preferably used. The thickness of the pressure-sensitive adhesive layer is not particularly limited, but is 0.5 μm to 50 μm, preferably 1 μm to 30 μm.

  The pressure-sensitive adhesive material containing a pigment can be used for various types of laminating such as a film and a film and a film and glass, and is one of the preferred forms as a method of incorporating a pigment.

  Since the display filter has a high surface temperature of the display panel or may have a higher temperature in the usage environment, the temperature of the display filter itself may increase. For this reason, when the dye is included in the display filter, the dye preferably has, for example, heat resistance at 80 ° C. that does not significantly deteriorate due to decomposition or the like. To specifically illustrate the heat resistance of the desirable dye, the absorption maintenance factor at the maximum absorption wavelength of the dye under an environment of 80 ° C. is 80% or more after holding for 250 hours, preferably 80% or more after 500 hours, Preferably, it is 80% or more after 1000 hours or more.

What is the absorption retention rate here?
(T0-Tmax, 1) / (T0-Tmax, 0)
Means.

  Here, T0 represents the transmittance | permeability in the wavelength which does not absorb at all, such as the member containing a pigment | dye, for example, the adhesive containing a pigment | dye.

  Tmax, 0 represents the transmittance at the maximum absorption wavelength, and (T0−Tmax, 0) represents the difference between T0 and Tmax, 0.

  Tmax, 1 represents the transmittance at the maximum absorption wavelength of the adhesive after being placed in each environment for a predetermined time, and (T0-Tmax, 1) represents the difference between T0 and Tmax, 1.

  It can be considered that the larger the value of the absorption maintenance ratio, the more the dye performance is maintained, that is, the durability. In addition to heat resistance, some dyes have poor light resistance, and the display itself may emit light, and external light may be deteriorated by ultraviolet rays or visible rays. In this case, a method of using a member containing an ultraviolet absorber or a member (layer) that does not transmit ultraviolet light on the side on which ultraviolet rays or visible rays are incident on the side containing the pigment, visible light having a wavelength that causes deterioration of the pigment. This can be overcome by using a known light shielding technique that reduces deterioration of the dye, such as a method using a member containing the absorbing dye or a member that does not transmit visible light. Of course, if a dye that is not deteriorated by ultraviolet rays or visible light can be used, it is not necessary to use the above technique in combination.

  As the desirable light resistance of the dye of the present invention, the absorption maintenance factor at the maximum absorption wavelength of the dye when irradiated with light in the visible region of 380 nm to 780 nm at an intensity of 50 mW / cm 2 is 80% after irradiation for 250 hours. Above, preferably 80% or more after irradiation for 500 hours or more, more preferably 80% or more after irradiation for 1000 hours or more. The same applies to humidity and a combined environment in addition to heat and light. When the colorant deteriorates, the transmission characteristics of the display filter itself may change, and the color tone may change. In addition, the near-infrared cutting ability may change.

  Furthermore, as a characteristic required for the coloring matter, solubility in an organic solvent is important in order to disperse in a medium or a coating film.

  The porphyrin compound represented by the general formula (1) of the present invention is very excellent in environmental resistance such as heat resistance and light resistance as compared with conventional dyes having maximum absorption at 440 nm to 510 nm, and has a long time. Therefore, it is possible to improve the display on the display without degrading the performance. Further, by selecting a specific substituent, it is possible to obtain a uniform display filter having very high solubility in an organic solvent.

  The color purity of any known display can be improved by the display filter containing the above-described pigment in the present invention. In particular, it can be suitably used for a plasma display, a liquid crystal display, and an organic electroluminescence display. As the application method, any known method can be adopted.

  Hereinafter, each member that can be used for the display filter will be briefly described.

  As the transparent substrate (C), those mainly in the form of a film and a plate, excellent in transparency, and having sufficient mechanical strength according to the use are preferable. The term “excellent transparency” as used herein means that the average luminous transmittance is 40% or more in the thickness in the used state (measurement method: JIS R3106). For example, a polymer film, a polymer plate, or a glass plate. In the present invention, a known transparent substrate as described above can be used without limitation.

  The conductive layer (D) preferably has at least an electromagnetic wave shielding function. This is because a display device such as a plasma display panel may generate leakage electromagnetic waves or near infrared rays due to its structure and operation principle, and may need to be shielded from these. Usually, in order to shield electromagnetic waves, the display surface is often covered with a highly conductive material. This is due to a mechanism in which the above-mentioned conductive material absorbs electromagnetic waves and develops an electromagnetic wave shielding ability to release them as electric charges.

  In order to apply this principle to a display filter, the conductive layer (D) is preferably transparent to visible light. Therefore, the conductive layer (D) specifically includes a single-layer metal thin film, an oxide semiconductor film, a multilayer thin-film transparent conductive thin film, a conductive mesh, a synthetic fiber coated with metal, a metal fiber mesh, Furthermore, a metal-coated one is a preferable example.

The conductivity of the conductive layer (D) required for shielding electromagnetic waves in various display devices such as plasma displays depends on the required electromagnetic wave standards and radiation intensity from plasma displays, but the surface resistance is 10 Ω / cm ² or less. Preferably, it is 3Ω / cm ² . In the case of strict electromagnetic wave standards required for consumer applications, it is preferably 1 Ω / cm ² or less, more preferably 0.1 Ω / cm ² or less. In order to shield near infrared rays emitted from a plasma display or the like, the transmittance of the display filter in the near infrared wavelength region of 800 to 1000 nm is preferably 20% or less.

  In the present invention, as the conductive layer (D), a multilayer transparent conductive thin film layer (a) obtained by laminating a metal thin film and a transparent high refractive index thin film, or a conductive mesh layer (b) can be suitably used. The multilayer transparent conductive thin film layer (a) has a lower cost than the conductive mesh layer and reflects near infrared rays due to the free electrons of the metal constituting the metal thin film. It has the feature of having both. On the other hand, the conductive mesh layer (b) can have higher conductivity without significantly degrading the optical characteristics. Therefore, when a high electromagnetic shielding function is required, for example, the above-described consumer use is required. Suitable for meeting strict electromagnetic wave standards.

  As a multilayer transparent conductive thin film layer (a) in which a metal thin film and a transparent high refractive index thin film are laminated, a dielectric such as indium oxide, zinc oxide or titanium oxide is formed on one main surface of the transparent substrate (C). A configuration in which the main high refractive index layer (c) and the metal thin film layer (d) mainly containing silver are laminated by repeating the stacking unit of (c) / (d) in the order of 1 to 6 times is preferable. Further, a structure in which all the metal thin film layers (d) are laminated so as to be sandwiched between the high refractive index layers (c) is more preferable. The larger the number of layers of the high refractive index layer (c) and the metal thin film layer (d), the better the balance between conductivity and transparency. However, in consideration of cost and quality stability, 11 layers or less, more preferably 9 layers or less, and particularly preferably 7 layers or less. In order to improve the environmental resistance of the transparent conductive thin film layer, an organic or inorganic protective layer may be provided on the surface of the transparent conductive thin film layer. Furthermore, in order to improve the environmental resistance of the metal thin film layer and the adhesion between the high refractive index layer and the metal thin film layer, a functional layer is provided between the high refractive index layer (c) and the metal thin film layer (d). It doesn't matter.

  As specific compounds constituting the high refractive index layer (c) and the metal thin film layer (d), known compounds can be used without limitation. For example, those described in Japanese Patent No. 3004222 can be suitably used. More specifically, examples of the high refractive index layer (c) include metal oxides such as indium oxide, indium-tin oxide (ITO), and titanium oxide. Moreover, as a metal thin film layer (d), silver and the alloy of silver and another metal can be mentioned as a preferable example. As a method for forming these thin film layers, any known method can be employed in addition to a vacuum film forming method such as a sputtering method, a vacuum deposition method, an ion plating method, and an ion beam assist method. Among these, a vacuum film forming method, particularly a sputtering method can be preferably used.

  As the conductive mesh layer (b), there can be used a fiber mesh obtained by vapor-depositing a metal on a fiber, an etching mesh that forms a pattern using a photolithography technique, and obtains a mesh by etching. More specifically, a metal mesh mainly using copper can be preferably used, but is not limited thereto. The shape of the mesh may be a lattice shape or a honeycomb shape, and is not particularly limited. This mesh can have a high electromagnetic shielding function. When the conductive mesh layer (b) is used as the conductive layer (D), it is preferable to use a layer that absorbs near-infrared rays or reflects near-infrared rays to provide a near-infrared blocking function. In particular, it is preferable to use a layer containing a dye that absorbs near infrared rays and absorbs little or no visible light. Of course, the transparent conductive thin film layer can be used.

  Specific functions of the functional transparent layer (E) include hard coat properties, antireflection properties, antiglare properties, antistatic properties, antifouling properties, gas barrier properties, near infrared ray cut properties, ultraviolet ray cut properties, and color tones. Although it is mentioned that it has at least one or more of known functions and functions such as a color function and a mesh flattening function, the function to be added is not limited to this. In particular, it is preferable to arrange the layer having an ultraviolet cutting ability on the human side. The functional transparent layer (E) can take any form such as a film, a film, an adhesive layer, and a composite thereof as long as it has the above-described functions such as antireflection properties. It does not specifically limit as a formation method of a functional transparent layer (E), It can form using all well-known techniques. The functional transparent layer (E) may be formed in two or more layers, and one layer may have a plurality of functions.

  More specifically, for example, those described in Japanese Patent No. 3004222 can be suitably used as these members. Moreover, the lamination | stacking method of these layers can use a well-known method without a restriction | limiting, More specifically, the method described in patent 3004222, Unexamined-Japanese-Patent No. 2002-40233, etc. can be employ | adopted. .

  Since the plasma display equipped with the display filter obtained as described above can remove unnecessary light emission emitted from the light source without deterioration in performance over a long period of time, the color purity of the luminescent color, particularly the blue color purity. Becomes an improved display. In addition, the display filter of the present invention can remove unnecessary light due to external light, so that a display with improved contrast in a bright place is obtained.

  The liquid crystal display or organic electroluminescence display using the display filter of the present invention is preferably characterized in that the display filter is disposed between the light source and the visual recognition part. Hereinafter, a liquid crystal display will be described as an example, but the same method can also be adopted in an organic electroluminescence display.

One of the preferred embodiments for implementing the display filter included in the liquid crystal panel has at least a transparent substrate (C), a functional transparent layer (E), and a toning layer (F) as necessary. And the dye of the present invention is contained in at least one of the constituent layers and constituent members.
As a method of incorporating the dye, the same method as described in the description of the plasma display filter can be used. The same applies to the amount of dye added.

  As the transparent substrate (C) and functional transparent layer (E) of the display filter provided in the liquid crystal panel, the same materials as those described in the description of the plasma display filter can be used. In addition, as a method for laminating the above layers, a conventionally known method can be adopted without limitation. As preferred materials and methods described above, materials and methods described in, for example, JP-A-2002-40233 can be employed.

  The liquid crystal display using the display filter of the present invention is (I) used by being attached to a component of the liquid crystal display via an adhesive layer, and (II) inserted between the light source of the liquid crystal display and the visual recognition part. A configuration to be used can be given as a suitable example.

  The liquid crystal display or organic electroluminescence display equipped with the display filter obtained as described above can remove unnecessary light emission emitted from the light source without deterioration of performance over a long period of time, similar to the above-mentioned plasma display, A display with improved color purity of the luminescent color, especially blue, and a display with improved contrast in a bright place. The display filter in the present invention may be used in combination of two or more types of filters. A plurality of the same type of filters may be used.

  In addition to the above, the display filter of the present invention can of course be used in combination with a known display such as a CRT display, a field emission display, or an inorganic electroluminescence display. In addition, those displays equipped with the display filter of the present invention can also remove unnecessary light emission over a long period of time and have excellent contrast, and provide a beautiful image, particularly as a display having a high blue color purity. I can do it.

  The present invention will be specifically described with reference to examples. The present invention is not limited by the following examples.

[Synthesis of Specific Example Compound (1-2)]
15.0 g of the compound represented by the following structural formula (2-a) was dissolved in 150 ml of N, N-dimethylformamide, and 31.8 g of bromine was added dropwise at 10-20 ° C. After stirring at room temperature for 4 hours, the mixture was discharged into 700 g of ice water and neutralized with an aqueous sodium hydroxide solution. The precipitate was collected by filtration, washed with water, washed with methanol, and dried to obtain 31 g of a compound represented by the following structural formula (2-b).

  Next, 26.1 g of the compound represented by the structural formula (2-b), 1.34 g of copper iodide, 2.13 g of bis (triphenylphosphine) palladium (II) dichloride and 1.05 g of triphenylphosphine are dissolved in 525 ml of tetrahydrofuran. Then, 36.4 g of triethylamine and 21.16 g of 3,3-dimethyl-1-butyne (purity 96%) were added. The mixture was stirred at room temperature under a nitrogen stream, and after completion of the reaction, insoluble matters were filtered, and the filtrate was concentrated under reduced pressure. To the concentrated residue, 500 ml of 85% aqueous methanol was added, stirred, filtered, washed with 85% aqueous methanol and dried to obtain a crude product. The crude product was purified by a silica gel column (developing solvent: toluene / hexane = 6: 4 vol. Ratio) to obtain 10.8 g of the specific example compound (1-2).

  From the following analysis results, it was confirmed to be the target product.

Elemental analysis value (C ₉₂ H ₉₂ N ₄ Ni)

MS (m / e): 1312 (M ^<+> )

The compound thus obtained showed an absorption maximum at 481.0 nm in a chloroform solution, and the gram extinction coefficient was 1.57 × 10 ⁵ ml / g. cm.

  Further, the obtained compound was mixed in an ethyl acetate / toluene (content ratio 50:50 mass percent) solvent so as to have a concentration of 1 mass%, and sonicated at room temperature for 30 minutes to be completely dissolved.

[Synthesis of Specific Example Compound (1-3)]
17.0 g of the compound represented by the following structural formula (3-a) was dissolved in 170 ml of N, N-dimethylformamide, and 35.8 g of bromine was added dropwise at 10-20 ° C. After stirring at room temperature for 4 hours, it was discharged into 800 g of ice water and neutralized with an aqueous sodium hydroxide solution. The precipitate was collected by filtration, washed with water, washed with methanol, and dried to obtain 32 g of a compound represented by the following structural formula (3-b).

  Next, 26.2 g of the compound represented by the structural formula (3-b), 1.34 g of copper iodide, 2.13 g of bis (triphenylphosphine) palladium (II) dichloride and 1.05 g of triphenylphosphine are dissolved in 525 ml of tetrahydrofuran. Then, 36.4 g of triethylamine and 21.16 g of 3,3-dimethyl-1-butyne (purity 96%) were added. The mixture was stirred at room temperature under a nitrogen stream, and after completion of the reaction, insoluble matters were filtered, and the filtrate was concentrated under reduced pressure. To the concentrated residue, 500 ml of 85% aqueous methanol was added, stirred, filtered, washed with 85% aqueous methanol and dried to obtain a crude product. The crude product was purified by a silica gel column (developing solvent: toluene / hexane = 6: 4 vol. Ratio) to obtain 13.3 g of the specific example compound (1-3).

  From the following analysis results, it was confirmed to be the target product.

Elemental analysis value (C ₉₂ H ₉₂ N ₄ OV)

MS (m / e): 1321 (M ^<+> )

The compound thus obtained showed an absorption maximum at 496.5 nm in a chloroform solution, and the gram extinction coefficient was 1.73 × 10 ⁵ ml / g. cm.

  Further, the obtained compound was mixed in an ethyl acetate / toluene (content ratio 50:50 mass percent) solvent so as to have a concentration of 1 mass%, and sonicated at room temperature for 30 minutes to be completely dissolved.

  The specific compound (1-2) is dispersed and dissolved in an ethyl acetate / toluene (content ratio 50:50 mass percent) solvent, and the pigment concentration in the resin when dried is 1000 ppm (parts per million by mass). Thus, a dye-containing diluent for an acrylic adhesive was prepared. Next, an acrylic pressure-sensitive adhesive (a copolymer of butyl acrylate and acrylic acid, trade name: DB bond, manufactured by Diabond Kogyo Co., Ltd.) / Dye-containing diluent (content ratio: 80:20 mass percent) was mixed. With respect to the surface on which the antireflection film is not formed of the antireflection film [antireflection film made by Nippon Oil & Fats Co., Ltd., which has an antireflection film formed on a polyethylene terephthalate film, thickness: 105 μm] It was continuously coated by the bar coater method and dried. Thereafter, a release film on which a silicone release layer was formed was bonded to the coated surface to produce an antireflection film with an adhesive containing a dye having a paste thickness of 25 μm.

  The release film of the prepared antireflection film with a dye-containing adhesive is peeled off and bonded to the front of a commercially available liquid crystal display [manufactured by Sharp Corporation, LC-15B1-S], and the antireflection film with an adhesive containing the dye is attached. A liquid crystal display comprising

  The chromaticity coordinates of the produced liquid crystal display were measured with a spectral radiance meter [CS-1000, manufactured by Konica Minolta Holdings, Inc.] to obtain red, green, and blue chromaticity coordinates. The color reproducibility of the produced liquid crystal display is determined by comparing the area of the triangle obtained by connecting each chromaticity coordinate representing the color reproduction range of the display device with the liquid crystal display equipped with an antireflection film that does not use a pigment. evaluated.

  As a result, assuming that the area of the triangle of the liquid crystal display provided with the antireflection film not using the dye is 100, the area of the triangle of the liquid crystal display provided with the antireflection film with the dye adhesive prepared is 106, The liquid crystal display using the dye was a display with improved color reproducibility.

(Comparative Example 1)
Under the same conditions as in Example 1, a compound represented by the structural formula (2-b) and a phenylacetylene were subjected to a coupling reaction to prepare a compound represented by the following structural formula (A-1).

The compound represented by the structural formula (A-1) exhibits an absorption maximum at 498.0 nm in a chloroform solution, and its gram extinction coefficient is 2.33 × 10 ⁵ ml / g. cm.
When mixed in an ethyl acetate / toluene (content ratio 50:50 mass percent) solvent to a concentration of 1 mass% and sonicated at room temperature for 30 minutes, there was undissolved residue. Further diluted and mixed and sonicated to a concentration of 0.5% by weight, but did not dissolve completely.

(Comparative Example 2)
When an antireflective film with a dye-containing adhesive was produced in the same manner as in Example 3 except that the compound (A-1) was used instead of the specific compound (1-2), points resulting from the dissolved residue of the dye A defect occurred.

  The display filter containing the porphyrin compound of the present invention can be used for any known display. The filter selectively absorbs unnecessary light emission between blue and green and contains a dye having excellent durability, thereby improving the color purity of the display without deteriorating the performance over a long period of time. Thus, a display capable of displaying a clear image with improved contrast in a bright place can be provided.

Claims (2)

The porphyrin compound shown by General formula (1).

[Wherein R represents an alkyl group having 12 or less carbon atoms, and M represents a divalent atomic group including two hydrogen atoms, a divalent metal, a trivalent metal, or a divalent group including a tetravalent metal. Represents the atomic group. ] A display filter comprising the porphyrin compound according to claim 1 in a base material.