JP4544914B2 - Dye for plasma display front panel and plasma display front panel using the same - Google Patents

Description

  The present invention relates to a dye for a plasma display front panel and a plasma display front panel using the same. In particular, the present invention relates to a dye for a plasma display front panel comprising a subphthalocyanine compound having excellent selective absorption ability for light in a specific wavelength range of 580 to 600 nm, and a plasma display front panel capable of producing a clear image by using the same. Is. Further, a plasma display comprising a subphthalocyanine compound capable of selectively and effectively absorbing light of 580 to 600 nm and a near infrared absorbing dye capable of selectively and effectively absorbing near infrared light on a longer wavelength side of 750 to 1200 nm. The present invention relates to a dye for a front panel and a plasma display front panel which can produce a clear image and can effectively suppress malfunction of a remote controller or the like.

  In recent years, PDPs (Plasma Display Panels) that are thin and applicable to large screens have attracted attention. A problem with PDPs is that near-infrared light is generated during plasma discharge, and this near-infrared light induces malfunctions of electrical devices such as televisions for home appliances, coolers, and video decks. For this reason, the plasma display front panel is blended with a compound having high visible light transmittance, high near-infrared light cutting efficiency, and excellent near-infrared selective absorption ability. As such a compound, a phthalocyanine compound having a specific structure is disclosed (for example, see Patent Document 1). Moreover, as a near-infrared shielding film having high near-infrared shielding properties and visible light transmittance, a transparent resin film layer, a transparent near-infrared shielding layer containing a near-infrared absorber, a transparent resin film layer, and the shielding layer A near-infrared shielding film is also reported in which a transparent color tone compensation layer containing a color material that compensates the color tone is laminated and a diimonium-based compound is used as a near-infrared absorber (for example, Patent Document 2). reference).

  The compounds disclosed in Patent Documents 1 and 2 absorb near-infrared light and suppress malfunction of a remote controller or the like, but have the ability to absorb orange light on the short wavelength side of 550 to 620 nm, particularly near 580 nm. Low. This orange light is one of the causes of blurring the image. For this reason, the plasma display front panel using the near-infrared absorption filter containing the compound as described above has a new problem that the image becomes unclear.

  In order to solve such problems, a near-infrared absorption filter that selectively absorbs only orange light (550 to 620 nm region) that blurs an image but hardly absorbs other visible light regions has been developed. (For example, refer to Patent Documents 3 and 4). Among these, Patent Document 3 contains one or more near-infrared absorbing dyes (A dyes) having an absorption maximum wavelength at 750 to 1200 nm, and has an absorption maximum wavelength at 575 to 595 nm and a half-value width of 40 nm. There is disclosed a near-infrared absorbing film in which a resin layer having a thickness of 1 to 50 microns containing one or more of the following B dyes is formed on a transparent substrate. Of the above dyes, as dye A, diimonium-based, nickel dithiolene complex-based, phthalocyanine-based, and cyanine-based compounds are exemplified. Examples of the dye having selective absorption of neon emission, that is, the dye B having an absorption maximum wavelength at 575 to 595 nm and a half width of 40 nm or less include squarylium compounds and cyanine compounds.

Patent Document 4 discloses a near-infrared absorbing material that uses a transparent resin coating film containing a near-infrared absorbing dye and a dye that selectively absorbs only a wavelength region of 550 to 620 nm. Among the above dyes, the near infrared absorbing dye includes a dithiol nickel complex, a diimonium compound, and a polymethine dye, and the cyanine dye is exemplified as a dye that selectively absorbs orange light (550 to 620 nm region).
JP 2001-106869 A JP 2001-133624 A JP 2002-187229 A JP 2002-200711 A

  However, the squarylium-based and cyanine-based compounds disclosed in Patent Documents 3 and 4 certainly absorb light in the 550 to 620 nm region, but it is difficult to say that this range of light absorption is sufficient. In addition, since the half width of absorption is wide, it absorbs light in a wavelength region outside the above range at the same time, particularly absorbs red light near 630 nm and green light near 545 nm, and the necessary RGB light from the plasma display panel. In particular, there is a problem that R light and G light cannot be sufficiently extracted and sufficient color purity cannot be achieved.

  Therefore, the present invention has been made in view of the above circumstances, and the front surface of a plasma display capable of achieving a clear image containing a compound capable of absorbing orange light in the 550 to 620 nm region more selectively and with high absorption ability. It aims at providing the pigment | dye for panels.

  Another object of the present invention includes a compound that selectively absorbs light in a narrow wavelength range of 580 to 600 nm and absorbs orange light with a high absorption capacity such that the minimum transmittance at 580 to 600 nm is 40% or less. It is to provide a dye for a plasma display front panel using a near infrared absorption filter. In the present specification, the “minimum transmittance at 580 to 600 nm” represents the minimum value of the transmittance in the wavelength range of 580 to 600 nm.

  Still another object of the present invention is to provide a clear infrared ray absorbing compound having a maximum absorption wavelength at 750 to 1200 nm, in addition to a compound capable of absorbing orange light in the 550 to 620 nm region more selectively and with high absorption ability. It is an object of the present invention to provide a dye for a plasma display front panel that can achieve an image and prevent malfunction of a remote controller or the like.

  Another object of the present invention is to provide a plasma display front panel containing a pigment as described above and having a clear image.

  Still another object of the present invention is to provide a plasma display front panel that contains a dye as described above, has a clear image, and does not cause a malfunction of the remote control.

  As a result of intensive studies on various compounds in order to achieve the above-mentioned objects, the present inventors have focused on subphthalocyanine compounds. That is, a subphthalocyanine compound into which at least one group containing sulfur or oxygen (i.e., -SR, -OR) is introduced selectively emits light in a narrow wavelength range of 580 to 600 nm (i.e., 40% or less). Such a compound that absorbs (with the lowest transmittance at 580 to 600 nm) and exhibits high transmittance for visible light other than the above range (ie, high transmittance at 400 to 700 nm excluding 580 to 600 nm). It has been found that the image can be sharpened by using as a filter for a plasma display front panel. The present inventors have also found that such a subphthalocyanine compound is excellent in solvent solubility, compatibility with a resin, moisture resistance, heat resistance, and light resistance. In addition to the above knowledge, by combining a sub-phthalocyanine compound as described above with a near-infrared absorbing compound having an absorption maximum wavelength at 750 to 1200 nm and using it for a filter of a plasma display front panel, an image can be sharpened. In addition, it has also been found that it is possible to effectively suppress a malfunction of a remote controller or the like by absorbing only near-infrared rays having a longer wavelength while maintaining transparency in a desired visible light region. The subphthalocyanine compound is conventionally used as a dye in a recording layer of an optical recording medium capable of recording / reproducing with respect to a laser beam having a wavelength of 520 to 690 nm (Japanese Patent Laid-Open No. 10-330633). Although it has been known that it is used as a pigment used for color pixels of liquid crystal displays (Japanese Patent Laid-Open No. 2004-10838), a subphthalocyanine compound having a specific group according to the present invention is more It has not been known that light in a narrow wavelength range can be selectively and efficiently absorbed, and that such a compound can be suitably used as a dye for a plasma display front panel. Based on the above findings, the present invention has been completed.

  That is, the object of the present invention is the following formula (1):

However, Z < ₁ > -Z < ₁₂ > represents a hydrogen atom, the C1-C20 alkyl group which may have a substituent, a halogen atom, -SR < ¹ >, or -OR < ² > each independently, In this case, at least one represents -SR ¹ or -OR ² ; each of R ¹ and R ² independently represents a phenyl group which may have a substituent, or an aralkyl which may have a substituent. Represents an alkyl group having 1 to 20 carbon atoms which may have a group or a substituent, and a plurality of R ¹ and R ² may be the same or different from each other; X is a halogen atom, hydroxy A group, an alkoxy group, an alkoxyalkoxy group, an alkylthioalkoxy group or a dialkylaminoalkoxy group,
It is achieved by a dye for a plasma display front panel characterized by comprising a subphthalocyanine compound represented by the formula:

  Another object of the present invention is achieved by a plasma display front panel using a near-infrared absorbing filter containing the dye and resin of the present invention.

  The pigment | dye for plasma display front panels of this invention is characterized by including the subphthalocyanine compound of the said Formula (1). The subphthalocyanine compound according to the present invention selectively and efficiently absorbs orange light which causes blurring of an image of 550 to 620 nm, particularly 580 to 600 nm, but the half width of absorption is extremely narrow at 33.5 nm or less. As a result, the transmittance in other visible light regions such as RGB light, particularly R light near 630 nm and G light having a short wavelength is maintained at a high level. In addition, the color purity can be improved without interfering with the required RGB light emission from the plasma display panel.

  Further, as described above, the subphthalocyanine compound according to the present invention can absorb orange light of 550 to 620 nm, particularly 580 to 600 nm, more selectively and efficiently, and therefore, when used as a dye for a plasma display front panel. A clear image can be provided. Furthermore, by using the subphthalocyanine compound according to the present invention in combination with a near-infrared absorbing dye having an absorption maximum wavelength of 750 to 1200 nm as a dye for a near-infrared absorbing filter of a plasma display front panel, only orange light is selectively used. It absorbs light efficiently and improves image sharpness, while at the same time effectively absorbing near-infrared rays with longer wavelengths that were previously difficult to shield, and more effectively suppressing malfunctions such as remote controls. it can.

In addition to the above advantages, the subphthalocyanine compound according to the present invention has a specific group of -SR ¹ and / or -OR ² introduced into the subphthalocyanine skeleton, so that it has excellent solvent solubility and compatibility with a resin, In addition, because it has the advantage of being excellent in moisture resistance, heat resistance, and light resistance, especially when the near infrared absorbing dye having the absorption maximum wavelength used together is inferior in organic solvent solubility and / or resin compatibility In particular, the above-mentioned drawbacks of near-infrared absorbing dyes can be compensated for, which is particularly effective.

  Hereinafter, the present invention will be described in detail.

  The first of the present invention is the following formula (1):

The present invention relates to a dye for a plasma display front panel, comprising a subphthalocyanine compound represented by the formula: This is based on the knowledge that the subphthalocyanine compound of the formula (1) absorbs orange light in a specific region of 550 to 620 nm, particularly 580 to 600 nm, more selectively and efficiently. The subphthalocyanine compound having such a specific structure has a narrower range, particularly 580 to 600 nm, compared to a dye that is known to absorb orange light (550 to 620 nm), which has been a cause of blurring of conventional images. Can be absorbed selectively and efficiently, and the half-value width of absorption is as narrow as 33.5 nm or less, and other visible light such as RGB light (especially pure R light near 630 nm or an approximate wavelength) G light) is hardly disturbed. For this reason, the subphthalocyanine compound according to the present invention can sharpen the image of PDP and improve the color purity as compared with the case of using a conventional dye. Further, the subphthalocyanine compound of the formula (1) is used as a pigment for a plasma display front panel in combination with a near-infrared absorbing pigment having an absorption maximum wavelength particularly at 750 to 1200 nm, so that only orange light (550 to 620 nm) is used. Absorbs selectively and efficiently to improve image sharpness, and effectively absorbs near-infrared rays with longer wavelengths that were previously difficult to shield, effectively suppressing malfunctions such as remote controls It has also been found that it can. Since the subphthalocyanine compound according to the present invention is excellent in solvent solubility and compatibility with a resin, particularly when the near-infrared absorbing dye is inferior in organic solvent solubility and / or compatibility with a resin, There is also an advantage that the drawbacks can be compensated. In addition, the subphthalocyanine compound according to the present invention also has an advantage of excellent weather resistance (moisture resistance, heat resistance, light resistance).

In the above formula (1), Z _{1 to} Z ₁₂ represent a hydrogen atom, an optionally substituted alkyl group having 1 to 20 carbon atoms, a halogen atom, —SR ¹ or —OR ² , and At least one of Z _{1 to} Z ₁₂ represents —SR ¹ or —OR ² , preferably —OR ² . At this time, at least one of Z _{1 to} Z ₁₂ is —SR ¹ or —OR ² , more preferably 3 to 9 is —SR ¹ or —OR ² , and particularly preferably 3 to 6 Are —SR ¹ or —OR ² , most preferably 3 and 6 are —OR ² . In this case, when a plurality of -SR ¹ and / or -OR ² are present, -SR ¹ or -OR ² may be present at any position of the subphthalocyanine skeleton, for example, Z _{1 to} Z ₄ has —SR ¹ or —OR ² and may not be present in that portion, or may be present almost equally or evenly in Z _{1 to} Z ₄ , Z _{5 to} Z ₈ and Z _{9 to} Z _12. Preferably, —SR ¹ or —OR ² is present in Z ₁ -Z ₄ , Z ₅ -Z ₈ and Z ₉ -Z ₁₂ substantially equally or evenly, more preferably evenly. Z _{1 to} Z ₁₂ may be the same or different, and when a plurality of R ¹ and R ² are present in one compound, R ¹ and R ² are Each substituent may be the same or different. By introducing —SR ¹ and / or —OR ² , in particular —OR ^2, into the subphthalocyanine compound, orange light in the region of 550 to 620 nm, while maintaining a high level of visible light transmittance other than orange light, In particular, only light in a narrow range of 580 to 600 nm can be selectively cut (that is, with a minimum transmittance of 580 to 600 nm of 40% or less), and the half width of absorption can be extremely narrow to 33.5 nm or less. It hardly interferes with transmission of other visible light such as RGB light, in particular, pure R light near 630 nm and G light having an approximate wavelength.

  In the above formula (1), the halogen atom includes a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, preferably a fluorine atom and a chlorine atom, the absorption wavelength can be easily controlled, and the synthesis can be carried out easily and inexpensively. Fluorine atoms are particularly preferred because they have excellent compatibility with resins as compared with hydrogen atoms and other halogen atoms, and also have the effect of improving light resistance and heat resistance.

  In the above formula (1), the unsubstituted alkyl group in the alkyl group which may have a substituent has 1 to 20 carbon atoms, preferably 1 to 12 carbon atoms, more preferably 1 to 8 carbon atoms. And, specifically, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group N-pentyl group, isopentyl group, neopentyl group, 1,2-dimethylpropyl group, 1,1-dimethylpropyl group, cyclopentyl group, n-hexyl group, cyclohexyl group, 4-methylpentyl group, 3-methylpentyl group 2-methylpentyl group, 1-methylpentyl group, 3,3-dimethylbutyl group, 2,3-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-triethyl Butyl group, 1,1,2-triethylbutyl group, 1-ethyl-2-methylpropyl group, 1-isopropylpropyl group, n-heptyl group, 2-methylhexyl group, 3-methylhexyl group, 4-methylhexyl Group, 5-methylhexyl group, 4-methylcyclohexyl group, 1,4-dimethylpentyl group, 2,4-dimethylpentyl group, 2-methyl-1-isopropylpropyl group, 1-ethyl-3-methylbutyl group, n -Octyl group, t-octyl group, 2-ethylhexyl group, 2,5-dimethylhexyl group, 2,5,5-trimethylpentyl group, 2,4 Dimethylhexyl group, 2,2,4-trimethylpentyl group, 3,5,5-trimethylhexyl group, n-nonyl group, n-decyl group, 4-ethyloctyl group, 4-ethyl-4,5-methylhexyl Group, n-undecyl group, n-dodecyl group, 1,3,5,7-tetraethyloctyl group, 4-butyloctyl group, 6,6-diethyloctyl group, n-pentadecyl group, 3,5-dimethylheptyl group 2,6-dimethylheptyl group, 2,4-dimethylheptyl group, 2,2,5,5-tetramethylhexyl group, 1-cyclohexyl-2,2-dimethylpropyl group and the like. Of these, a methyl group, an ethyl group, and an isopropyl group are preferable, and a methyl group and an ethyl group are more preferable.

Examples of the substituent of the alkyl group include a halogen atom, an alkoxy group, a hydroxyalkoxy group, an aralkylalkoxy group, an alkoxyalkoxy group, a halogenated alkoxy group, a nitro group (—NO ₂ ), an amino group (—NH ₂ ), Examples thereof include an alkylamino group, an alkylcarbonyloxy group, an alkylthio group, an alkoxycarbonyl group, an alkylaminocarbonyl group, and an alkoxysulfonyl group. These types of substituents may be the same or different when a plurality of substituents are substituted.

  In this case, the halogen atom includes a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, preferably a fluorine atom and a chlorine atom.

  The alkoxy group as a substituent is a linear, branched or cyclic alkoxy group having 1 to 20 carbon atoms, preferably 1 to 12 carbon atoms, more preferably 1 to 8 carbon atoms. Methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, isobutoxy group, sec-butoxy group, tert-butoxy group, n-pentyloxy group, isopentyloxy group, neopentyloxy group, 1,2-dimethyl-propoxy group, n-hexyloxy group, cyclohexyloxy group and the like can be mentioned. Of these, a methoxy group, an ethoxy group, and an isopropoxy group are preferable, and a methoxy group and an ethoxy group are more preferable.

  The hydroxyalkoxy group as a substituent is a linear, branched or cyclic hydroxyalkoxy group having 2 to 20 carbon atoms, preferably 2 to 12 carbon atoms, more preferably 2 to 8 carbon atoms. And hydroxyethoxy group.

  The aralkylalkoxy group as a substituent is a linear, branched or cyclic hydroxyalkoxy group having 6 to 20 carbon atoms, preferably 6 to 12 carbon atoms, more preferably 2 to 8 carbon atoms. Benzyloxy group, p-chlorobenzyloxy group, p-methoxybenzyloxy group and the like.

  The alkoxyalkoxy group as a substituent is a linear, branched or cyclic alkoxyalkoxy group having 1 to 20 carbon atoms, preferably 1 to 12 carbon atoms, more preferably 1 to 8 carbon atoms. 2-methoxyethoxy group, 1-methoxybutan-2-yloxy group, 1-methoxybutan-1-yloxy group, 1-methoxypropan-2-yloxy group, 2- (2-methoxyethoxy) ethoxy group, 2- Ethoxyethoxy group, 2- (ethoxyethoxy) ethoxy group, 2-ethoxypropan-2-yloxy group, 2-iso-propoxyethoxy group, 2-butoxyethoxy group, 2-iso-butoxyethoxy group, 2-t-butoxy An ethoxy group, 2- (2-butoxyethoxy) ethoxy group, etc. are mentioned.

  Examples of the halogenated alkyl group as a substituent include those in which a part of a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, preferably 1 to 8 carbon atoms, is halogenated. , Chloromethyl group, bromomethyl group, fluoromethyl group, trifluoromethyl group, trichloromethyl group, tribromomethyl group, chloroethyl group, bromoethyl group, fluoroethyl group, 2,2,2-trichloroethyl group, bromoethyl group, chloro A propyl group, a bromopropyl group, etc. are mentioned.

  The alkylamino group as a substituent is an alkylamino group having 1 to 20 carbon atoms, preferably 1 to 12 carbon atoms, more preferably 1 to 8 carbon atoms, specifically, a methylamino group or an ethylamino group. , N-propylamino group, n-butylamino group, sec-butylamino group, n-pentylamino group, n-hexylamino group, n-heptylamino group, n-octylamino group, 2-ethylhexylamino group, dimethyl Amino group, diethylamino group, di-n-propylamino group, di-n-butylamino group, di-sec-butylamino group, di-n-pentylamino group, di-n-hexylamino group, di-n- A heptylamino group, a di-n-octylamino group, etc. are mentioned. Of these, a methylamino group, an ethylamino group, an n-propylamino group, and an n-butylamino group are preferable.

  The alkylcarbonyloxy group as a substituent is an alkylcarbonyloxy group having 2 to 20 carbon atoms, preferably 2 to 12 carbon atoms, more preferably 2 to 8 carbon atoms. Specifically, an acetyloxy group, ethyl Carbonyloxy group, n-propylcarbonyloxy group, iso-propylcarbonyloxy group, n-butylcarbonyloxy group, iso-butylcarbonyloxy group, sec-butylcarbonyloxy group, t-butylcarbonyloxy group, n-pentylcarbonyl Examples thereof include an oxy group, an n-hexylcarbonyloxy group, a cyclohexylcarbonyloxy group, an n-heptylcarbonyloxy group, a 3-heptylcarbonyloxy group, and an n-octylcarbonyloxy group.

  The alkylthio group as a substituent is an alkylthio group having 1 to 20 carbon atoms, preferably 1 to 12 carbon atoms, more preferably 1 to 8 carbon atoms, and specifically includes a methylthio group, an ethylthio group, and an n-propylthio group. Group, iso-propylthio group, n-butylthio group, iso-butylthio group, sec-butylthio group, t-butylthio group, n-pentylthio group, n-hexylthio group, cyclohexylthio group, n-heptylthio group, n-octylthio group , 2-ethylhexylthio group and the like.

  The alkoxycarbonyl group as a substituent has 1 to 8 carbon atoms which may contain a hetero atom in the alkyl group part of the alkoxy group, preferably 1 to 5 alkoxycarbonyl, or 3 to 3 carbon atoms which may contain a hetero atom. 8, preferably 5 to 8 cyclic alkoxycarbonyl. Specifically, hydroxycarbonyl group, methoxycarbonyl group, ethoxycarbonyl group, n-propyloxycarbonyl group, iso-propyloxycarbonyl group, n-butyloxycarbonyl group, iso-butyloxycarbonyl group, sec-butyloxycarbonyl Group, t-butyloxycarbonyl group, n-pentyloxycarbonyl group, n-hexyloxycarbonyl group, cyclohexyloxycarbonyl group, n-heptyloxycarbonyl group, n-octyloxycarbonyl group, 2-ethylhexyloxycarbonyl group, etc. Can be mentioned. Of these, a methoxycarbonyl group and an ethoxycarbonyl group are preferred.

  The alkylaminocarbonyl group as a substituent is an alkylaminocarbonyl group having 2 to 20 carbon atoms, preferably 2 to 12 carbon atoms, more preferably 2 to 8 carbon atoms, specifically, an aminocarbonyl group, methyl Aminocarbonyl group, ethylaminocarbonyl group, n-propylaminocarbonyl group, n-butylaminocarbonyl group, sec-butylaminocarbonyl group, n-pentylaminocarbonyl group, n-hexylaminocarbonyl group, n-heptylaminocarbonyl group N-octylaminocarbonyl group, 2-ethylhexylaminocarbonyl group, dimethylaminocarbonyl group, diethylaminocarbonyl group, di-n-propylaminocarbonyl group, di-n-butylaminocarbonyl group, di-sec-butylaminocarbonyl group , Di-n Pentyl aminocarbonyl group, di -n- hexylamino group, di -n- heptyl aminocarbonyl group, and di -n- octyl aminocarbonyl group.

  The alkoxysulfonyl group as a substituent is an alkoxysulfonyl group having 1 to 20 carbon atoms, preferably 1 to 12 carbon atoms, more preferably 1 to 8 carbon atoms, specifically, a methoxysulfonyl group or an ethoxysulfonyl group. Etc.

Further, in the above formula (1), “R ¹ ” and “R ² ” in the substituents —SR ¹ and —OR ² have a phenyl group which may have a substituent, or a substituent. Or an alkyl group having 1 to 20 carbon atoms which may have an aralkyl group or a substituent. In this case, R ¹ and R ² may be the same or different, and even when a plurality of R ¹ and R ² are present in one compound, R ¹ and R ² May be the same or different in each case. Here, examples of the aralkyl group include a benzyl group, a phenethyl group, and a diphenylmethyl group. In addition, the definition of the substituent and the like is the same as the definition related to the above substituent, and the same definition as the above definition applies to the alkyl group having 1 to 20 carbon atoms. The description is omitted.

In the present invention, the combination of Z _{1 to} Z ₁₂ selects only orange light in the 550 to 620 nm region, particularly light in a narrow range of 580 to 600 nm, while maintaining a high transmittance of visible light other than orange light. (Ie, with a minimum transmittance of 580 to 600 nm of 40% or less) and an absorption half width of 33.5 nm or less, and other visible light such as RGB light, particularly around 630 nm Is not particularly limited as long as it hardly interferes with transmission of pure R light or G light having an approximate wavelength, but preferably Z _{1 to} Z ₁₂ are a halogen atom, —SR ¹ and —OR. composed of ² alone, more preferably it consists of only a halogen atom and -OR ^2, even more preferably fluorine atom, only chlorine atoms and -OR ² Made by, and most preferably is preferably composed of only a fluorine atom and -OR ^2.

  Further, in the above formula (1), X represents a halogen atom, a hydroxy group (—OH), an alkoxy group, an alkoxyalkoxy group, an alkylthioalkoxy group or a dialkylaminoalkoxy group. In this case, the halogen atom includes a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, preferably a fluorine atom, a chlorine atom and a bromine atom, and particularly preferably a chlorine atom and a bromine atom.

The alkoxy group as the substituent “X” is a linear, branched or cyclic alkoxy group having 1 to 20 carbon atoms, preferably 1 to 12 carbon atoms, more preferably 1 to 8 carbon atoms. Specifically, methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, isobutoxy group, sec-butoxy group, tert-butoxy group, n-pentyloxy group, isopentyloxy group, neopentyl group Oxy group, n-octyloxy group, 1,2-dimethyl-propoxy group, n-hexyloxy group, cyclohexyloxy group, 3-methylpentan-2-yloxy group, 3-methylpentan-3-yloxy group, 4- Methylpentoxy group, 4-methylpentan-2-yloxy group, 1,3-dimethylbutoxy group, 1-isopropylpropoxy group, , 3-dimethylbutoxy group, 3,3-dimethylbutan-2-yloxy group, 2-methylhexane-2-yloxy group, 2,4-dimethylpentan-3-yloxy group, 1,1-dimethylpentane-1- Yloxy group, 2,2-dimethylhexane-3-yloxy group, 2,3-dimethylhexane-2-yloxy group, 2,5-dimethylhexane-2-yloxy group, 2,5-dimethylhexane-3-yloxy group 3,4-dimethylhexane-3-yloxy group, 3,5-dimethylhexane-3-yloxy group, 2-ethylhexyloxy group, 2-methylheptoxy group, 2-methylheptan-2-yloxy group, 3-methylheptane -3-yloxy group, 4-methylheptan-3-yloxy group, 4-methylheptan-4-yloxy group, 2 Methyloctane-3-yloxy group, n-dodecyloxy group, 4-methylcyclohexyloxy group, 4-ethylcyclohexyloxy group, 2-n-propylcyclohexyloxy group, 4-t-butylcyclohexyloxy group, adamantane- A 1-yloxy group, a borneol group, etc. are mentioned. Of these, a methoxy group, an ethoxy group, an isopropoxy group, and an n-octyloxy group are preferable.

  The alkoxyalkoxy group as the substituent “X” is preferably a linear or branched alkoxyalkoxy group having 2 to 12 carbon atoms, more preferably 2 to 8 carbon atoms. Specifically, 2-methoxyethoxy group, 1-methoxybutan-2-yloxy group, 1-methoxybutan-1-yloxy group, 1-methoxypropan-2-yloxy group, 2- (2-methoxyethoxy) ethoxy Group, 2-ethoxyethoxy group, 2- (ethoxyethoxy) ethoxy group, 2-ethoxypropan-2-yloxy group, 2-iso-propoxyethoxy group, 2-butoxyethoxy group, 2-iso-butoxyethoxy group, 2 -T-butoxyethoxy group, 2- (2-butoxyethoxy) ethoxy group and the like can be mentioned.

  The alkylthioalkoxy group as the substituent “X” is preferably a linear or branched alkylthioalkoxy group having 2 to 12 carbon atoms, more preferably 2 to 8 carbon atoms. Specifically, 2-methylthioethoxy group, 2-ethylthioethoxy group, 2-n-propylthioethoxy group, 2-iso-propylthioethoxy group, 2-n-butylthioethoxy group, 2-iso-butyl A thioethoxy group, 3-methylthiopropoxy group, 4-ethylthiobutoxy group, 4-butylthiobutoxy group and the like can be mentioned.

  The dialkylaminoalkoxy group as the substituent “X” is preferably a linear or branched dialkylaminoalkoxy group having 3 to 12 carbon atoms, more preferably 3 to 8 carbon atoms. Specifically, 2-dimethylaminoethoxy group, 2- (2-dimethylaminoethoxy) ethoxy group, 4-dimethylaminobutoxy group, 1-dimethylaminopropan-2-yloxy group, 2-diethylaminoethoxy group, 2- (2-Diethylaminoethoxy) ethoxy group, 3-diethylaminopropoxy group, 1-diethylaminopropoxy group, 2-di-iso-propylaminoethoxy group, 2-di-n-butylaminoethoxy group.

  Among the examples of the substituent “X”, a halogen atom, particularly a chlorine atom, a bromine atom and a fluorine atom are preferable, and a chlorine atom and a bromine atom are particularly preferable as the substituent “X”.

  Accordingly, particularly preferred specific examples of the subphthalocyanine compound of the formula (1) include the following compounds.

  In the above structural formula, R is a halogen atom, a methyl group, an ethyl group, a methoxy group, an ethoxy group, a methoxycarbonyl group, an ethoxycarbonyl group, particularly a chlorine atom, a methyl group, a methoxy group, an ethoxy group, and a methoxycarbonyl group. When there are a plurality of substituents R (that is, n is 2 to 4), they may be the same or different. Moreover, n shows the number which the substituent R couple | bonds with a benzene ring, 0-4, Preferably it is 0-3, More preferably, it is 0-2, Most preferably, it is 2. The bonding position of the substituent R is selectively limited to orange light in the 550 to 620 nm region, particularly light in a narrow range of 580 to 600 nm, while maintaining a high level of transmittance of visible light other than orange light (that is, Other than visible light such as RGB light, particularly pure R light around 630 nm, and the like, and the half width of absorption is extremely narrow, 33.5 nm or less (with a minimum transmittance of 580 to 600 nm of 40% or less). There is no particular limitation as long as it does not substantially impede the transmission of G light having an approximate wavelength. For example, when n is 1, the substituent R is preferably present at the 2-position of the benzene ring. When n is 2, the substituent R is preferably present at the 2-position and 5-position or 2-position and 6-position of the benzene ring. When n is 3, the substituent R is benzene. It is preferable to exist in the 2-position, 4-position and 6-position of the ring. X is a chlorine atom, a bromine atom and a fluorine atom, particularly a chlorine atom and a bromine atom.

  The subphthalocyanine compound according to the present invention can selectively and efficiently absorb orange light (550 to 620 nm) with a minimum transmittance at 580 to 600 nm of 40% or less. If the selective absorption of orange light of 550 to 620 nm, particularly 580 to 600 nm, is low, the image may be unclear. For this reason, the subphthalocyanine compound according to the present invention will be described in detail below, but it is preferable that the transmittance decrease when processed into a near-infrared absorption filter occurs in the wavelength range of 550 to 620 nm, particularly 580 to 600 nm. If the decrease in transmittance deviates from the above range, there is a risk that transmission of pure R light (630 nm) or transmission of G light close to the wavelength of orange light may be hindered. This is because the purity may not be achieved. The subphthalocyanine compound according to the present invention is described in detail below. When processed into a near-infrared absorption filter, the minimum transmittance at 580 to 600 nm is 40% or less, more preferably 35% or less, most preferably It is preferable that it is 30% or less. This is because if it deviates from the above range, the orange light cannot be sufficiently absorbed and the image may become unclear.

  The subphthalocyanine compound according to the present invention has a very narrow half-width of absorption of 33.5 nm or less. For this reason, the subphthalocyanine compound according to the present invention hardly interferes with transmission of other visible light such as RGB light, in particular, pure R light near 630 nm and G light having an approximate wavelength. At this time, when the half-width of absorption exceeds 33.5 nm, the subphthalocyanine compound has a wavelength range other than 550 to 620 nm, particularly 580 to 600 nm, particularly R light and orange light of 630 nm. This is because the transmission of near G light may be hindered, R light and G light may not be sufficiently extracted, and sufficient color purity may not be achieved. The half width of absorption of the subphthalocyanine compound according to the present invention is preferably 33.5 nm or less, more preferably 32 nm or less, and most preferably 31.5 nm or less.

  The method for producing the subphthalocyanine compound of the above formula (1) is not particularly limited, and is a method described in JP-A-10-330633, JP-A-2004-10838, JP-T-2003-500510, or the like. For example, a method obtained by modifying the above method in the same manner as a known method can be used. Hereinafter, preferred embodiments of the method for producing a subphthalocyanine compound according to the present invention will be described.

  That is, first, in a suitable solvent, the following formula (2):

A phthalonitrile derivative represented by the following formula (3) is reacted with a boron halide:

Y represents a halogen atom,
A subphthalocyanine in which a halogen atom is coordinated to a boron atom represented by the formula (1) is obtained. In the above formula (2), the substituent Z is appropriately selected depending on the substituents Z _{1 to} Z ₁₂ in the formula (1) representing the subphthalocyanine compound according to the present invention. Further, in the formula (1), when X is a halogen atom, the subphthalocyanine of the formula (3) produced by the first step is obtained as the target subphthalocyanine compound of the present invention. Next, the subphthalocyanine of the formula (3) thus obtained is reacted with an alcohol represented by the formula (4): X—OH, and Y in the subphthalocyanine is substituted with X to form a boron atom. A subphthalocyanine compound of the formula (1) in which the substituent X is coordinated is obtained (second stage).

The starting phthalonitrile derivative of the formula (2) can be synthesized by a conventionally known method such as the method disclosed in JP-A No. 64-45474, or a commercially available product can be used. Preferably, the phthalonitrile derivative of formula (2) is obtained by reacting a halogenated phthalonitrile compound with HSR ¹ and / or HOR ² . In this case, the halogenated phthalonitrile compound is not particularly limited, but tetrafluorophthalonitrile, tetrachlorophthalonitrile, tetrabromophthalonitrile, etc. are preferably used, and tetrafluorophthalonitrile, tetrachlorophthalonitrile are particularly preferably used. . The ratio of HSR ¹ and / or HOR ² is appropriately selected depending on the structure of the desired phthalonitrile derivative. Further, the total amount of HSR ¹ and / or HOR ² used is not particularly limited as long as these reactions can proceed to produce a desired phthalonitrile derivative, and is usually appropriately selected stoichiometrically. For example, when the subphthalocyanine compounds (A) to (F) are produced, the total amount of HSR ¹ and / or HOR ² is preferably 1.0 with respect to 1 mol of the halogenated phthalonitrile compound. ˜6.0 mol, particularly preferably 1.1 to 2.5 mol.

In addition, the synthesis reaction of the phthalonitrile derivative of the above formula (2) may be performed without a solvent or in an organic solvent, but is preferably performed in an organic solvent. Organic solvents that can be used at this time include a halogenated phthalonitrile compound as a starting material, HSR ¹ , HOR ² and a product having a low reactivity with respect to the phthalonitrile derivative of formula (2), preferably inert. And is not particularly limited as long as the reaction can proceed efficiently, for example, benzene, toluene, xylene, nitrobenzene, monochlorobenzene, dichlorobenzene, trichlorobenzene, 1-chloronaphthalene, 1-methylnaphthalene, ethylene glycol, And inert solvents such as benzonitrile; and non-protons such as pyridine, N, N-dimethylformamide, N-methyl-2-pyrrolidinone, N, N-dimethylacetophenone, triethylamine, tri-n-butylamine, dimethyl sulfoxide, sulfolane Sex polarity A solvent, acetonitrile, acetone, methyl ethyl ketone, etc. are mentioned. Of these, 1-chloronaphthalene, 1-methylnaphthalene, benzonitrile, acetonitrile, acetone, and methyl ethyl ketone are preferable, and benzonitrile, acetonitrile, acetone, and methyl ethyl ketone are more preferable. When the reactivity is low, HSR ¹ or HOR ² itself may be used as a reaction solvent. The amount of the organic solvent used when the solvent is used is not particularly limited, but the concentration of the halogenated phthalonitrile compound is usually 10 to 60 (w / v)%, preferably 20 to 50 (w / v)%. The amount is such that

The reaction conditions for the halogenated phthalonitrile compound and HSR ¹ and / or HOR ² are not particularly limited as long as these reactions proceed efficiently. For example, the reaction temperature is preferably −50 to 150 ° C., more preferably −10 to 100 ° C., and the reaction time is preferably 1 to 24 hours, more preferably 1 to 10 hours. The reaction may be performed under normal pressure or under pressure, but is usually performed under normal pressure. The reaction between the halogenated phthalonitrile compound and HSR ¹ and / or HOR ² is accompanied by the generation of hydrogen halide (eg, hydrogen fluoride). In order to remove this hydrogen halide, these traps are used. It is preferable to use an agent. Specific examples of the trapping agent when using the trapping agent include calcium carbonate, calcium hydroxide, magnesium hydroxide, magnesium chloride and magnesium carbonate. Among these, calcium carbonate and calcium hydroxide are preferable. . Further, the amount of the trapping agent used when using the trapping agent is not particularly limited as long as it can efficiently remove hydrogen halide generated during the reaction, but with respect to 1 mol of the halogenated phthalonitrile compound, Usually, it is 1.0-4.0 mol, Preferably it is 1.1-2.0 mol.

  The boron halide used in the first stage is not particularly limited as long as the reaction with the phthalonitrile derivative of the formula (2) can proceed efficiently. For example, boron tribromide, boron trichloride, Examples thereof include boron trifluoride and boron triiodide. Of these, boron tribromide and boron trichloride are preferably used. Further, the amount of boron halide used is not particularly limited as long as the reaction with the phthalonitrile derivative of formula (2) efficiently proceeds and the desired subphthalocyanine of formula (3) is efficiently produced. However, it is preferably 0.3 to 3.0 mol, more preferably 0.5 to 2.0 mol, with respect to 1 mol of the phthalonitrile derivative of the formula (2).

  The first step may be performed in the absence of a solvent or in an organic solvent, but is preferably performed in an organic solvent. As the solvent used in the first step, the starting material is a phthalonitrile derivative of formula (2) and a boron halide and a product having a low reactivity with respect to the subphthalocyanine of formula (3), preferably It is not particularly limited as long as it is inactive and the reaction between the phthalonitrile derivative and the boron halide can proceed efficiently. For example, trichlorobenzene, dichlorobenzene, naphthalene, chloronaphthalene, nitrobenzene, sulfolane, quinoline, etc. A boiling point solvent etc. are mentioned. The said solvent may be used independently or may be used with the form of a 2 or more types of mixture. The amount of the solvent used is not particularly limited as long as the reaction between the phthalonitrile derivative and the boron halide can proceed efficiently, but the concentration of the phthalonitrile derivative is usually 10 to 60 (w / v)%, preferably Is such an amount as 20-40 (w / v)%.

  The reaction conditions for the first stage are not particularly limited as long as the reaction between the phthalonitrile derivative and the boron halide proceeds efficiently. For example, the reaction temperature is preferably 100 to 240 ° C, more preferably 130 to 190 ° C, and the reaction time is preferably 1 to 12 hours, more preferably 1 to 5 hours. The reaction may be performed under normal pressure or under pressure, but is usually performed under normal pressure.

  The reaction in the first stage is carried out in the presence of a catalyst for the purpose of promoting the reaction between the phthalonitrile derivative and the boron halide to increase the amount of subphthalocyanine produced by the formula (3). Also good. The catalyst that can be used in this case is not particularly limited, and examples thereof include organic bases such as pyridine, picoline, triethylamine, N-methylpyrrolidone, and 1,5-diazabicyclo [5,4,0] undecene (DBU). . The amount of the catalyst used when the catalyst is used is not particularly limited as long as it can accelerate the reaction between the phthalonitrile derivative and the boron halide, but is 0.1 to 5 with respect to 1 mol of the phthalonitrile derivative. Mol, more preferably 0.5 to 2 mol.

  In order to purify the subphthalocyanine of the formula (3) thus formed, the above reaction product is put into a poor solvent that dissolves unreacted impurities and byproducts without dissolving much of the subphthalocyanine. Alternatively, a method of crystallizing desired subphthalocyanine by introducing a poor solvent into the reaction product can be used. By further stirring and washing the crystallized product thus obtained with a poor solvent, the purity of the target subphthalocyanine can be further increased. The poor solvent that can be used in the above method is not particularly limited as long as it does not dissolve subphthalocyanine so much and can dissolve unreacted impurities and by-products of impurities, for example, aliphatic hydrocarbons such as hexane and octane, Examples thereof include alcohols such as methanol, ethanol and isopropyl alcohol, and water-soluble solvents such as acetonitrile and acetone. In addition, the above poor solvent can be used alone, but when the target subphthalocyanine has high solubility and is difficult to purify, it is preferably 5 to 40% by mass for the purpose of improving the precipitation of subphthalocyanine. More preferably, 10 to 30% by mass of water mixed with the poor solvent is used in the crystallization, stirring and washing steps.

  When the subphthalocyanine of the formula (3) thus formed is used as a precursor in the next second step, the subphthalocyanine may be used as it is in the form of a reaction solution or as described above. Although it may be used after being purified by a known purification means such as filtration, washing, drying, etc., it is preferable to use it as it is in the second stage in view of the labor of the reaction.

  The alcohol represented by the formula (4): X—OH used in the second stage reacts with the subphthalocyanine of the formula (3), so that Y in the subphthalocyanine is efficiently substituted with X to form a boron atom. Although it will not restrict | limit especially if the desired subphthalocyanine compound of the formula (1) coordinated with the substituent X is obtained, For example, 2-methyl-2-hexanol, 2,4-dimethyl-3-pen Tanol, 1,1-dimethyl-1-pentanol, 2,2-dimethyl-3-hexanol, 2,5-dimethyl-2-hexanol, 2,5-dimethyl-3-hexanol, 2-ethyl-1-hexanol 2-methylheptanol, 2-methyl-2-heptanol, 3-methyl-3-heptanol, 4-methyl-4-heptanol, 2-methyl-3-octanol, 2- Tokiethanol, 1-methoxy-2-butanol, 1-methoxy-1-butanol, 1-methoxy-2-propanol, 2- (2-methoxyethoxy) ethanol, 2-ethoxyethanol, 2- (ethoxyethoxy) ethanol, 1-Ethoxy-2-propanol, 2-iso-propyloxyethanol, 2-butoxyethanol, 2-iso-butoxyethanol, 2-tert-butoxyethanol, 2- (2-butoxyethoxy) ethanol, 2-dimethylaminoethanol 2- (2-dimethylaminoethoxy) ethanol, 4-dimethylamino-1-butanol, 1-dimethylamino-2-propanol, 3-dimethylamino-1-propanol, 2-dimethylamino-2-methyl-1- Propanol, 2-diethylaminoethanol 2- (2-diethylaminoethoxy) ethanol, 3-diethylaminopropanol, 1-diethylaminopropanol, 2-di-iso-propylaminoethanol, 2-di-n-butylaminoethanol, 2-methylthioethanol, 2-ethylthio Ethanol, 2-n-propylthioethanol, 2-iso-propylthioethanol, 2-n-butylthioethanol, 2-iso-butylthioethanol, 1-adamantanol, 2-adamantanol, tetrahydrofurfuryl alcohol, Borneol, 1-methylcyclohexanol, 2-methylcyclohexanol, 3-methylcyclohexanol, 4-methylcyclohexanol, 2-ethylcyclohexanol, 4-ethylcyclohexanol, 2-n-propyl Examples thereof include clohexanol and 4-tert-butylcyclohexanol. In addition, the said alcohol may be used independently or may be used with the form of a 2 or more types of mixture.

  The amount of the alcohol added is not particularly limited as long as it is an amount capable of efficiently reacting with the subphthalocyanine of the formula (3) to produce a sufficient amount of the desired subphthalocyanine compound.

  In the second step, the reaction of the subphthalocyanine of formula (3) with the alcohol is carried out using the solvent used in the first step as it is when the subphthalocyanine of formula (3) is used without purification. Alternatively, the same solvent may be added, another solvent may be used in combination, or another solvent may be substituted. Solvents that can be used when other solvents are used in combination or substituted with other solvents are the reaction with the subphthalocyanine and alcohol of formula (3) as the raw material and the subphthalocyanine compound of formula (1) as the product. It is not particularly limited as long as it is low in activity, preferably inert, and can proceed with these reactions efficiently. For example, aromatic hydrocarbons such as benzene, toluene and xylene can be used. The said solvent may be used independently or may be used with the form of a 2 or more types of mixture. The total amount of the solvent used is not particularly limited as long as the reaction of subphthalocyanine and alcohol can proceed efficiently, but the concentration of subphthalocyanine is usually 10 to 60 (w / v)%, preferably 20 to The amount is 50 (w / v)%.

  The reaction conditions in the second stage are not particularly limited as long as the reaction between the subphthalocyanine of formula (3) and the alcohol proceeds efficiently. For example, the reaction temperature is preferably 10 to 150 ° C., more preferably 50 to 100 ° C., and the reaction time is preferably 1 to 24 hours, more preferably 1 to 12 hours. The reaction may be performed under normal pressure or under pressure, but is usually performed under normal pressure.

  The subphthalocyanine compound of the formula (1) thus formed may be purified by the same method as described in detail for the purification of the subphthalocyanine, but after the reaction, the solvent is distilled off from the reaction solution. Then, by purifying the residue by recrystallization or column chromatography, the target subphthalocyanine compound of the formula (1) may be obtained efficiently and with high purity without going through a complicated production process.

  The subphthalocyanine compound according to the present invention as described above and / or obtained by the above method transmits a desired visible light region including RGB light with little or no absorption, and transmits from 550 to 620 nm, particularly from 580 to 600 nm. Can be absorbed selectively and efficiently (ie, with a minimum transmittance of 580 to 600 nm of 40% or less), and the half width of absorption is extremely narrow at 33.5 nm or less. Since it hardly interferes with the transmission of visible light, particularly pure R light around 630 nm and G light having an approximate wavelength, RGB required from the plasma display panel when used as a dye for the front panel of the plasma display The color purity can be improved and the screen can be made clear without hindering light emission.

  Moreover, it is preferable that the pigment | dye for plasma display front panels of this invention further contains the near-infrared absorption compound which has an absorption maximum wavelength in at least 1 type of 750-1200 nm in addition to the said subphthalocyanine compound. By further including such a compound, it is possible to effectively absorb near-infrared rays on the longer wavelength side, which is conventionally difficult to shield, and at the same time achieve the effect of more effectively suppressing malfunctions such as remote controls. Because.

  The near-infrared absorbing compound that can be used in the above embodiment is not particularly limited as long as it has an absorption maximum wavelength at 750 to 1200 nm, and known compounds can be used. In this case, when the near-infrared absorbing compound has low absorption of orange light of 550 to 620 nm, particularly 580 to 600 nm, the effect of the subphthalocyanine compound according to the present invention can be exhibited particularly effectively, which is preferable. The near-infrared absorbing compound may be used alone, but is preferably used in the form of a mixture of two or more. More preferably, the near-infrared absorbing compound having an absorption maximum wavelength at 750 to 1200 nm is at least one kind of dye having an absorption maximum wavelength at 900 to 1100 nm (hereinafter referred to as “dye A”) and at least one kind of 800 to It is composed of a dye having an absorption maximum wavelength at 900 nm (hereinafter referred to as “Dye B”).

  In the present invention, the dye A is not particularly limited as long as it has an absorption maximum wavelength at 900 to 1100 nm, and a known compound can be used, but a diimonium compound and a phthalocyanine compound are preferably used. Among these, as specific examples of diimonium compounds, JP-A Nos. 2001-174626, 2003-114323, 2002-303720, 2002-138203, 2002-178039, JP-A Examples thereof include diimonium compounds disclosed in JP-A-10-180922. Alternatively, a commercially available product may be used as the diimonium compound, for example, “IRG-022” or “IRG-040” manufactured by Nippon Kayaku Co., Ltd., “CIR-1081” manufactured by Nippon Carlit Co., Ltd. and so on. Specific examples of the phthalocyanine compound include JP-A No. 2004-18561, JP-A No. 2002-822193, JP-A No. 2001-133623, JP-A No. 2001-106689, JP-A No. 2000-26748, and JP-A No. 2000-63693. And phthalocyanine compounds disclosed in JP-A-10-182959. Alternatively, commercially available phthalocyanine compounds may be used. For example, Excolor IR-1, Excolor IR-2, Excolor 801K, Excolor 802K, Excolor 803K, Excolor 810K, Excolor 812K, manufactured by Nippon Shokubai Co., Ltd. Excolor IR-10, Excolor IR-10A, Excolor IR-14, Excolor IR-12, TX-EX810K; SIR-159 manufactured by Mitsui Toatsu Dye Co., Ltd. In addition, the said pigment | dye A may be used individually or may be used with the form of 2 or more types of mixtures.

  The dye B is not particularly limited as long as it has an absorption maximum wavelength at 800 to 900 nm, and a known compound can be used, but preferably a metal complex, a metal compound, a phthalocyanine compound, a naphthalocyanine compound, or a cyanine compound. Etc. Among these, specific examples of metal complexes include nickel, platinum, palladium and copper complex compounds disclosed in JP-A No. 2003-262719; copper complexes disclosed in JP-A No. 2001-174626; -230134, JP-A-10-217380, JP-A-2002-132176, JP-A-2002-303720, and the like. Specific examples of the metal compound include a copper compound disclosed in JP-A No. 2001-174626. Specific examples of the phthalocyanine compound include, in addition to those listed for the dye A, JP-A-9-249814, JP-A-10-78509, JP-A-11-269399, JP-A-2000-229980, and JP-A-2000-229980. Examples thereof include phthalocyanine compounds disclosed in 2002-123180, JP-A 2003-222721, JP-A 2004-126262, and the like. Specific examples of the naphthalocyanine compound include naphthalocyanine compounds disclosed in JP2003-222721, JP2002-114790, JP2002-123180A, and the like. Specific examples of the cyanine compound include cyanine compounds disclosed in JP2003-173020A and JP2001-305722A. Among these, metal complexes, metal compounds, cyanine compounds and JP-A-9-249814, JP-A-10-78509, JP-A-11-269399, JP-A-2000-229980, JP-A-2002-123180, JP The phthalocyanine compounds, particularly metal complexes and metal compounds disclosed in 2003-222721, JP-A-2004-126262, etc., have a low absorption of orange light of 550 to 620 nm, particularly 580 to 600 nm, There is a drawback that the solubility and the compatibility with the resin are low. As described above, since the subphthalocyanine compound according to the present invention can selectively and efficiently absorb orange light of 550 to 620 nm, particularly 580 to 600 nm, the disadvantage of the dye B is effective. Can be supplemented. In addition, as described above, since the subphthalocyanine compound according to the present invention has excellent solvent solubility and compatibility with the resin as described above, when using the dye B as described above, By using the subphthalocyanine compound according to the present invention, the solubility of the whole dye can be increased, and the above-mentioned drawbacks can be compensated. For this reason, the subphthalocyanine compound according to the present invention is particularly effective when the dye B having low orange light absorption, solubility in an organic solvent, or compatibility with a resin is used. In addition, the said pigment | dye B may be used individually or may be used with the form of 2 or more types of mixtures.

  In the above embodiment, the mixing ratio of the dyes A and B is not particularly limited as long as it is a ratio that can effectively absorb long-wavelength near-infrared rays and more effectively suppress malfunctions such as a remote control. The mass ratio of B is preferably 0.1 to 6: 1, more preferably 0.7 to 4: 1.

  Further, the blending ratio of the subphthalocyanine compound of formula (1) and the near-infrared absorbing compound in the case where the dye for plasma display front panel of the present invention further contains a near-infrared absorbing compound also causes the image to become unclear. Although it is not particularly limited as long as it is a ratio that can selectively and efficiently absorb orange light (550 to 620 nm), effectively absorb near-infrared light of a long wavelength, and more effectively suppress malfunction of a remote controller or the like. The mass ratio of the subphthalocyanine compound of formula (1) and the near infrared absorbing compound is preferably 1: 1 to 10, more preferably 1: 3 to 5. At this time, if the blending ratio of the subphthalocyanine compound is less than 1:10, long-wavelength near infrared rays can be sufficiently absorbed, but the blending amount of the subphthalocyanine compound is insufficient, and orange light (550 to 620 nm) is sufficiently absorbed. This is not possible and the image may become unclear. On the other hand, when the blending ratio of the near-infrared absorbing compound is less than 1: 1, the orange light (550 to 620 nm) is sufficiently absorbed and the image is clear, but the long-wavelength near infrared can be effectively absorbed. Otherwise, malfunction of the remote control or the like may occur.

  A second aspect of the present invention relates to a plasma display front panel using a near infrared absorption filter containing the dye and resin of the present invention as described above. As described above, the subphthalocyanine compound according to the present invention has a narrower range than that of a dye that is known to absorb orange light (550 to 620 nm), which is a cause of blurring of an image in the past. It can absorb light of 600 nm selectively and efficiently with the minimum transmittance at 580 to 600 nm of 40% or less, and the half width of absorption is extremely narrow as 33.5 nm or less, and other visible light such as RGB light (especially , Pure R light in the vicinity of 630 nm and G light whose wavelength is close to each other). Therefore, the use of the near-infrared filter containing the subphthalocyanine compound according to the present invention for the near-infrared filter of the plasma display front panel can significantly improve the sharpness of the PDP image. In addition to the above advantages, in addition to the above-mentioned advantages, a near-infrared absorbing dye having an absorption maximum wavelength at 750 to 1200 nm in addition to the subphthalocyanine compound is included in the near-infrared filter. Infrared rays can be effectively absorbed, and malfunctions such as remote control can be more effectively suppressed. Therefore, a plasma display using such a near-infrared filter has a clear image and does not adversely affect the wavelengths used by remote control of peripheral electronic devices, transmission optical communication, etc., and prevents their malfunction. Can do.

  In the near-infrared absorbing filter according to the present invention, the amount of the dye for plasma display front panel added to the resin is not particularly limited as long as the above-described advantages can be effectively exhibited. 5 to 15 parts by mass, more preferably 3 to 8 parts by mass of the plasma display front panel dye is added to the resin. At this time, when the amount of the dye is less than 0.5 parts by mass, the amount of the dye is insufficient, the orange light (550 to 620 nm) cannot be sufficiently absorbed, and other visible light such as RGB light is also absorbed. As a result, the image may become unclear, and when a near-infrared absorbing compound is further included, long-wavelength near-infrared light cannot be effectively absorbed, and a malfunction of a remote control or the like may occur.

  The near-infrared absorption filter according to the present invention contains at least the above-mentioned dye for plasma display front panel in the base material, but "containing in the base material" as referred to in the present invention is contained inside the base material, The state applied to the surface of the base material, the state sandwiched between the base material, and the like are also meant. Examples of the substrate include a transparent resin plate, a transparent film, and transparent glass. The method for producing the near-infrared absorption filter according to the present invention using the dye for the plasma display front panel is not particularly limited. For example, the following three methods can be used.

  That is, (i) a method of kneading a resin for a plasma display front panel according to the present invention in a resin and thermoforming it to produce a resin plate or film; (ii) a paint containing the dye for a plasma display front panel according to the present invention (Liquid or pasty material) and a method of coating on a transparent resin plate, transparent film or transparent glass plate; and (iii) a dye for plasma display front panel according to the present invention contained in an adhesive, and a laminated resin And a method for producing a plate, a laminated resin film, a laminated glass, and the like.

  First, in the above method (i), the resin material is preferably as transparent as possible when a resin plate or resin film is used. Specific examples include polyethylene, polystyrene, polyacrylic acid, and polyacrylic ester. , Vinyl acetate, polyacrylonitrile, polyvinyl chloride, polyvinyl fluoride, and other vinyl compounds, and addition polymers of these vinyl compounds, polymethacrylic acid, polymethacrylic acid esters, polyvinylidene chloride, polyvinylidene fluoride, polycyanide vinylidene , Vinylidene fluoride / trifluoroethylene copolymers, vinylidene fluoride / tetrafluoroethylene copolymers, vinyl compounds such as vinylidene cyanide / vinyl acetate copolymers, or copolymers of fluorinated compounds, polytrifluoroethylene , Polite Fluorine-containing resins such as fluoroethylene and polyhexafluoropropylene, polyamides such as nylon 6 and nylon 66, polyimides, polyurethanes, polypeptides, polyesters such as polyethylene terephthalate, polycarbonates, polyoxymethylenes, polyethylene oxides, polypropylene oxides and other poly Examples include ether, epoxy resin, polyvinyl alcohol, polyvinyl butyral, etc., but are not limited to these resins, such as high hardness, high transparency resin, thiourethane type, etc. that can replace glass Thermosetting resin, Hals Hybrid IR-G205 (manufactured by Nippon Shokubai Co., Ltd.), resin described in JP-A No. 2002-249721, ARTON (manufactured by Nippon Synthetic Rubber Co., Ltd.), ZEONEX (Nippon Zeon Corporation) It is also preferable to use optical resins such as OPTOREZ (manufactured by Hitachi Chemical Co., Ltd.), O-PET (manufactured by Kanebo Co., Ltd.), etc.

  Depending on the base resin used, the processing temperature, filming conditions, etc. may vary slightly. Usually, (a) the dye for plasma display front panel according to the present invention is added to the base resin powder or pellets and heated to 150 to 350 ° C. , A method of forming a resin plate by melting, (a) a method of forming a film with an extruder, and (c) a raw fabric with an extruder, and 2 to 5 times at 30 to 120 ° C. For example, there is a method of forming a film having a thickness of 10 to 200 μm by stretching uniaxially or biaxially. In addition, when kneading, additives used for ordinary resin molding such as an ultraviolet absorber and a plasticizer may be added. The addition amount of the pigment for the plasma display front panel according to the present invention is usually 0.01 to 5% by mass, although it varies depending on the thickness of the resin to be produced, the target absorption intensity, the target visible light transmittance and the like. Moreover, the resin plate and the resin film which used the casting method by block polymerization of the pigment | dye for plasma display front panels and methyl methacrylate by this invention can also be produced.

  The above method (ii) includes a method in which the pigment for plasma display front panel according to the present invention is dissolved in a binder resin and an organic solvent to form a paint, and the pigment for plasma display front panel according to the present invention is atomized to several μm or less. For example, there is a method of dispersing in an acrylic emulsion to obtain a water-based paint. In the former method, usually, aliphatic ester resin, acrylic resin, melamine resin, urethane resin, aromatic ester resin, polycarbonate resin, aliphatic polyolefin resin, aromatic polyolefin resin, polyvinyl resin, polyvinyl alcohol resin, polyvinyl System modified resins (PVB, EVA, etc.) or copolymer resins thereof are used as the binder resin. Furthermore, optical resins such as ARTON (manufactured by Nippon Synthetic Rubber Co., Ltd.), ZEONEX (manufactured by Nippon Zeon Co., Ltd.), OPTPOREZ (manufactured by Hitachi Chemical Co., Ltd.) and O-PET (manufactured by Kanebo Co., Ltd.) can also be used. As the solvent, a halogen-based, alcohol-based, ketone-based, ester-based, aliphatic hydrocarbon-based, aromatic hydrocarbon-based, ether-based solvent, or a mixture thereof can be used.

  The concentration of the dye for the plasma display front panel according to the present invention varies depending on the thickness of the coating, the target absorption strength, the target visible light transmittance, etc., but is usually 0.1 to 15% by mass based on the weight of the binder resin. It is. Moreover, binder resin density | concentration is 1-50 weight% normally with respect to the whole coating material. Similarly, in the case of the acrylic emulsion water-based paint, it is obtained by dispersing a finely pulverized pigment for plasma display front panel according to the present invention into a size of 950 to 500 nm in an uncolored acrylic emulsion paint. In the coating material, additives such as ultraviolet absorbers, antioxidants and the like that are usually used in coating materials may be added.

  The paint produced by the above method is coated on a transparent resin film, transparent resin plate, transparent glass, etc. with a bar coder, blade coater, spin coater, reverse coater, die coater or spray, etc. An external absorption filter can be produced. A protective layer can be provided to protect the coating surface, or a transparent resin plate, a transparent resin film, or the like can be bonded to the coating surface. A cast film is also included in the method.

  In the method (iii), as an adhesive, a general silicone-based, urethane-based, acrylic-based resin or laminated glass polyvinyl butyral adhesive (PVA), ethylene-vinyl acetate adhesive (EVA) For example, a known transparent adhesive for laminated glass can be used. Transparent resin plates using an adhesive added with 0.1 to 15% by mass of a pigment for a plasma display front panel according to the present invention, resin plates and resin films, resin plates and glass, resin films, resin films and glass, A filter is made by bonding glass together. There is also a method of thermocompression bonding. Furthermore, the film or plate produced by the above method can be attached to glass or a resin plate, if necessary. The thickness of the filter varies depending on the specifications of the plasma display to be produced, but is usually about 0.1 to 10 mm. Moreover, in order to raise the light resistance of a filter, the transparent film (UV cut film) containing a UV absorber can also be affixed on the outer side.

The near-infrared absorption filter according to the present invention selectively and efficiently absorbs orange light (550 to 620 nm) and effectively absorbs long-wavelength near-infrared light to prevent malfunction of a remote control or the like. As a filter, it can be installed on the front of the display. If the selective absorption of orange light of 550 to 620 nm, particularly 580 to 600 nm, is low, the image may be unclear. Therefore, the near-infrared absorption filter according to the present invention has a decrease in transmittance in the wavelength range of 580 to 600 nm, and the minimum transmittance at 580 to 600 nm is 40% or less. Light (550 to 620 nm) can be selectively and efficiently absorbed, the half width of absorption is as narrow as 33.5 nm or less, and other visible light such as RGB light (especially pure R light around 630 nm) And transmission of G light whose wavelength is approximate) is hardly disturbed. If the selective absorption of orange light of 550 to 620 nm, particularly 580 to 600 nm, is low, the image may be unclear. For this reason, in the near-infrared absorption filter according to the present invention, it is preferable that the transmittance decrease occurs in a wavelength range of 550 to 620 nm, particularly 580 to 600 nm. If the decrease in transmittance deviates from the above range, there is a risk that transmission of pure R light near 630 nm or G light close to the wavelength of orange light may be hindered. R light and G light cannot be extracted sufficiently and sufficient color purity is obtained. This is because it may not be achieved. The near infrared absorption filter according to the present invention preferably has a minimum transmittance at 580 to 600 nm of 40% or less, more preferably 35% or less, and most preferably 30% or less. This is because if it deviates from the above range, the orange light cannot be sufficiently absorbed and the image may become unclear.

  In the present specification, the transmittance is the transmittance measured using a spectrophotometer (manufactured by Shimadzu Corporation: UV-3100) with a specimen prepared in the same manner as described in the following examples. Means. “Transmission decrease occurs in the wavelength range of 580 to 600 nm” means that the transmittance decreases by 40% or more at around 580 nm and 600 nm, respectively.

  Further, the near-infrared absorption filter according to the present invention has a lower visible light transmittance, so that the sharpness of the image is lowered. Therefore, the higher the visible light transmittance of the filter is better, preferably 40% or more, more preferably. Is 50% or more. Further, as described above, it is preferable that the near-infrared absorption filter cuts near-infrared light and more effectively suppresses the malfunction of the remote control or the like. In this case, the near-infrared light cut area is the remote control or transmission system light. It is preferably 750 to 1200 nm used for communication, more preferably 750 to 1100 nm, particularly preferably 800 to 1000 nm, and the average light transmittance in the region is 20% or less, more preferably 10% or less. Preferably there is. It is also preferable to add another dye having absorption in the visible region in order to change the color tone of the filter. It is also possible to produce a filter containing only the color tone dye and to bond it later. In particular, when an electromagnetic wave cut layer such as sputtering is provided, the color tone is important because the hue may be greatly different from the original filter color.

In order to make the filter obtained by the above method more practical, an electromagnetic wave cut layer, an antireflection (AR) layer, and a non-glare (AG) layer that block electromagnetic waves emitted from the plasma spray can be provided. Their production method is not particularly limited. For example, for the electromagnetic wave cut layer, a sputtering method such as a metal oxide can be used. Usually, In ₂ O ₃ (ITO) to which Sn is added is generally used, but the dielectric layer and the metal layer are formed on the substrate. By alternately laminating them by sputtering or the like, light of 1100 nm or more can be cut from near infrared rays, far infrared rays to electromagnetic waves. The dielectric layer is a transparent metal oxide such as indium oxide or zinc oxide, and the metal layer is generally silver or a silver-palladium alloy, and usually three layers and five layers starting from the dielectric layer. 7 or 11 layers are laminated. In this case, the heat emitted from the display can be cut at the same time, but since the dye for plasma display front panel of the present invention is also excellent in the heat ray shielding effect, the heat resistance effect can be further improved. As the substrate, the filter containing the phthalocyanine compound of the present invention may be used as it is, or after being sputtered on a resin film or glass, it may be combined with the filter containing the dye for the plasma display front panel of the present invention. Good. Moreover, when actually performing electromagnetic wave cutting, it is necessary to install an electrode for grounding. In order to suppress the reflection of the surface and improve the transmittance of the filter, the antireflection layer is made of an inorganic substance such as a metal oxide, fluoride, boride, carbide, nitride, sulfide, vacuum deposition method, sputtering method, There are a method of laminating a single layer or a multilayer by an ion plating method, an ion beam assist method, or the like, a method of laminating a resin having a different refractive index such as an acrylic resin or a fluororesin, or the like. Moreover, the film which gave the antireflection process can also be affixed on this filter. Further, if necessary, a non-glare (AG) layer can be provided. The non-glare (AG) layer can be formed by coating fine particles of silica, melamine, acrylic, etc. with ink in order to scatter transmitted light for the purpose of widening the viewing angle of the filter. The ink can be cured by thermal curing or photocuring. Further, a non-glare-treated film can be pasted on the filter. Further, if necessary, a hard coat layer can be provided.

  The configuration of the plasma spray spray filter can be changed as necessary. Usually, an antireflection layer is provided on the near-infrared absorption filter containing the dye of the present invention and, if necessary, a near-infrared absorbing compound, and if necessary, a non-glare layer is provided on the opposite side of the antireflection layer. Moreover, when combining an electromagnetic wave cut layer, it can produce by using an near-infrared absorption filter as a base material, providing an electromagnetic wave cut layer on it, or bonding a near-infrared absorption filter and the filter which has an electromagnetic wave cut ability together. In that case, an antireflection layer can be further produced on both sides, or if necessary, an antireflection layer can be produced on one side and a non-glare layer can be produced on the opposite side. In addition, when adding a dye having absorption in the visible region for color correction, the method is not limited. The near-infrared absorption filter according to the present invention selectively and efficiently absorbs orange light (550 to 620 nm), particularly 580 to 600 nm, which causes the conventional image to become unclear. The plasma display front panel of the present invention has a very clear image because it hardly or at all prevents the transmission of visible light (in particular, G light having an approximate wavelength). In addition, as described above, the near-infrared absorption filter according to the present invention has a high visible light transmittance, so that the clearness of the display is not impaired and sufficient color purity can be ensured. Further, when the near-infrared absorbing filter according to the present invention further contains a near-infrared absorbing compound, in order to efficiently cut near-infrared light emitted from the display at 750 to 1200 nm, particularly near 800 to 1000 nm, It does not adversely affect the wavelengths used by transmission optical communication and the like, and can prevent their malfunction.

Hereinafter, the present invention will be described in more detail with reference to examples. The maximum absorption wavelength (λ _max ), the half width of absorption, and the spectral transmittance referred to in this specification are values measured by the following methods. In the following examples, “SubPc” represents subphthalocyanine.

<Maximum absorption wavelength (λ _max ), half width of absorption, and spectral transmittance measurement method>
Using a spectrophotometer (manufactured by Shimadzu Corporation: UV-3100), the maximum absorption wavelength (λ _max ) of the subphthalocyanine compound and the half width of absorption at that time were measured in toluene. For other dyes, the maximum absorption wavelength (λ _max ) was measured in acetone in the case of a phthalocyanine compound, and in dichloromethane in the case of a nickel complex dye and a diimmonium compound, instead of toluene. .

Further, the transmittance at 830 nm, 880 nm, 920 nm, and 980 nm, which are particularly strong emission wavelengths, as the emission wavelength of xenon emitted from the plasma display, using the near-infrared absorption filter prepared in the following examples as a test piece. And the minimum transmittance (T _min ) at 580 to 600 nm, which is a particularly intense orange emission wavelength of neon.

Synthesis example 1
To a 100 ml four-necked flask was added 11.23 g (20.7 mmol) of 3- (2,6-dimethylphenoxy) -4,5-bis (4-methoxyphenylthio) -6-fluorophthalonitrile, vanadium trichloride. 0.978 g (6.22 mmol), 0.81 g of octanol and 14.19 g of benzonitrile were charged and then kept under reflux for about 4 hours with stirring. Thereafter, 30 g of benzonitrile was added and cooled to 60 ° C., 16.05 g (124 mmol) of 2-ethylhexylamine was added, and the mixture was kept at 60 ° C. with stirring for about 6 hours. After cooling, the reaction solution was filtered, the filtrate was crystallized dropwise in a mixed solution of acetonitrile and water, and further washed with a mixed solution of acetonitrile and water. By vacuum drying, VOPc {4- (CH ₃ O) PhS} ₈ {2,6- (CH ₃ ) ₂ PhO} ₄ {CH ₃ (CH ₂ ) ₃ CH (C ₂ H ₅ ) CH ₂ NH} ₄ 9.18 g of {3- (2,6-dimethylphenoxy) -4,5-bis (4-methoxyphenylthio) -6-fluorophthalonitrile, yield 66.3 mol%} was obtained.

Synthesis example 2
In a 100 ml four-necked flask, 10 g (20.7 mmol) of 3- (2,6-dimethylphenoxy) -4,5-bis (phenylthio) -6-fluorophthalonitrile and 0.978 g of vanadium trichloride (6. 22 mmol), 0.81 g of octanol and 14.19 g of benzonitrile, and then kept under reflux for about 4 hours with stirring. Thereafter, 30 g of benzonitrile was added and cooled to 60 ° C., 12.81 g (124 mmol) of 3-ethoxypropylamine was added, and the mixture was kept at 60 ° C. with stirring for about 6 hours. After cooling, the reaction solution was filtered, the filtrate was crystallized dropwise in a mixed solution of acetonitrile and water, and further washed with a mixed solution of acetonitrile and water. By vacuum drying, 7.70 g {3- (2,6-dimethyl) of VOPc (PhS) ₈ {2,6- (CH ₃ ) ₂ PhO} ₄ {(CH ₃ CH ₂ O (CH ₂ ) ₃ NH) ₄ was obtained. Yield of 63.9 mol% relative to (phenoxy) -4,5-bis (phenylthio) -6-fluorophthalonitrile}.

Example 1
Synthesis of BClSubPc (2,5-Cl ₂ PhO) ₆ F ₆ Under a nitrogen stream, 120 g of 1-chloronaphthalene was charged into a 200 ml four-necked flask and 4,5-bis (2,5-dichlorophenoxy) Add 40 g (0.082 mol) of 3,6-difluorophthalonitrile and stir at room temperature for 0.5 hour. Next, boron trichloride gas was liquefied with dry ice, and 7.07 g (0.06 mol) was added dropwise. Then, it heated up to 150 degreeC over about 2 hours, and was made to react for 2 hours. The reaction product thus obtained was cooled to room temperature, transferred to a 3 liter beaker, and about 1600 ml of hexane was added with stirring to precipitate crystals. Further, the crystals were taken out by pressure filtration with nitrogen gas. About 820 ml of hexane was added to the crystal taken out and stirred to perform washing and purification. Thereafter, the crystals were taken out again by pressure filtration with nitrogen gas. The extracted crystal was vacuum-dried at about 180 ° C. overnight to obtain about 41.2 g (yield: 99.8 mol%) of BClSubPc (2,5-Cl ₂ PhO) ₆ F ₆ .

When the maximum absorption wavelength (λ _max ) and the half width of absorption of BClSubPc (2,5-Cl ₂ PhO) ₆ F ₆ thus obtained were measured, the maximum absorption wavelength (λ _max ) was 594.5 nm. The absorption half width was 31 nm.

Furthermore, 10 parts by mass of a commercially available fluorene-based polyester copolymer, 0.09 parts by mass of the thus obtained subphthalocyanine compound BClSubPc (2,5-Cl ₂ PhO) ₆ F ₆ , JP-A No. 2001-106869 Phthalocyanine [CuPc (2,5-Cl ₂ PhO) ₈ {2,6- (CH ₃ ) ₂ PhO} ₄ (PhCH ₂ NH) ₄ ] (λ _max : 807 nm) prepared in the same manner as Example 8 of 0.1 part by mass, phthalocyanine [VOPc (2,5-Cl ₂ PhO) ₈ {2,6- (CH ₃ ) ₂ PhO} ₄ produced in the same manner as in Example 7 of JP-A-2001-106869 _{(PhCH 2 NH) 4] (} λ max: 870nm) 0.13 parts by weight, manufactured in the same manner as in example 9 of JP-a-2001-106689 Patent Publication Phthalocyanines _{[VOPc (PhS) 8 {2,6-} (CH 3) 2 PhO} 4 (PhCH 2 NH) 4] (λ max: 912nm) 0.09 parts by weight, in the same manner as in Synthesis Example 1 Synthesis Phthalocyanine [VOPc {4- (CH ₃ O) PhS} ₈ {2,6- (CH ₃ ) ₂ PhO} ₄ {CH ₃ (CH ₂ ) ₃ CH (C ₂ H ₅ ) CH ₂ NH} ₄ ] ( (λ _max : 962 nm) 0.15 parts by mass was dissolved and mixed in 89.44 parts by mass of dichloromethane to prepare a resin coating liquid. The resin coating liquid thus prepared was applied onto a commercially available polyethylene terephthalate film (about 50 μm) so that the dry film thickness was 10 μm, dried at room temperature, and further dried at 80 ° C. A transparent coating film (near infrared absorption filter) containing an infrared absorber and a subphthalocyanine compound that absorbs orange light was obtained.

  Next, 2.7 parts by mass of an ultraviolet absorber (manufactured by Ciba Specialty Chemicals Co., Ltd., TINUVIN 384) and an antioxidant (manufactured by Ciba Specialty Chemicals Co., Ltd.) are formed on the transparent coating film thus obtained. , IRGANOX-1010) 0.9 part by mass, acrylic adhesive (manufactured by Toa Gosei Co., Ltd., Aron S-1601) 96.4 parts by mass, a mixture obtained by mixing the dried coating with a thickness of 15 μm The transparent adhesive layer containing an ultraviolet absorber was laminated | stacked so that it might become.

A near-infrared absorption filter is manufactured by sticking the adhesive surface of a transparent coating film containing a pigment that absorbs orange light and a near-infrared absorber to the 3 mm thick tempered glass substrate using a roll laminator. did. The optical properties of the near infrared absorption filter [minimum transmittance (%) at 580 to 600 nm (T _min ) and transmittance at 830 nm, 880 nm, 920 nm and 980 nm (hereinafter the same)] were measured according to the method described above. The results are shown in Table 1.

Example 2
In Example 1, the composition of the near-infrared absorber was changed to phthalocyanine [CuPc (2,5-Cl ₂ PhO) ₈ {2,6- produced in the same manner as in Example 8 of JP-A No. 2001-106869. (CH ₃ ) ₂ PhO} ₄ (PhCH ₂ NH) ₄ ] (λ _max : 807 nm) 0.1 part by mass, phthalocyanine [VOPc (2) produced in the same manner as in Example 7 of JP-A No. 2001-106869 _{, 5-Cl 2 PhO) 8} {2,6- (CH 3) 2 PhO} 4 (PhCH 2 NH) 4] (λ max: 870nm) 0.13 parts by weight, of JP-a 2001-106689 JP example Phthalocyanine [VOPc (PhS) ₈ {2,6- (CH ₃ ) ₂ PhO} ₄ (PhCH ₂ NH) ₄ ] (λ _max : 912 nm) produced in the same manner as in Example 9. 0.07 parts by mass, synthesized in the same manner as in Synthesis Example 2 above, phthalocyanine VOPc (PhS) ₈ {2,6- (CH ₃ ) ₂ PhO} ₄ {(CH ₃ CH ₂ O (CH ₂ ) ₃ NH) ₄ (Λ _max : 928 nm) 0.02 parts by mass, phthalocyanine synthesized in the same manner as in Synthesis Example 1 [VOPc {4- (CH ₃ O) PhS} ₈ {2,6- (CH ₃ ) ₂ PhO} ₄ { A near-infrared absorption filter was produced in the same manner as in Example 1 except that 0.13 parts by mass of CH ₃ (CH ₂ ) ₃ CH (C ₂ H ₅ ) CH ₂ NH} ₄ ] (λ _max : 962 nm) was used. The optical properties were measured. The results are shown in Table 1.

Example 3
In Example 1, the composition of the near-infrared absorber was changed to phthalocyanine [CuPc (2,5-Cl ₂ PhO) ₈ {2,6- produced in the same manner as in Example 8 of JP-A No. 2001-106869. (CH ₃ ) ₂ PhO} ₄ (PhCH ₂ NH) ₄ ] (λ _max : 807 nm) 0.1 part by mass, phthalocyanine [VOPc (2) produced in the same manner as in Example 7 of JP-A No. 2001-106869 _{, 5-Cl 2 PhO) 8} {2,6- (CH 3) 2 PhO} 4 (PhCH 2 NH) 4] (λ max: 870nm) 0.13 parts by weight, diimmonium compound (N, N, N ' , N'- tetrakis (p- diethylaminophenyl)-p-benzoquinone - bis (immonium) hexafluoroantimonate) (lambda _max: 1090 nm) 0.25 weight Except that the can in the same manner as in Example 1, to produce a near-infrared absorption filter was measured the same optical characteristics. The results are shown in Table 1.

Example 4
In Example 3, 33 parts by weight of Hals Hybrid IR-G205 (manufactured by Nippon Shokubai Co., Ltd., acrylic resin) was used instead of 10 parts by weight of the fluorene-based polyester copolymer, and instead of 89.44 parts by weight of dichloromethane. A near-infrared absorption filter was produced in the same manner as in Example 3 except that 66.44 parts by mass of toluene was used, and the optical characteristics thereof were measured. The results are shown in Table 1.

Example 5
Phthalocyanine [CuPc (2,5-Cl ₂ PhO) ₈ {2,6- (CH ₃ ) ₂ PhO} ₄ (PhCH ₂ NH) ₄ ] (λ _max : 807 nm) 0.1 parts by mass, phthalocyanine [VOPc (2 , 5-Cl ₂ PhO) ₈ {2,6- (CH ₃ ) ₂ PhO} ₄ (PhCH ₂ NH) ₄ ] (λ _max : 870 nm) 0.13 parts by mass, and phthalocyanine [VOPc (PhS) ₈ {2 , 6- (CH ₃ ) ₂ PhO} ₄ (PhCH ₂ NH) ₄ ] (λ _max : 912 nm) Instead of 0.09 part by mass, the nickel complex dye Bis (1,2-diphenylene-1,2- dithiol) nickel (λ _max : 854.5 nm) using 0.074 parts by mass and using phthalocyanine [VOPc {4- (CH ₃ O) PhS } ₈ {2,6- (CH ₃ ) ₂ PhO} ₄ {CH ₃ (CH ₂ ) ₃ CH (C ₂ H ₅ ) CH ₂ NH} ₄ ] (λ _max : 962 nm) instead of 0.15 parts by mass , 0.25 parts by mass of a diimonium compound (N, N, N ′, N′-tetrakis (p-diethylaminophenyl) -p-benzoquinone-bis (imonium) · hexafluoroantimonate) (λ _max : 1090 nm) A near-infrared absorption filter was produced in the same manner as in Example 1 except that it was used, and the optical characteristics thereof were measured. The results are shown in Table 1.

Example 6
In Example 5, 33 parts by weight of Hals Hybrid IR-G205 (manufactured by Nippon Shokubai Co., Ltd., acrylic resin) was used instead of 10 parts by weight of the fluorene polyester copolymer, and instead of 89.44 parts by weight of dichloromethane. A near-infrared absorption filter was produced in the same manner as in Example 5 except that 66.44 parts by mass of toluene was used, and the optical characteristics thereof were measured. The results are shown in Table 1.

As shown in Table 1 above, the near-infrared absorption filter containing the subphthalocyanine compound according to the present invention has a minimum transmittance (T _min ) of 40% or less of orange light that causes an image of 580 to 600 nm to be blurred. It is shown to absorb selectively and efficiently. Further, as described in Example 1 above, the maximum absorption wavelength (λ _max ) of BClSubPc (2,5-Cl ₂ PhO) ₆ F ₆ , which is a subphthalocyanine compound according to the present invention, is 594.5 nm and Since the full width at half maximum is as narrow as 31 nm, the near-infrared absorption filter containing a subphthalocyanine compound according to the present invention has a transmittance of visible light outside the wavelength range of 580 to 600 nm, particularly R light near 630 nm and G light having a close wavelength. It is considered that a high level can be maintained. Therefore, the near-infrared absorption filter of the present invention containing the subphthalocyanine compound according to the present invention can improve the color purity without hindering the emission of necessary RGB light from the panel even when used in a plasma display front panel. it is conceivable that.

Example 7
When the near-infrared absorption filter described in Examples 1 to 6 was attached to the front portion of the plasma display and the red color was observed, a very beautiful red color was observed. In addition, when an electric device that performs operation control with a remote control was installed at a position 2.5 m from the display and observed whether a malfunction was induced, a malfunction was induced when no filter was attached. When the near-infrared absorption filter described in 6 was attached to the front surface of the plasma display, no induction of malfunction was observed.

  From this, since the near-infrared absorption filter by Example 1-6 of this invention contains the near-infrared absorber which has an absorption maximum wavelength in 750-1200 nm in addition to a subphthalocyanine compound, improvement of the color purity of a panel In addition, it is considered that the near-infrared rays having a longer wavelength than that which has been difficult to shield can be effectively absorbed so that the malfunction of the remote controller can be more effectively suppressed.

  By using a near-infrared absorption filter including a subphthalocyanine compound having a specific structure (formula (1)) for the plasma display front panel, orange light of 550 to 620 nm, particularly 580 to 600 nm, is selectively and efficiently absorbed. However, it is possible to produce a plasma display with clear images and improved color purity that absorbs little or no other visible light region including other RGB light.

  In addition, by using a near-infrared absorption filter comprising a subphthalocyanine compound having the formula (1) and a near-infrared absorption dye having an absorption maximum wavelength at 750 to 1200 nm as a near-infrared absorption filter for a plasma display front panel, the above-described advantages can be obtained. In addition, it is possible to produce a plasma display that does not adversely affect the wavelengths used by peripheral electronic devices such as remote controllers and transmission optical communications, and that does not malfunction.

Claims (5)

Any of the following formulas (A) to (D):

In the formula, R is a halogen atom, a methyl group, an ethyl group, a methoxy group, an ethoxy group, a methoxycarbonyl group, or an ethoxycarbonyl group, and a plurality of substituents R may be present, either the same or different. N represents the number of substituents R bonded to the benzene ring, and is 0 to 4, X is a halogen atom, a hydroxy group, an alkoxy group, an alkoxyalkoxy group, an alkylthioalkoxy group or a dialkylaminoalkoxy Represents a group,
And a subphthalocyanine compound that selectively absorbs light in the wavelength range of 580 to 600 nm . The dye for a plasma display front panel according to claim 1, wherein the subphthalocyanine compound is represented by the formula (A) or (B).   The dye for a plasma display front panel according to claim 1 or 2, further comprising at least one near-infrared absorbing compound having an absorption maximum wavelength at 750 to 1200 nm.   The plasma display front panel which uses the near-infrared absorption filter containing the pigment | dye and resin of any one of Claims 1-3.   A sub-phthalocyanine compound of the formula (1) according to claim 1 or 2 having a maximum absorption in a wavelength range of 580 to 600 nm and a half-value width of absorption of 33.5 nm or less. The plasma display front panel according to claim 4, wherein the minimum transmittance at 600 nm is 40% or less.