JP5484841B2 - Phthalocyanine compounds - Google Patents

Description

  The present invention relates to a phthalocyanine compound. Specifically, the present invention uses a phthalocyanine compound having a maximum absorption wavelength in the near infrared wavelength region of 800 to 1100 nm, particularly 850 to 1000 nm, and excellent in light resistance in an adhesive material (adhesive layer), and the phthalocyanine compound. It is related with the near-infrared absorption filter which becomes.

  The phthalocyanine compound of the present invention has a translucent or transparent heat ray shielding material for the purpose of shielding heat rays, a heat ray absorbing laminated glass for automobiles, a heat ray shielding film or a heat ray shielding resin glass, a high visible light transmittance and Near-infrared absorbing filters with high near-infrared light cutting efficiency, especially near-infrared absorbing filters for plasma display panels, near-infrared absorbing agents for non-contact fixing toners such as flash fixing, and near-infrared absorbing agents for heat-retaining and storing fibers Infrared absorbents for fibers that have camouflage performance (camouflage performance) for reconnaissance by infrared rays, optical recording media using semiconductor lasers, filters for liquid crystal displays with a xenon lamp as a backlight, writing in optical character readers, etc. Near infrared absorbing dye for reading, near infrared photosensitizer, heat sensitive Photothermal exchange agents such as photo- and heat-sensitive stencils, laser heat-fusing photo-heat exchange agents that use laser beams to fuse, near-infrared absorption filters, eye strain prevention agents, photoconductive materials, etc., and tissue permeability Photosensitive dye for tumor treatment that absorbs light with good long wavelength range, color cathode ray tube selective absorption filter, color toner, inkjet ink, anti-counterfeiting ink, anti-counterfeiting bar code ink, near infrared absorption Excellent when used as a marking agent for positioning inks, photos and films, and goggle lenses and shielding plates, as a dyeing agent for sorting when recycling plastics, and as a preheating aid when molding PET bottles. It is effective. Considering the above-described characteristics in particular, the phthalocyanine compound of the present invention can be suitably used for a near infrared absorption filter, particularly a near infrared absorption filter for a plasma display panel.

  In recent years, flat panel displays have attracted attention as displays that can be made thin and have a large screen. Among them, a plasma display panel (PDP: Plasma Display Panel), a liquid crystal display (LCD: Liquid Crystal Display), and the like have been widely spread and attracted attention. PDPs are thin and easy to increase in screen size, so in recent years, there is an increasing expectation as a next-generation display with a thin and large screen. However, the PDP excites the xenon gas to excite the phosphor and thereby develops color, but near infrared rays are generated when the xenon gas is excited to discharge. This near-infrared light may cause malfunctions in peripheral electronic devices such as remote control devices such as TVs for home appliances, coolers, and video decks, as well as transmission optical communication. It is necessary to install and reduce near-infrared radiation.

  On the other hand, in the plasma display, the color purity of red light greatly decreases due to strong light emission near 590 nm. In addition, neon gas which is the main component of Penning gas for exciting the phosphor always emits orange neon light in the vicinity of 585 nm regardless of the emission color. For this reason, the plasma display has a color correction filter that selectively absorbs light in the 580 to 600 nm region in order to reduce these and obtain colors close to natural colors. In addition, in the plasma display, in addition to the near-infrared absorption filter and the color correction filter, it is necessary to dispose an electromagnetic wave shielding filter capable of effectively blocking electromagnetic waves; In other words, the plasma display is composed of a single front filter in which materials in the form of films having various functions such as infrared absorption, electromagnetic wave shielding, color correction, and antireflection are laminated. There are a large number of layer structures such as a coating layer, an adhesive layer, a protective film, and a release film of each functional substance formed on the substrate, and the production process is complicated and troublesome. In view of such a problem, various methods for reducing the number of films used for the front filter have been studied.

  Specifically, the release film and the protective film are materials that are discarded after laminating the respective films at the time of producing the front filter. When the functions of the respective films are integrated, the amount of use can be reduced. Furthermore, since the adhesive layer is also used to laminate each film, if the number of necessary films is reduced, the amount of use will be reduced, and the base film to be coated will also integrate the functions of the film etc. It is considered that the number of used sheets is reduced.

  Among these methods, a method of including an infrared absorbing dye in an adhesive layer has been proposed as an effective method (see, for example, Patent Document 1). Here, examples of the infrared absorbing dye generally include anthraquinone, phthalocyanine, cyanine, dithiol-metal complex, and diimmonium. Of these, phthalocyanine dyes generally have high visible light transmittance, high near-infrared light cutting efficiency, excellent near-infrared selective absorption ability, and excellent heat resistance and light resistance. A phthalocyanine compound having a simple structure has been reported (see, for example, Patent Documents 2 and 3).

  Patent Document 2 discloses a phthalocyanine compound having a structure in which a substituent, a hydrogen atom, or a halogen atom is introduced via an —OR group at the α-position and two oxygen atoms at the β-position of the phthalocyanine skeleton. Such a phthalocyanine compound has sharp absorption at 700 to 800 nm, a high molecular extinction coefficient of 150,000 or more, and excellent long-term stability and light resistance. It is reported that it is suitable for a recording material of an optical recording medium (optical disc, optical card, etc.) using a semiconductor laser (paragraph “0012”). Further, as a specific structure of the phthalocyanine compound, a structure derived from catechol at the β-position is disclosed (paragraphs “0023” to “0024”).

Patent Document 3 discloses that the formula (1): M _k Pc (—O—R—O—) _x (—YR ¹ ) _y (—Z) _z (—SO ₃ A) _n [R is substituted. Or a substituted 1,2-arylene group, x represents an integer of 1 to 8]. Such a phthalocyanine compound exhibits a strong absorption maximum in the near infrared region (750 to 900 nm) of the electromagnetic spectrum (paragraph “0001”). Further, preferred phthalocyanine compounds are disclosed in which a structure derived from catechol is introduced at all α and β positions (paragraphs “0017”, “0026”, “0033”, “0037”).

JP 2007-119722 A Japanese Patent Laid-Open No. 7-179042 Japanese Patent Laid-Open No. 10-1481

  However, since the phthalocyanine compound disclosed in Patent Document 2 has a structure in which a substituent, a hydrogen atom or a halogen atom via two oxygen atoms is introduced in the α-position and in the β-position, the phthalocyanine Does not have an amine group (—NHR) in the skeleton. For this reason, the phthalocyanine compound disclosed in Patent Document 2 has a maximum absorption wavelength in the 700 to 800 nm region (paragraph “0012”), but absorbs light in a longer wavelength region (800 to 1000 nm) of near infrared rays. Is difficult. In fact, the maximum absorption wavelength of the phthalocyanine compound produced in the examples is only about 720 nm (see Table 2 in paragraph “0128”). Moreover, the phthalocyanine compound preferably disclosed in Patent Document 3 has a structure in which a structure derived from catechol is introduced at all α and β positions. Such a phthalocyanine compound also does not have an amine group (—NHR) in the phthalocyanine skeleton, as in the above examples, and therefore cannot have a maximum absorption wavelength in a long wavelength region. In fact, the maximum absorption wavelength of the phthalocyanine compound produced in the examples is 832 nm at the maximum (paragraph “0034”). In addition to the above, it is difficult to introduce a catechol-derived structure at all the α and β positions as in this phthalocyanine compound.

  Therefore, the present invention has been made in view of the above circumstances, and has a maximum absorption wavelength in the near-infrared wavelength region of 800 to 1000 nm, particularly 850 to 1000 nm, and is excellent in light resistance and weather resistance in an adhesive material (adhesive layer). And it aims at providing the phthalocyanine compound which manufacture is easy.

  Another object of the present invention is to provide a near-infrared absorbing filter containing the phthalocyanine compound, particularly a near-infrared absorbing filter for a plasma display panel.

  As a result of intensive studies to achieve the above object, the present inventors have introduced a structure derived from catechol or 1,2-benzenedithiol so as to straddle one α and β positions of the phthalocyanine skeleton, and the rest. By introducing an amine group (—NR′R ″) at the four α-positions, the obtained phthalocyanine compound exhibits excellent light resistance and weather resistance even when mixed in an adhesive material (adhesive layer). In addition, the inventors have found that the maximum absorption wavelength can be lengthened, and that a higher gram extinction coefficient can be achieved. After reacting phthalonitrile with a compound of formula H—A—R, reaction with catechol of formula: H—X—Ar—X′—H or 1,2-benzenedithiol derivative Thus, -X-Ar-X'- can be accurately introduced into the four α-positions of the phthalocyanine skeleton and the four β-positions adjacent to the α-position, thereby increasing the desired phthalocyanine compound. Based on the above findings, the present inventors have completed the present invention.

  That is, the above object is achieved by the following formula (1):

In the formula, X and X ′ each independently represent an oxygen atom (—O—) or a sulfur atom (—S—); Ar each independently has an optionally substituted o— Represents a phenylene group, an o-naphthylene group which may have a substituent, or an o-anthrylene group which may have a substituent, wherein the substituent is a halogen atom, having 1 to 20 carbon atoms Represents an alkyl group, -OY (Y represents an alkyl group having 1 to 20 carbon atoms), or -SY '(Y' represents an alkyl group having 1 to 20 carbon atoms); Each independently represents an oxygen atom (—O—), a sulfur atom (—S—) or a single bond (—); each R independently represents an optionally substituted phenyl group or Has a naphthyl group, an aralkyl group which may have a substituent, or a substituent Represents an optionally substituted alkyl group having 1 to 20 carbon atoms; R ′ and R ″ each independently represents a hydrogen atom, a phenyl group which may have a substituent, or a substituent. Represents an aralkyl group which may be substituted or an alkyl group having 1 to 20 carbon atoms which may have a substituent; M represents a metal-free, metal, metal oxide or metal halide;
Or a positional isomer thereof.

  Another object of the present invention is achieved by a near-infrared absorbing filter comprising the phthalocyanine compound of the present invention, particularly a near-infrared absorbing filter for a plasma display panel.

  The phthalocyanine compound of the present invention is excellent in light resistance in an adhesive (adhesive layer) while exhibiting high near-infrared cut efficiency in the wavelength range of 800 to 1100 nm, particularly 850 to 1000 nm. Moreover, the phthalocyanine compound of the present invention can be produced with high purity and high yield by a simple process without requiring complicated steps.

  Therefore, the phthalocyanine compound of the present invention has a translucent or transparent heat ray shielding material for the purpose of shielding heat rays, a heat ray absorbing laminated glass for automobiles, a heat ray shielding film or a heat ray shielding resin glass, and a visible light transmittance. Near-infrared absorbing filter with high and high near-infrared light cutting efficiency, especially near-infrared absorbing filter for plasma display panel, near-infrared absorbing agent for non-contact fixing toner such as flash fixing, and near-infrared for thermal insulation fiber Absorbents, infrared absorbers for fibers with camouflage performance against scouting by infrared rays, optical recording media using semiconductor lasers, filters for liquid crystal displays with xenon lamps as backlights, optical character readers, etc. Near-infrared absorbing dye for writing or reading, near-infrared light Photosensitizer, photothermal exchange agent such as thermal transfer and thermal stencil, photothermal exchange agent for laser fusion that heat-fuses resin using laser beam, near infrared absorption filter, anti-eye strain or photoconductive material, etc. Furthermore, a photosensitive dye for tumor treatment that absorbs light in a long wavelength region with good tissue permeability, a color cathode ray tube selective absorption filter, color toner, ink for inkjet, anti-counterfeiting ink, anti-counterfeiting bar code ink, Used for near-infrared absorbing ink, marking agents for positioning photos and films, goggles lenses and shielding plates, dyeing agents for sorting when recycling plastics, and pre-heating aids when molding PET bottles In particular, it exhibits an excellent effect. Considering the above-described characteristics in particular, the phthalocyanine compound of the present invention can be suitably used for a near infrared absorption filter, particularly a near infrared absorption filter for a plasma display panel.

It is a figure which shows the specific method of a weather resistance test. It is a graph which shows the light absorbency in wavelength range 400-1100nm of the phthalocyanine (101) of the synthesis example 5-1, the comparative phthalocyanine (A) of the comparative example 1, and the comparative phthalocyanine (B) of the comparative example 2. In Example 6, the phthalocyanines (101) and (109) to (111) obtained in Synthesis Examples 5-1 and 5-10 to 12 and the comparative phthalocyanines (A) and (B) obtained in Comparative Examples 1 and 2 were used. It is a graph which shows the weather resistance test result of ().

  Hereinafter, the present invention will be described in detail.

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

In the formula, X and X ′ each independently represent an oxygen atom (—O—) or a sulfur atom (—S—); Ar each independently has an optionally substituted o— Represents a phenylene group, an o-naphthylene group which may have a substituent, or an o-anthrylene group which may have a substituent, wherein the substituent is a halogen atom, having 1 to 20 carbon atoms Represents an alkyl group, -OY (Y represents an alkyl group having 1 to 20 carbon atoms), or -SY '(Y' represents an alkyl group having 1 to 20 carbon atoms); Each independently represents an oxygen atom (—O—), a sulfur atom (—S—) or a single bond (—); each R independently represents an optionally substituted phenyl group or Has a naphthyl group, an aralkyl group which may have a substituent, or a substituent Represents an optionally substituted alkyl group having 1 to 20 carbon atoms; R ′ and R ″ each independently represents a hydrogen atom, a phenyl group which may have a substituent, or a substituent. Represents an aralkyl group which may be substituted or an alkyl group having 1 to 20 carbon atoms which may have a substituent; M represents a metal-free, metal, metal oxide or metal halide;
It is related with the phthalocyanine compound shown by these, or its positional isomer.

  The phthalocyanine compound of the present invention has high visible light transmittance, high near-infrared light cutting efficiency, excellent near-infrared absorption ability, excellent solvent solubility, excellent resin compatibility, excellent heat resistance, excellent It has light resistance and excellent weather resistance. Generally, a resin having a low glass transition point (Tg) is used for the adhesive layer of the near-infrared absorption filter for plasma display panels. Therefore, the adhesive layer has flexibility and a small amount of solvent remains. In addition, it contains a lot of impurities. Here, the impurities move relatively freely in the adhesive layer due to the above-mentioned characteristics of the adhesive layer. When a dye is put into such an adhesive layer, the dye is likely to come into contact with the freely moving impurities, so that the dyes are easily affected by the adverse effects of the impurities (for example, modification by the functional group of the adhesive). This was a factor that deteriorated the properties of the pigment. For this reason, conventionally, the dye is not included in the adhesive layer, and a near-infrared absorption filter is separately provided.

  In contrast, the phthalocyanine compound of the present invention has a structure derived from catechol or 1,2-benzenedithiol (that is, -X-Ar-X'-) so as to straddle one α and β positions of the phthalocyanine skeleton. It is characterized by that. Since the structure of -X-Ar-X'- is bonded (fixed) to the phthalocyanine skeleton at two positions, the benzene ring portion of the phthalocyanine skeleton is difficult to move freely. Therefore, even when the phthalocyanine compound of the present invention is placed in the adhesive layer, contact with impurities does not occur so much, so that deterioration of properties of the phthalocyanine compound due to impurities can be significantly suppressed / prevented. Therefore, the phthalocyanine compound of the present invention has excellent effects even in the adhesive layer (high visible light transmittance, high near-infrared light cutting efficiency, excellent near-infrared absorption ability, excellent solvent solubility, and excellent resin compatibility. Solubility, excellent heat resistance, excellent light resistance and excellent weather resistance, etc.) and particularly excellent light resistance. In addition, the presence of a structure derived from catechol or 1,2-benzenedithiol (that is, -X-Ar-X'-), compared with the case where two sites are bonded with two molecules using phenol or benzenethiol, Since two sites can be bonded by one molecule, the molecular weight of the phthalocyanine compound itself can be lowered, and the amount of reagent used can be reduced. For this reason, the phthalocyanine compound of the present invention increases the gram extinction coefficient (ε) (for example, if there is a dye having the same gram extinction coefficient, a dye having a lower molecular weight expresses the same absorption performance in a smaller amount). Therefore, excellent effects with a small amount of phthalocyanine compound (high visible light transmittance, high near infrared light cut efficiency, excellent near infrared absorption ability, excellent solvent solubility, excellent resin compatibility) Solubility, excellent heat resistance, excellent light resistance and excellent weather resistance).

  Therefore, the phthalocyanine compound of the present invention has a translucent or transparent heat ray shielding material for the purpose of shielding heat rays, a heat ray absorbing laminated glass for automobiles, a heat ray shielding film or a heat ray shielding resin glass, and a visible light transmittance. Near-infrared absorbing filter with high and high near-infrared light cutting efficiency, especially near-infrared absorbing filter for plasma display panel, near-infrared absorbing agent for non-contact fixing toner such as flash fixing, and near-infrared for thermal insulation fiber Absorbents, infrared absorbers for fibers with camouflage performance against scouting by infrared rays, optical recording media using semiconductor lasers, filters for liquid crystal displays with xenon lamps as backlights, optical character readers, etc. Near infrared absorbing dye for writing or reading, near infrared light sensitization , Photothermal exchange agents such as thermal transfer and thermal stencil, photothermal exchange agent for laser fusion that heat-seals resin using laser beam, near infrared absorption filter, anti-eye strain or photoconductive material, etc. Photosensitive dye for tumor treatment that absorbs light in the long wavelength range with good transparency, color cathode ray tube selective absorption filter, color toner, ink for inkjet, anti-counterfeiting ink, anti-counterfeiting bar code ink, near red When used as an external absorption ink, marking agent for positioning of photographs and films, goggles lenses and shielding plates, dyeing agents for sorting when recycling plastics, and preheating aids when molding PET bottles It exhibits an excellent effect. Considering the above-described characteristics in particular, the phthalocyanine compound of the present invention can be suitably used for a near infrared absorption filter, particularly a near infrared absorption filter for a plasma display panel.

  Moreover, the phthalocyanine compound of the present invention has a maximum absorption wavelength (λmax) in a wavelength region of 700 to 1100 nm in the near infrared region. Here, in particular, when a phthalocyanine compound is used for a near infrared absorption filter, particularly a near infrared absorption filter for a plasma display panel, the phthalocyanine compound is used for other remote controllers and infrared data communication of 700 to 1100 nm, especially in the surroundings. It is preferable to have a maximum absorption wavelength (λmax) in a wavelength range of 800 to 1100 nm, more preferably 850 to 1000 nm. In this specification, the maximum absorption wavelength (λmax) of the phthalocyanine compound is a value obtained by measuring the maximum absorption wavelength (λmax) of the phthalocyanine compound in chloroform using a spectrophotometer (manufactured by Shimadzu Corporation: UV-1650PC). (Nm).

  Further, the gram extinction coefficient of the phthalocyanine compound of the present invention is not particularly limited. However, in consideration of the use as described above, particularly a near infrared absorption filter, particularly a near infrared absorption filter for a plasma display panel, preferably 40 As mentioned above, More preferably, it is 50 or more, More preferably, it is 60 or more. Moreover, since the upper limit of the gram extinction coefficient of the phthalocyanine compound of the present invention is preferably as high as possible, it is not particularly limited, but is usually 120, and preferably 100. In the present specification, the gram extinction coefficient of the phthalocyanine compound was measured according to the following method. In a measuring flask, 80 mg of a phthalocyanine compound was dissolved in chloroform so as to have a concentration of 0.016 g / L. The solution thus prepared was placed in a 1 cm square Pyrex cell, and the transmission spectrum was measured using a spectrophotometer (manufactured by Shimadzu Corporation: UV-1650PC). Further, when the measured absorbance is A, the gram extinction coefficient was calculated by the following formula.

  The positional isomer of the phthalocyanine compound represented by the above formula (1) is also included in the technical scope of the present invention. Here, the “positional isomer” generally refers to isomers having different substituent positions in the molecule produced when phthalocyanine is produced from phthalonitrile. In the present specification, the positional isomer in the phthalocyanine compound represented by the above formula (1) means the structure of (1), (1a), (1b), (1c) as shown in the figure below. In the present specification, a unit represented by the following formula is referred to as a “phthalocyanine structural unit”, that is, the phthalocyanine compound of the present invention has four phthalocyanine structural units and a central metal (“ M ").

  Here, the positional isomers of the phthalocyanine compound represented by the formula (1) include not only the case where all the phthalocyanine structural units have the above structure but also the case where a part thereof has the structure of the above positional isomer.

  In general, the phthalocyanine compound has the following formula (2):

In the present specification, in the above formula (2), Z ₂ , Z ₃ , Z ₆ , Z ₇ , Z ₁₀ , Z ₁₁ , Z ₁₄ , Z ₁₅ of the phthalocyanine skeleton are collectively shown. The “β-position” and Z ₁ , Z ₄ , Z ₅ , Z ₈ , Z ₉ , Z ₁₂ , Z ₁₃ , and Z ₁₆ of the phthalocyanine skeleton are collectively referred to as “α-position”. Therefore, the substituents for substituting the substituents of Z ₂ , Z ₃ , Z ₆ , Z ₇ , Z ₁₀ , Z ₁₁ , Z ₁₄ , Z ₁₅ of the phthalocyanine skeleton at the eight β-positions of the phthalocyanine nucleus or simply “ β-position substituents ”and Z ₁ , Z ₄ , Z ₅ , Z ₈ , Z ₉ , Z ₁₂ , Z ₁₃ , and Z ₁₆ substituents of the phthalocyanine skeleton at the eight α-positions of the phthalocyanine nucleus. Also referred to as a substituent to be substituted or simply “substituent at the α-position”.

  In the above formula (1), M represents a metal-free, metal, metal oxide or metal halide. Here, metal-free means an atom other than a metal, for example, two hydrogen atoms. Examples of the metal include manganese, such as iron, magnesium, nickel, cobalt, copper, palladium, zinc, vanadium, titanium, indium, and tin. Examples of the metal oxide include titanyl, vanadyl, manganese oxide and the like. Examples of the metal halide include aluminum chloride, indium chloride, germanium chloride, tin chloride, and silicon chloride. Preferred are metals, metal oxides or metal halides, specifically zinc, copper, cobalt, nickel, iron, vanadyl, titanyl, indium chloride, tin chloride, more preferably copper, vanadyl and zinc. It is.

  In the above formula (1), the substituent “—X—Ar—X′—” is a substituent that exists across the α-position and the β-position of the phthalocyanine skeleton. Thus, the structure in which the substituent “—X—Ar—X′—” is bonded (fixed) to the phthalocyanine skeleton at two positions in the phthalocyanine skeleton suppresses the movement of the benzene ring portion of the phthalocyanine skeleton. . Therefore, since the substituent of the phthalocyanine compound of the present invention is fixed in the adhesive layer and has a stable structure, even if it is put in the adhesive layer, it is not easily attacked by impurities (contact with impurities hardly occurs). It is possible to significantly suppress and prevent deterioration of characteristics. Therefore, the phthalocyanine compound of the present invention has excellent effects even in the adhesive layer (high visible light transmittance, high near-infrared light cutting efficiency, excellent near-infrared absorption ability, excellent solvent solubility, and excellent resin compatibility. It is possible to exhibit excellent light resistance while maintaining solubility, excellent heat resistance and excellent light resistance and weather resistance. In addition to the above advantages, the molecular weight of the phthalocyanine compound itself can be kept low due to the presence of the structure derived from the substituent “—X—Ar—X′—”. For this reason, it is possible to increase the gram extinction coefficient (ε) of phthalocyanine compounds, and therefore excellent effects with a small amount of phthalocyanine compounds (high visible light transmittance, high near infrared light cut efficiency, excellent near red color) External absorption ability, excellent solvent solubility, excellent compatibility with resin, excellent heat resistance, excellent light resistance, excellent weather resistance, etc.).

  As is clear from formula (1), there are four substituents “—X—Ar—X′—” per phthalocyanine compound. The substituents “X”, “X ′” and “Ar” in these substituents “—X—Ar—X′—” may be the same or different in each phthalocyanine structural unit. May be.

  In the above formula (1), X and X ′ represent an oxygen atom (—O—) or a sulfur atom (—S—). In this case, X and X ′ may be the same or different, but are preferably the same. X and X ′ may be the same or different in each phthalocyanine structural unit.

  Ar represents an o-phenylene group which may have a substituent, an o-naphthylene group which may have a substituent, or an o-anthrylene group which may have a substituent. In this case, Ar may also be the same or different in each phthalocyanine structural unit. In consideration of the molecular weight (gram extinction coefficient) and solubility of the resulting phthalocyanine compound, Ar is an o-phenylene group which may have a substituent or an o-naphthylene group which may have a substituent. Is preferred.

  Here, Ar may be unsubstituted or may have a substituent. In the latter case, the substituent optionally present in Ar includes a halogen atom, an alkyl group having 1 to 20 carbon atoms, -OY (Y represents an alkyl group having 1 to 20 carbon atoms), Or -SY '(Y' represents an alkyl group having 1 to 20 carbon atoms). The halogen atom is a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, preferably a fluorine atom, a chlorine atom or a bromine atom, more preferably a fluorine atom or a chlorine atom. The alkyl group having 1 to 20 carbon atoms is a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, and preferably a linear or branched group having 1 to 8 carbon atoms. Chain alkyl group. 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, n-hexyl group, cyclohexyl group, 1,3-dimethylbutyl group, 1-isopropylpropyl group, 1,2-dimethylbutyl group, n-heptyl group, 1,4-dimethylpentyl group, 2 -Methyl-1-isopropylpropyl group, 1-ethyl-3-methylbutyl group, n-octyl group, 2-ethylhexyl group and the like can be mentioned. Of these, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, and a tert-butyl group are preferable, and a tert-butyl group is particularly preferable. -OY (Y represents an alkyl group having 1 to 20 carbon atoms) is a linear, branched or cyclic alkoxyl group having 1 to 20 carbon atoms, preferably 1 to 8 carbon atoms. Straight, branched or cyclic alkoxyl groups. 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, neo Examples include pentyloxy group, 1,2-dimethyl-propoxy group, n-hexyloxy group, cyclohexyloxy group, 1,3-dimethylbutoxy group, 1-isopropylpropoxy group and the like. Among these, a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, an isobutoxy group, a sec-butoxy group, and a tert-butoxy group are preferable. -SY '(Y' represents an alkyl group having 1 to 20 carbon atoms) is a linear, branched or cyclic alkylthio group having 1 to 20 carbon atoms, preferably 1 carbon atom. An alkylthio group in which up to 8 linear, branched or cyclic alkyl groups are bonded to a sulfur atom. Examples of the alkyl group bonded to the sulfur atom are the same as those described above for the alkyl group, Is an alkylthio group having 1 to 4 carbon atoms. Among the above, the substituent optionally present in Ar is preferably a linear or branched alkyl group or alkoxyl group having 1 to 8 carbon atoms, particularly preferably a tert-butyl group. Here, the number of bonds of the substituent to Ar is not particularly limited, but considering the light resistance of the resulting phthalocyanine compound, reactivity of the cyclization reaction, etc., preferably 1 to 4, more preferably 1 to 3, Even more preferably, one or two. Also, the bonding position of the substituent to Ar is not particularly limited. For example, when one substituent is bonded to the o-phenylene group as Ar, the substituent may be bonded to either the 3-position or the 4-position of the o-phenylene group. When two are bonded, the substituent may be bonded to any of the 3, 4-position, 3, 5-position, 3, 6-position, and 4, 5-position of the o-phenylene group, preferably 4, 5 Join the place. Among these, Ar is a catechol-derived group having a substituent at the 4- and 5-positions (catechol unit; that is, in formula (1), X and X ′ are an oxygen atom or a sulfur atom, and Ar is o-phenylene. Particularly preferred). In addition, when one substituent is bonded to the o-naphthylene group as Ar, the substituent is preferably bonded to any of the 1, 2 and 3 positions of the o-naphthylene group, and the o-naphthylene group is bonded to the o-naphthylene group. When two are bonded, the substituent is preferably bonded to the o-naphthylene group at any one of the 1,2-position and the 2,3-position.

  In the above formula (1), R ′ and R ″ may have a hydrogen atom, a phenyl group which may have a substituent, an aralkyl group which may have a substituent, or a substituent. Represents an alkyl group having 1 to 20 carbon atoms, wherein R ′ and R ″ may be the same or different, and each phthalocyanine structural unit is the same It may be different or different. Thus, when —N (R ′) (R ″) is present at the α-position of the phthalocyanine skeleton, the maximum absorption wavelength is increased while maintaining the visible light transmittance high (ie, suppressing the absorption of visible light). Moreover, the maximum absorption wavelength of the resulting phthalocyanine compound can be easily controlled by appropriately selecting R ′ and R ″ in the substituent —N (R ′) (R ″). Therefore, even if the phthalocyanine compound of the present invention is used as a near-infrared absorption filter (malfunction prevention filter) for a plasma display, it effectively cuts near-infrared light emitted from the display and has a high visible light transmittance, which is excellent. Specifically, the visible light transmittance of the phthalocyanine compound is at least 65% or more, preferably 70% or more. Preferred.

  Here, the alkyl group having 1 to 20 carbon atoms as R ′ and R ″ is a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, preferably 1 carbon atom. -8 linear or branched alkyl groups, specifically methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl Group, n-pentyl group, isopentyl group, neopentyl group, 1,2-dimethylpropyl group, n-hexyl group, cyclohexyl group, 1,3-dimethylbutyl group, 1-isopropylpropyl group, 1,2-dimethylbutyl group N-heptyl group, 1,4-dimethylpentyl group, 2-methyl-1-isopropylpropyl group, 1-ethyl-3-methylbutyl group, n-octyl group, 2-ethylhexyl group Sil group, nonyl group, decyl group, undecyl group, dodecyl group, tetradecyl group, octadecyl group, icosyl group, 3-methyl-1-isopropylbutyl group, 2-methyl-1-isopropyl group, 1-tert-butyl-2 -Methylpropyl group, n-nonyl group, 3,5,5-trimethylhexyl group, etc. Among them, 2-ethylhexyl group and n-hexyl group are preferable. Also, aralkyl as R ′ and R ″ Examples of the group include, but are not limited to, a benzyl group, a phenethyl group, a diphenylmethyl group, and the like. Moreover, the substituent which exists depending on the case in the said phenyl group or aralkyl group, and the substituent which exists depending on the said alkyl group are explained in full detail below.

  Among the above, it is preferable that one of R ′ and R ″ is a hydrogen atom and the other is an alkyl group having 1 to 20 carbon atoms, more preferably one of R ′ and R ″ is a hydrogen atom. And the other is an n-octyl group, 2-ethylhexyl group, n-hexyl group; an alkyl group having 1 to 3 aryl groups having 1 to 3 aryl groups as substituents, particularly preferably R ′ and One of R ″ is a hydrogen atom and the other is a 2-ethylhexyl group or an n-hexyl group; or one of R ′ and R ″ is a hydrogen atom and the other is substituted with a phenyl group as 1 or A methyl group or an ethyl group having two. Here, for example, -N (R ') (R ") in which R' is a hydrogen atom and R" is a methyl group having two phenyl groups includes a benzhydrylamino group, and R ' —N (R ′) (R ″) in which is a hydrogen atom and R ″ is an ethyl group having one phenyl group includes a 1- or 2-phenylethylamino group.

  In the above formula (1), A represents an oxygen atom (—O—), a sulfur atom (—S—) or a single bond (—). In this case, A may be the same or different in each phthalocyanine structural unit. R is a phenyl group or naphthyl group which may have a substituent, an aralkyl group which may have a substituent, or an alkyl having 1 to 20 carbon atoms which may have a substituent. Represents a group. In this case, R may be the same or different in each phthalocyanine structural unit.

  Here, the alkyl group having 1 to 20 carbon atoms as R is a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, preferably 1 to 8 carbon atoms. It is a linear or branched alkyl group. 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, n-hexyl group, cyclohexyl group, 1,3-dimethylbutyl group, 1-isopropylpropyl group, 1,2-dimethylbutyl group, n-heptyl group, 1,4-dimethylpentyl group, 2 -Methyl-1-isopropylpropyl group, 1-ethyl-3-methylbutyl group, n-octyl group, 2-ethylhexyl group and the like can be mentioned. Among these, a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an n-pentyl group, an n-hexyl group, and an n-octyl group are preferable, and an ethyl group, an n-propyl group, an n-butyl group, An n-hexyl group is particularly preferred. Examples of the aralkyl group as R include, but are not limited to, benzyl group, phenethyl group, diphenylmethyl group and the like. Among the above, R is preferably a phenyl group or a naphthyl group which may have a substituent, and more preferably an unsubstituted or substituted phenyl group. When R has a substituent, the substituent is not limited to the above, and the substituents described in detail below can also be used in the same manner. In addition, the number and position of the substituents bonded to the phenyl group are not limited to the above. Specifically, the number of bonds of the substituent to the phenyl group may be any integer of 1 to 5, preferably 1 to 4, more preferably 1 to 3, and most preferably 1 or 2. is there. Moreover, the bonding position of the substituent to the phenyl group is not particularly limited.

  Hereinafter, the substituent which may exist in the phenyl group or the aralkyl group will be described. Examples of the substituent optionally present in the phenyl group or aralkyl group include, for example, a halogen atom, an acyl group, an alkyl group, a phenyl group, an alkoxyl group, a halogenated alkyl group, a halogenated alkoxyl group, a nitro group, an amino group, Alkylamino group, alkylcarbonylamino group, arylamino group, arylcarbonylamino group, carbonyl group, alkoxycarbonyl group, alkylaminocarbonyl group, alkoxysulfonyl group, alkylthio group, carbamoyl group, aryloxycarbonyl group, oxyalkyl ether group, Although a cyano group etc. can be illustrated, it is not limited to these. These substituents can be substituted with 1 to 5 phenyl groups or aralkyl groups, and the types of these substituents may be the same or different when a plurality of substituents are substituted. Some of the above substituents are shown below with more specific examples.

  First, among the substituents optionally present in the phenyl group or aralkyl group, the halogen atom is a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, preferably a fluorine atom or a chlorine atom.

  Among the substituents optionally present in the phenyl group or aralkyl group, the acyl group includes an acetyl group, an ethylcarbonyl group, a propylcarbonyl group, a butylcarbonyl group, a pentylcarbonyl group, a hexylcarbonyl group, a benzoyl group, p -Tert-butylbenzoyl group etc. are mentioned, Among these, an ethylcarbonyl group is preferable.

  Of the substituents optionally present in the phenyl group or aralkyl group, the alkyl group is a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, preferably 1 carbon atom. ~ 8 linear, branched or cyclic alkyl groups. 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, n-hexyl group, cyclohexyl group, 1,3-dimethylbutyl group, 1-isopropylpropyl group, 1,2-dimethylbutyl group, n-heptyl group, 1,4-dimethylpentyl group, 2 -Methyl-1-isopropylpropyl group, 1-ethyl-3-methylbutyl group, n-octyl group, 2-ethylhexyl group and the like can be mentioned. Of these, a methyl group and an ethyl group are preferred. More specifically, examples of the phenyl group having an alkyl group include 2-methylphenyl group, 4-methylphenyl group, 4-ethylphenyl group, 2,6-dimethylphenyl group, 2,6-diethylphenyl group. and so on.

  Of the substituents optionally present in the phenyl group or aralkyl group, the alkoxyl group is a linear, branched or cyclic alkoxyl group having 1 to 20 carbon atoms, preferably 1 to 8 carbon atoms. Straight, branched or cyclic alkoxyl groups. 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, neo Examples include pentyloxy group, 1,2-dimethyl-propoxy group, n-hexyloxy group, cyclohexyloxy group, 1,3-dimethylbutoxy group, 1-isopropylpropoxy group and the like. Of these, methoxy and ethoxy groups are preferred. More specifically, examples of the phenyl group having an alkoxyl group include a 4-methoxyphenyl group, a 4-ethoxyphenyl group, a 2,6-dimethoxyphenyl group, and a 2,6-diethoxyphenyl group.

  Among the substituents optionally present in the phenyl group or aralkyl group, the halogenated alkyl group is a halogenated part of a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms. Preferably, a part of a linear, branched or cyclic alkyl group having 1 to 8 carbon atoms is halogenated. Specific examples include chloromethyl group, bromomethyl group, trifluoromethyl group, chloroethyl group, 2,2,2-trichloroethyl group, bromoethyl group, chloropropyl group, bromopropyl group and the like.

  Among the substituents optionally present in the phenyl group or aralkyl group, the halogenated alkoxyl group is a halogenated part of a linear, branched or cyclic alkoxyl group having 1 to 20 carbon atoms. Preferably, a part of a linear, branched or cyclic alkoxyl group having 1 to 8 carbon atoms is halogenated. Specific examples include chloromethoxy group, bromomethoxy group, trifluoromethoxy group, chloroethoxy group, 2,2,2-trichloroethoxy group, bromoethoxy group, chloropropoxy group, bromopropoxy group and the like.

  Of the substituents optionally present in the phenyl group or aralkyl group, the alkylamino group is an alkylamino group having an alkyl moiety having 1 to 20 carbon atoms, preferably an alkyl having 1 to 8 carbon atoms. An alkylamino group having a moiety. Specifically, (di) methylamino group, (di) ethylamino group, (di) n-propylamino group, (di) n-butylamino group, (di) sec-butylamino group, (di) n -Pentylamino group, (di) n-hexylamino group, (di) n-heptylamino group, (di) n-octylamino group, (di) 2-ethylhexylamino group, and the like. Of these, a methylamino group, an ethylamino group, an n-propylamino group, an n-butylamino group, an n-hexylamino group, and a 2-ethylhexylamino group are preferable.

  Among the substituents optionally present in the above phenyl group or aralkyl group, the alkoxycarbonyl group is a C 1-8, preferably 1-5 carbon atom which may contain a hetero atom in the alkyl group part of the alkoxyl group. Or a cyclic alkoxycarbonyl group having 3 to 8, preferably 5 to 8 carbon atoms which may contain a hetero atom. Specific examples include methoxycarbonyl group, ethoxycarbonyl group, n-propoxycarbonyl group, isopropoxycarbonyl group, n-butoxycarbonyl group, isobutoxycarbonyl group, sec-butoxycarbonyl group, tert-butoxycarbonyl group and the like. . Of these, a methoxycarbonyl group and an ethoxycarbonyl group are preferred.

  On the other hand, the unsubstituted alkyl group having 1 to 20 carbon atoms may be any of linear, branched or cyclic alkyl groups having 1 to 20 carbon atoms, preferably carbon. It is a linear or branched alkyl group having 1 to 8 atoms. 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, n-hexyl group, cyclohexyl group, 1,3-dimethylbutyl group, 1-isopropylpropyl group, 1,2-dimethylbutyl group, n-heptyl group, 1,4-dimethylpentyl group, 2 -Methyl 1-isopropylpropyl group, 1-ethyl-3-methylbutyl group, n-octyl group, 2-ethylhexyl group and the like can be mentioned.

  Here, the substituent which exists depending on the case in the alkyl group will be described. Examples of the substituent optionally present in the alkyl group having 1 to 20 carbon atoms include a halogen atom, an alkoxyl group, a hydroxyalkoxyl group, an alkoxyalkoxyl group, a halogenated alkoxyl group, a nitro group, an amino group, and an alkyl group. Examples thereof include, but are not limited to, an amino group, an alkoxycarbonyl group, an alkylaminocarbonyl group, an alkoxysulfonyl group, and an aryl group. These types of substituents may be the same or different when a plurality of substituents are substituted. More specific examples of some of these substituents may be those listed above as more specific examples of some of the substituents optionally present in the phenyl group or aralkyl group. This is omitted here. Further, specific examples of the aryl group as a substituent are not particularly limited, and examples thereof include a phenyl group and a naphthyl group, and a phenyl group is preferable.

  In the present invention, the substituents “—A—R” and “—N— (R ′) (R ″)” introduced at the α-position and the β-position are homogeneous in the phthalocyanine structural unit (each benzene ring of the phthalocyanine skeleton). (The same number of substituents are present on each benzene ring). That is, four —A—R and four —N (R ′) (R ″) are present one at each of the α-position and β-position of each benzene ring of the phthalocyanine skeleton. The compound production process is easy, and various properties (visible light transmittance, near infrared light cut efficiency, near infrared absorption ability, solvent solubility, compatibility with resin, heat resistance, light resistance and weather resistance) Etc.) can be improved.

  Accordingly, preferred examples of the phthalocyanine compound of the present invention include the following compounds. In the following examples, M of the phthalocyanine compound of the above formula (1) is not defined. The phthalocyanine compound of the present invention is not limited to this, and it goes without saying that the phthalocyanine compound exemplified below is a metal-free, metal oxide or metal halide. Moreover, although the positional isomer is not described in the following examples, it goes without saying that the positional isomer of each phthalocyanine compound is also included.

  The method for producing the phthalocyanine compound or the positional isomer thereof according to the present invention is not particularly limited, and a conventionally known method such as JP-A No. 2001-106869 or JP-A No. 2005-220060 can be appropriately used. However, a method in which a phthalonitrile compound and a metal salt are cyclized in a molten state or in an organic solvent is preferably used. Hereinafter, particularly preferred embodiments of the method for producing the phthalocyanine compound of the present invention or the positional isomer thereof will be described. However, the present invention is not limited to the following preferred embodiments.

  That is, the following formula (3):

A cyclization reaction of a phthalonitrile compound represented by the following formula with one selected from the group consisting of metal oxides, metal carbonyls, metal halides, and organic acid metals (also collectively referred to as “metal salts” in this specification) By doing so, the phthalocyanine compound (1) can be produced. In the above formula (3), the substituents “X”, “X ′”, “Ar”, “A”, “R”, “R ′” and “R” ”are the desired phthalocyanine compounds (1) And is the same as the definition of the above formula (1), and the description is omitted here. For this reason, when the said substituent in each phthalocyanine structural unit differs, multiple types of phthalonitrile compounds which have a substituent corresponding to each substituent are used. In addition, since the positional isomer of the phthalocyanine compound can be similarly produced using the phthalonitrile compound of the above formula (3) and the positional isomer thereof in the same manner as described below, Description of the method for producing the regioisomer of the phthalocyanine compound is omitted.

  In the above production method, the phthalonitrile compound of the formula (3) is appropriately selected according to the desired phthalocyanine structure, and four different phthalonitrile compounds may be used, or only one phthalonitrile compound may be used. May be.

  Or following formula (4):

However, X, X ′, Ar, A and R have the same definition as in the above formula (1), and Z is a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, preferably a fluorine atom and Represents a chlorine atom, particularly preferably a fluorine atom,
Is cyclized with a compound selected from the group consisting of metal oxides, metal carbonyls, metal halides and organic acid metals, and then the reaction product is further represented by the following formula: H-N ( R ′) (R ″) (wherein R ′ and R ″ have the same definitions as in the above formula (1)) and a reaction with an amino compound (hereinafter also simply referred to as “amino compound”) The phthalocyanine compound of the present invention may be produced by

  Specifically, the phthalonitrile compound of the above formula (4) is subjected to a cyclization reaction with one selected from the group consisting of metal oxides, metal carbonyls, metal halides, and organic acid metals, whereby an amino group (the above formula A compound (phthalocyanine derivative) having no —N (R ′) (R ″)) in (1) is synthesized, and then the phthalocyanine derivative synthesized in this way is further reacted with an amino compound of the above formula. In this method, the nucleophilic substitution reactivity with the amino group of the amino compound of the above formula is significantly higher when it is a halogen atom. It utilizes the fact that it hardly exhibits nucleophilic substitution reactivity, and a halogen atom reacts with an amino compound of the above formula to give an amino group (in the formula (1) above). The -N (R ') (R ")) can be selectively introduced into a desired position. Therefore, an amino group (—N (R ′) (R ″) in the above formula (1)) can be efficiently introduced at a desired position of the phthalocyanine skeleton, and the purity and yield of the target phthalocyanine compound are improved. And a phthalocyanine having a maximum absorption wavelength at an arbitrary position of 850 to 1000 nm.

In the above embodiment, the phthalonitrile compound of the formula (2) as a starting material can be synthesized by a conventionally known method such as the method disclosed in JP-A No. 64-45474 or JP-A No. 2007-230999. Moreover, a commercial item can also be used. Preferably, the following method is used. However, the method for producing the phthalocyanine compound of the present invention is not limited by the following method. Specifically, in the above formula (1), when A is an oxygen atom or a sulfur atom, the halogenated phthalonitrile represented by the formula (5) is represented by the formula (6) as shown in the following reaction formula. ): Obtained by reacting with a compound represented by H-A-R. In this case, in the formula (5), Z ₁ , Z ₂ , Z ₃ and Z ₄ are each independently a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, preferably a fluorine atom and a chlorine atom. Particularly preferably, it represents a fluorine atom. Moreover, in said Formula (6), A and R are the definitions similar to said Formula (1). In the following description, the same substituents are defined in the same manner as described above, and thus their descriptions are omitted.

  Thus, by previously introducing the substituent -A-R at the 4-position of the halogenated phthalonitrile of the formula (5), the reaction product of the formula (7) obtained here and the formula (8) of the next step: By the reaction with the compound of HX-Ar-X′H, the substituent —X—Ar—X— can be introduced so as to cross the 5,6 position of the reaction product of formula (7). In the reaction between the halogenated phthalonitrile represented by the formula (5) and the compound represented by the formula (6): H—A—R, the nucleophilic substitution reaction first occurs at the 4-position from the viewpoint of reactivity. For this reason, the substituent —A—R is selectively introduced into the β-position (4-position or 5-position) of the halogenated phthalonitrile of the formula (5) by the above reaction.

  In the above reaction, when a plurality of compounds of the formula (6) (H-A-R) are used, each mixing ratio of the compound of the formula (6) (H-A-R) is the target phthalo It is appropriately selected depending on the structure of the nitrile compound. The amount of the compound of formula (6) used is not particularly limited as long as these reactions can proceed to produce the desired reaction product of formula (7). When one substituent —A—R is introduced into the fluorinated phthalonitrile, the amount of the compound of formula (6) (H—A—R) added stoichiometrically is the halogen of formula (5). Although it is equivalent to phthalonitrile, it is preferable to add more compound (H-A-R) of the formula (6) to the halogenated phthalonitrile of the formula (5) in view of reaction efficiency and the like. Specifically, the compound (HAR) of the formula (6) is preferably 0.8 to 10 mol, more preferably 1 to 3 mol per 1 mol of the halogenated phthalonitrile of the formula (5). The halogenated phthalonitrile of formula (5) is reacted in a molar amount.

  The reaction of the halogenated phthalonitrile of the formula (5) and the compound of the formula (6) may be performed in the absence of a solvent or in an organic solvent, but is preferably performed in an organic solvent. Examples of the organic solvent that can be used at this time include acetonitrile, benzonitrile, acetone, methyl ethyl ketone, and methyl isobutyl ketone. Of these, methyl ethyl ketone, acetonitrile, benzonitrile, and methyl isobutyl ketone are preferable, and methyl ethyl ketone and acetonitrile are more preferable. The amount of the organic solvent used when the solvent is used is preferably such that the solid content of the halogenated phthalonitrile of formula (5) and the compound of formula (6) (H-A-R) is a concentration in the organic solvent. Is such an amount that it is 5 to 50% by mass, more preferably 10 to 40% by mass.

  The addition form of the halogenated phthalonitrile of the formula (5) and the compound of the formula (6) is not particularly limited. For example, when the above reaction is carried out in an organic solvent, the above reaction may be carried out in a stepwise or batchwise or separately from the halogenated phthalonitrile of formula (5) and the compound of formula (6). Continuously added to an organic solvent; a) a compound of formula (6) is added stepwise or continuously to a solution of the halogenated phthalonitrile of formula (5) in an organic solvent; c) The halogenated phthalonitrile of formula (5) is added stepwise or continuously to a solution of the compound of formula (6) dissolved in an organic solvent; d) the halogenated phthalonitrile of formula (5) is added to an organic solvent. Stepwise or continuously, a solution dissolved in (5) is added to a solution in which the compound of formula (6) is dissolved in an organic solvent; e) a solution in which the compound of (6) is dissolved in an organic solvent is added stepwise. Or continuously, halogenation of formula (5) The Taronitoriru performed such as by adding a solution in an organic solvent. Among these, in consideration of the above reaction efficiency and the like, the addition method of a) and o) is preferable, and the addition method of o) is particularly preferable. In the above (e) and (e), the organic solvent used may be the same or different in the halogenated phthalonitrile of the formula (5) and the compound of the formula (6). , Preferably the same.

  In addition, the reaction of the halogenated phthalonitrile of the formula (5) with the compound of the formula (6) is carried out by using these trapping agents in order to remove hydrogen halide (for example, hydrogen fluoride) generated during the reaction. It is preferable to use it. Specific examples of the trapping agent when using the trapping agent include potassium fluoride, potassium carbonate, calcium carbonate, calcium hydroxide, magnesium hydroxide, magnesium chloride, and magnesium carbonate. Potassium fluoride, calcium carbonate and calcium hydroxide are preferred, and potassium fluoride and calcium carbonate are most preferred. 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 and the like generated during the reaction, but 1 mol of the halogenated phthalonitrile of the formula (5) The amount is usually 1 to 10 mol, preferably 1.05 to 5 mol. In addition, when using the trapping agent, the trapping agent may be added at any time, but is preferably added to the halogenated phthalonitrile of the formula (5) or the compound of the formula (6), more preferably Add a solution of the halogenated phthalonitrile of formula (5) in an organic solvent or a solution of the compound of formula (6) in an organic solvent, and more preferably use the halogenated phthalonitrile of formula (5) as an organic solvent. Add to dissolved solution.

  The reaction conditions for the halogenated phthalonitrile of the above formula (5) and the compound of the formula (6) are not particularly limited as long as this reaction proceeds. Specifically, the reaction between the halogenated phthalonitrile of formula (5) and the compound of formula (6) is performed at a reaction temperature of -20 to 120 ° C, more preferably -10 to 80 ° C for 1 to 24 hours. More preferably, it is performed for 2 to 12 hours.

In addition, in the above formula (1), the production method of the phthalocyanine compound when A is a single bond is not particularly limited, and for example, a known method such as the method described in JP-A-2007-230999 is required. It can be used after modification. Hereinafter, preferred embodiments of the method will be described. That is, as shown in the following reaction formula, in the presence of an alkali metal halide and / or an alkaline earth metal halide, the halogenated phthalonitrile represented by the formula (5) is converted to the formula (6 ′): R— It is obtained by reacting with a compound represented by MgQ [wherein Q is a halogen atom, preferably a chlorine atom, a bromine atom or an iodine atom, more preferably a bromine atom or an iodine atom]. In this case, in the formula (5), Z ₁ , Z ₂ , Z ₃ and Z ₄ are each independently a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, preferably a fluorine atom and a chlorine atom. Particularly preferably, it represents a fluorine atom. Moreover, in said formula (6 '), R is the definition similar to said formula (1). In the following description, the same substituents are defined in the same manner as described above, and thus their descriptions are omitted.

  According to the above reaction, by using the alkali metal halide and / or the alkaline earth metal halide, the attack on the cyano group of the compound of the above formula (6 ′) (Grignard reagent) is suppressed, and in the formula (5) The selectivity of the substitution reaction from the halogenated phthalonitrile shown (the yield of the substituted product) can be improved. That is, in the reaction between the halogenated phthalonitrile represented by the formula (5) and the compound represented by the formula (6 ′): R—MgQ, the nucleophilic substitution reaction first occurs at the 4-position from the viewpoint of reactivity. . For this reason, the substituent -R is selectively introduced into the β-position (4-position or 5-position) of the halogenated phthalonitrile of the formula (5) by the above reaction.

  In the above reaction, the alkali metal halide and / or the alkaline earth metal halide is not particularly limited. Specifically, as the alkali metal halide, lithium halide is preferably used, and lithium chloride and lithium bromide are more preferable. Further, as the alkaline earth metal halide, magnesium fluoride, magnesium chloride, magnesium bromide, and calcium chloride are preferably used. Among these, lithium chloride is most preferable in consideration of the solubility in a solvent and the influence of reactivity and selectivity. Here, the alkali metal halide and the alkaline earth metal halide may be used alone or in combination of two or more, or one or more of these may be used as appropriate. They may be used in combination.

  The compound of the above formula (6 ′) (hereinafter also referred to as “Grignard reagent”) can be produced from a known organic halide by the known method as shown below. The Grignard reagent may be a commercially available product. For example, it can be easily produced by adding an organic halide or an organic halide solution to a solvent (usually an ether solvent, preferably tetrahydrofuran (THF)) added with magnesium. Since the Grignard reagent is unstable with respect to water or the like, its preparation must be performed in an atmosphere excluding moisture, for example, in an inert gas (preferably nitrogen or argon) atmosphere, and the solvent is also dehydrated. You need to use something. Further, the amount of magnesium used for preparing the Grignard reagent is usually at least 1 time, 1.5 times or less, preferably 1.3 times or less, more preferably 1.2 times the theoretically required amount. It is as follows. The concentration of the Grignard reagent solution is preferably about 0.1 to 2 (mol / L), more preferably about 1 (mol / L).

  Further, since the Grignard reagent is unstable with respect to water or the like, the solution prepared with the Grignard reagent is preferably used as it is for the synthesis reaction. Usually, in the coupling of the Grignard reagent and the halogenated phthalonitrile represented by the formula (5), the reaction is performed by adding the Grignard reagent solution to the halogenated phthalonitrile of the formula (5) as a substrate or a solution thereof. Is done. Although such an addition form is preferable, the substrate or the solution thereof may be added to the Grignard reagent solution, or the Grignard reagent solution and the substrate solution may be simultaneously added to and mixed in the reaction vessel.

  The solvent used in the above reaction is not particularly limited, and a solvent in which an additive (an alkali metal halide and / or an alkaline earth metal halide), a Grignard reagent, and a halogenated phthalonitrile of the formula (5) is dissolved is used. be able to. In order to prevent the Grignard reagent from being decomposed, it is preferable to use a sufficiently dehydrated solvent. Preferred solvents are ether solvents, more preferred are THF and diethyl ether. The said solvent may be used independently or may be used with the form of a 2 or more types of mixture.

  Addition and mixing of the Grignard reagent solution and the halogenated phthalonitrile of the formula (5), and stirring for sufficiently proceeding with the subsequent coupling reaction are performed in an atmosphere from which moisture has been removed, for example, an inert gas (preferably nitrogen or Argon) is preferably performed in an atmosphere.

  A coupling reaction between the Grignard reagent and the halogenated phthalonitrile of the formula (5) as a substrate in the presence of an alkali metal halide or the like is carried out by subjecting at least one of the Grignard reagent solution and the substrate solution to halogenation. It can be carried out by mixing an Grignard reagent solution and a substrate solution containing an alkali metal or the like. In addition, when using a substrate solution, the concentration is not particularly limited, but in order to improve the reaction rate, the concentration of the substrate solution is preferably as high as possible.

  In order to promote coordination or interaction with a Grignard reagent such as an alkali metal halide, it is preferable to use a Grignard reagent solution containing an alkali metal halide or the like in the reaction. More preferably, both the Grignard reagent solution and the substrate solution contain an alkali metal halide and / or an alkaline earth metal halide.

  The total addition amount of the alkali metal halide and / or alkali metal halide is not particularly limited, but is preferably 0.1 to 5 mol, more preferably 0.5 to 4 mol, per 1 mol of magnesium in the Grignard reagent. More preferably, it is about 1-3 mol.

  In the Grignard reagent and the substrate (halogenated phthalonitrile of the formula (5)), the amount of Mg in the Grignard reagent is preferably 1 to 3 mol, more preferably 1. It is preferable to make it react so that it may become 2-2 mol, More preferably, it is 1.3-1.7 mol. That is, for example, when an attempt is made to produce a monosubstituted product of a halogen-containing aromatic nitrile compound using a Grignard reagent having one magnesium in one molecule, the amount of Grignard reagent per mole of the substrate is preferably 1 to 3 moles, more preferably 1.2 to 2 moles, even more preferably 1.3 to 1.7 moles, and when the production of disubstituted products is planned, the amount of Grignard reagent per mole of substrate is preferably 2 It is -6 mol, More preferably, it is 2.4-4 mol, More preferably, it is 2.6-3.4 mol.

  The mixing and reaction of the Grignard reagent and the substrate is preferably performed at a low temperature in order to suppress side reactions. However, too low temperatures are too expensive for special equipment and cooling. In consideration of this, the mixing and reaction temperature is preferably 50 ° C to -35 ° C, more preferably 40 ° C to -20 ° C, and further preferably 30 to -5 ° C.

  During and after mixing the Grignard reagent and the substrate, the reaction is usually allowed to proceed sufficiently by stirring the reaction solution at the above temperature. This stirring time is preferably about 1 hour to several days, more preferably about 10 to 48 hours, and still more preferably about 24 hours. Next, the reaction can be terminated by mixing the acidic aqueous solution and the reaction solution.

  By such a reaction, reaction products of the above formulas (7) and (7 ′) are obtained. Here, the reaction products of the formulas (7) and (7 ′) are used as they are in the next step. Although it may use for reaction with the compound of Formula (8): HX-Ar-X'H, after refine | purifying, it uses for reaction with the compound of Formula (8): HX-Ar-X'H of the following process. It is preferable. Here, the purification method is not particularly limited, and known methods such as washing, solvent extraction, column chromatography using silica gel, alumina, etc., filtration, distillation, preferably solid distillation, recrystallization, reprecipitation, and sublimation can be used. Can be used.

  The reaction product of formula (7) or (7 ') obtained by the above reaction is then subjected to reaction with a compound of formula (8): HX-Ar-X'H. Here, in the reaction products of the formulas (7) and (7 ′), since the —A—R group has already been introduced at the 4-position of phthalonitrile, as shown in the following reaction formula, By the reaction with the compound of (8), X—Ar—X ′ can be introduced with a high probability so as to straddle the 5- and 6-positions of phthalonitrile.

  In the above reaction, when a plurality of compounds of formula (8) (HX—Ar—X′H) are used, as in the case of formula (6) above, the mixing ratio of each of the compounds of formula (8) is These are appropriately selected according to the structure of the target phthalonitrile compound. The amount of the compound of formula (8) used is an amount that can produce the desired compound of formula (9) by the reaction of the reaction product of formula (7) with the compound of formula (8). There is no particular limitation. The addition amount of the compound of formula (8) is stoichiometrically equivalent to the reaction product of formula (7), but considering the reaction efficiency and the like, the compound of formula (8) is converted to formula (7). Preferably, it is added in an amount of 0.8 to 1.2 mol, more preferably 0.9 to 1.1 mol, per 1 mol of the compound.

  The reaction between the reaction product of formula (7) and the compound of formula (8) may be carried out in the absence of a solvent or in an organic solvent, but is preferably carried out in an organic solvent. Examples of the organic solvent that can be used at this time include acetonitrile, benzonitrile, acetone, methyl ethyl ketone, and methyl isobutyl ketone. Of these, methyl ethyl ketone, acetonitrile, benzonitrile, and methyl isobutyl ketone are preferable, and methyl ethyl ketone and acetonitrile are more preferable. The amount of the organic solvent used when the solvent is used is such that the concentration in the organic solvent of the solid content of the reaction product of formula (7) and formula (8) is preferably 1 to 30% by mass, more preferably The amount is 2 to 20% by mass.

  The addition form of the reaction product of formula (7) and the compound of formula (8) is not particularly limited. For example, when the above reaction is carried out in an organic solvent, the above reaction may be carried out in a step or in a batch or separately from the reaction product of formula (7) and the compound of formula (8). Successively added to the organic solvent; b) adding the compound of formula (8) stepwise or continuously to the solution of the reaction product of formula (7) dissolved in the organic solvent; ) The reaction product of formula (7) is added stepwise or continuously to a solution of the compound of formula (8) dissolved in an organic solvent; d ') the reaction product of formula (7) is added to the organic solvent. Stepwise or continuously, the solution dissolved in (5) is added to the solution in which the compound of formula (8) is dissolved in an organic solvent; Or continuously, by adding the reaction product of formula (7) to a solution dissolved in an organic solvent, etc. Is Nawa. Among these, in consideration of the reaction efficiency and the like, the addition method (a) and e ') is preferable, and the addition method (v) is particularly preferable. In addition, in the above d ') and e'), the type of the organic solvent used may be the same or different for the reaction product of formula (7) and the compound of formula (8). Are preferably the same.

  The reaction between the reaction product of formula (7) and the compound of formula (8) uses these trapping agents to remove hydrogen halide (eg, hydrogen fluoride) generated during the reaction. It is preferable to do. Specific examples of the trapping agent when using the trapping agent include potassium fluoride, potassium carbonate, calcium carbonate, calcium hydroxide, magnesium hydroxide, magnesium chloride, and magnesium carbonate. Potassium fluoride, calcium carbonate and calcium hydroxide are preferred, and potassium fluoride and calcium carbonate are most preferred. Further, the amount of the trapping agent used when the trapping agent is used is not particularly limited as long as it is an amount capable of efficiently removing hydrogen halide and the like generated during the reaction, but it is 1 mol of the reaction product of the formula (7). On the other hand, it is 1-10 mol normally, Preferably it is 1.05-5 mol. Further, when using the trapping agent, the trapping agent may be added at any time, but is preferably added to the reaction product of the formula (7) or the compound of the formula (8), more preferably the formula A solution in which the reaction product of (7) is dissolved in an organic solvent or a solution in which the compound of formula (8) is dissolved in an organic solvent, and more preferably a solution in which the reaction product of formula (7) is dissolved in an organic solvent. Add to.

  The reaction conditions for the reaction product of the above formula (7) and the compound of the formula (8) are not particularly limited as long as this reaction proceeds. Specifically, the reaction between the reaction product of formula (7) and the compound of formula (8) is carried out at a reaction temperature of -20 to 120 ° C, more preferably -10 to 80 ° C for 1 to 24 hours. Preferably it is performed for 2 to 12 hours.

  By such a reaction, the compound of the above formula (9) is obtained. Here, the compound of the formula (9) may be subjected to the next cyclization reaction as it is, but after purification, It is preferable to use for this cyclization reaction. Here, the purification method is not particularly limited, and known methods such as washing, solvent extraction, column chromatography using silica gel, alumina, etc., filtration, distillation, preferably solid distillation, recrystallization, reprecipitation, and sublimation can be used. Can be used.

  The compound of the formula (9) obtained by the above reaction is cyclized with one selected from the group consisting of metal oxides, metal carbonyls, metal halides, and organic acid metals, whereby one α-position of the phthalocyanine skeleton is obtained. A phthalocyanine compound in which is a halogen atom (hereinafter also referred to as “phthalocyanine precursor”) is obtained. The phthalocyanine precursor thus obtained is further represented by the following formula: H—N (R ′) (R ″) (where R ′ and R ″ have the same definitions as in the above formula (1)). The phthalocyanine compound of the present invention can be produced by reacting with the amino compound shown (hereinafter also simply referred to as “amino compound”).

  Here, in the cyclization reaction, the compound of the formula (9) obtained by the above reaction and one selected from the group consisting of metals, metal oxides, metal carbonyls, metal halides, and organic acid metals are in a molten state or an organic solvent. It is preferable to make it react in. The metal, metal oxide, metal carbonyl, metal halide, and organic acid metal that can be used at this time are particularly limited as long as those corresponding to M of the phthalocyanine of formula (1) obtained after the reaction can be obtained. For example, M in the above formula (1) is a metal such as iron, copper, zinc, vanadium, titanium, indium and tin, a metal halide such as chloride, bromide or iodide, oxidation of the metal Examples thereof include metal oxides such as vanadium, titanyl oxide and copper oxide, organic acid metals such as acetate, complex compounds such as acetylacetonate, and metal carbonyls such as carbonyl iron. Of these, preferred are metals, metal oxides and metal halides, more preferred are vanadium trichloride, copper (I) chloride, copper (II) chloride, zinc iodide and tin chloride, and particularly preferred are three. Vanadium chloride, copper (I) chloride, and zinc iodide.

  In the above method, the cyclization reaction can be carried out in the absence of a solvent, but it is preferably carried out using an organic solvent. The organic solvent may be any inert solvent that has low reactivity with the compound of the formula (9), and preferably does not exhibit reactivity, such as benzene, toluene, xylene, nitrobenzene, monochlorobenzene, dichlorobenzene. , Trichlorobenzene, 1-chloronaphthalene, 1-methylnaphthalene, ethylene glycol, and benzonitrile and other inert solvents; and pyridine, N, N-dimethylformamide, N-methyl-2-pyrrolidinone, N, N-dimethylacetophenone And aprotic polar solvents such as triethylamine, tri-n-butylamine, dimethyl sulfoxide, and sulfolane. Of these, 1-chloronaphthalene, 1-methylnaphthalene and benzonitrile are preferably used, and benzonitrile is more preferably used.

  The reaction conditions of the compound of the above formula (9) and the metal compound are not particularly limited as long as the reaction proceeds. For example, 100 parts of an organic solvent (hereinafter referred to as “parts by mass”) is meant. 2) to 50 parts, preferably 10 to 40 parts of the total amount of the compound of formula (9), and 1.0 to 4 of the metal compound relative to 4 mol of the compound of formula (9). The reaction is carried out at a reaction temperature of 30 to 250 ° C., preferably 80 to 200 ° C. for 1 to 40 hours, preferably 2 to 30 hours. Let After the reaction, a phthalocyanine derivative that can be used in the next step can be efficiently and highly purified by filtration, washing, and drying according to a conventionally known phthalocyanine synthesis method.

  By the above reaction, a phthalocyanine precursor having no amino group (—N (R ′) (R ″)) at the α-position of the phthalocyanine skeleton is produced. ) (R ″) (wherein R ′ and R ″ have the same definitions as in the above formula (1)), by reaction with an amino compound (hereinafter also simply referred to as “amino compound”), The phthalocyanine compounds of the invention are produced.

  The reaction between the phthalocyanine precursor and the amino compound can be carried out by mixing in the presence of an inert liquid that is not reactive with the compound used for the reaction, if necessary, and heating to a certain temperature. Preferably, it is carried out by heating to a certain temperature in the amino compound to be reacted. Examples of the inert liquid include 1,2,4-trimethylbenzene, benzonitrile, acetonitrile, N-methylpyrrolidone, dimethylformamide, toluene, xylene, and the like. These may be used alone or as a mixture of two or more. Can be used.

  In the above reaction, an amino group (—N (R ′) (R ″)) can be selectively introduced into the α-position of the phthalocyanine precursor. Here, the addition amount of the amino compound of the above formula is the α of the phthalocyanine precursor. The amount is not particularly limited as long as the amino group (—N (R ′) (R ″)) can be selectively introduced into the position. Preferably, the addition amount of the amino compound of the above formula is charged in the range of 1 to 48 mol, more preferably 4 to 40 mol, with respect to 1 mol of the phthalocyanine precursor.

  Next, for the purpose of trapping the generated hydrogen halide, inorganic components such as calcium carbonate and calcium hydroxide are added to the reaction product in an amount of 1 to 16 mol, preferably 3 to 1 mol with respect to 1 mol of the phthalocyanine derivative. You may charge a trap agent in the range of 8 mol. In this case, the trapping agent that can be used is the same as that in the cyclization reaction. The reaction conditions for the phthalocyanine precursor and amino compound are not particularly limited as long as the reaction proceeds. For example, the reaction temperature is preferably 20 to 200 ° C., more preferably 30 to 150 ° C., and the reaction time is preferably 1 to 40 hours, more preferably 2 to 30 hours. In addition, after the reaction, according to a conventionally known synthesis method by substitution reaction of phthalocyanine, inorganic components are filtered, and the amino compound is distilled off or washed, thereby producing the target phthalocyanine compound of the present invention in a complicated production process. It can be obtained efficiently and with high purity without going through.

  The phthalocyanine compound of the present invention thus produced exhibits excellent light resistance in an adhesive (adhesive layer) while exhibiting high near-infrared cut efficiency in the wavelength range of 800 to 1100 nm, particularly 850 to 1000 nm. . Therefore, the phthalocyanine compound of the present invention has a translucent or transparent heat ray shielding material for the purpose of shielding heat rays, a heat ray absorbing laminated glass for automobiles, a heat ray shielding film or a heat ray shielding resin glass, and a visible light transmittance. Near-infrared absorbing filter with high and high near-infrared light cutting efficiency, especially near-infrared absorbing filter for plasma display panel, near-infrared absorbing agent for non-contact fixing toner such as flash fixing, and near-infrared for thermal insulation fiber Absorbents, infrared absorbers for fibers with camouflage performance against scouting by infrared rays, optical recording media using semiconductor lasers, filters for liquid crystal displays with xenon lamps as backlights, optical character readers, etc. Near-infrared absorbing dye for writing or reading, near-infrared light Photosensitizer, photothermal exchange agent such as thermal transfer and thermal stencil, photothermal exchange agent for laser fusion that heat-fuses resin using laser beam, near infrared absorption filter, anti-eye strain or photoconductive material, etc. Furthermore, a photosensitive dye for tumor treatment that absorbs light in a long wavelength region with good tissue permeability, a color cathode ray tube selective absorption filter, color toner, ink for inkjet, anti-counterfeiting ink, anti-counterfeiting bar code ink, Used for near-infrared absorbing ink, marking agents for positioning photos and films, goggles lenses and shielding plates, dyeing agents for sorting when recycling plastics, and pre-heating aids when molding PET bottles In particular, it exhibits an excellent effect. Considering the above-described characteristics in particular, the phthalocyanine compound of the present invention can be suitably used for a near infrared absorption filter, particularly a near infrared absorption filter for a plasma display panel.

  Therefore, the second aspect of the present invention relates to a near-infrared absorption filter containing the phthalocyanine compound of the present invention, particularly a near-infrared absorption filter for plasma display panels. Here, the phthalocyanine compound of the present invention may be included in the near-infrared absorption filter alone or in the form of a mixture of two or more. Hereinafter, the near infrared absorption filter for PDP which is a particularly preferable embodiment of the present invention will be described in detail.

  The near-infrared absorption filter for PDP of the present invention contains the phthalocyanine compound of the present invention in a base material, and when it is contained in the base material referred to in the present invention, of course, it is contained inside the base material. That means a state where it is applied to the surface of the substrate, a state where it is sandwiched between the substrate, and the like. Examples of the substrate include a transparent resin plate, a transparent film, and transparent glass. The method for producing the filter for a plasma display panel of the present invention using the phthalocyanine compound is not particularly limited. For example, the following three methods can be used.

  The filter for a plasma display panel according to the present invention contains a phthalocyanine compound represented by the above formula (1) in a base material. Of course, this means a state where it is applied to the surface of the substrate, a state where it is sandwiched between the substrates, and the like. Examples of the substrate include a transparent resin plate, a transparent film, and transparent glass. The method for producing the filter for a plasma display panel of the present invention using the phthalocyanine compound is not particularly limited. For example, the following three methods can be used.

  (1) A method in which the above phthalocyanine compound is kneaded into a resin and thermoformed to produce a resin plate or film; (2) A paint (liquid or paste) containing the above phthalocyanine compound is produced, and a transparent resin A method of coating on a plate, a transparent film or a transparent glass plate; and (3) a method of producing a laminated resin plate, a laminated resin film, a laminated glass or the like by incorporating the phthalocyanine compound into an adhesive. Among these, as described above, the phthalocyanine compound of the present invention exhibits excellent stability even in the pressure-sensitive adhesive. For this reason, it is preferable that the phthalocyanine compound of this invention is used with the form of said (3). In this way, by providing near-infrared absorption in the adhesive layer, the number of necessary films can be reduced, and at the same time, the number of films used can also be reduced by integrating the functions of films, etc. ,preferable.

  First, in the method (1) in which the above phthalocyanine compound is kneaded into a resin and heat-molded, the resin material is preferably as transparent as possible when it is made into a resin plate or a resin film. , Polystyrene, polyacrylic acid, polyacrylic ester, polyvinyl acetate, polyacrylonitrile, polyvinyl chloride, polyvinyl fluoride, and other vinyl compounds, and addition polymers of those vinyl compounds, polymethacrylic acid, polymethacrylic acid esters, Vinyl compounds such as polyvinylidene chloride, polyvinylidene fluoride, poly (vinylidene fluoride), vinylidene fluoride / trifluoroethylene copolymer, vinylidene fluoride / tetrafluoroethylene copolymer, vinylidene cyanide / vinyl acetate copolymer, or fluorides Compound Copolymers, fluorine-containing resins such as polytrifluoroethylene, polytetrafluoroethylene, polyhexafluoropropylene, polyamides such as nylon 6 and nylon 66, polyimides, polyurethanes, polypeptides, polyesters such as polyethylene terephthalate, polycarbonates, Polyether, such as polyoxymethylene, polyethylene oxide, polypropylene oxide, epoxy resin, polyvinyl alcohol, polyvinyl butyral, etc. can be mentioned, but is not limited to these resins, high hardness to be a glass substitute, Highly transparent resin, thermosetting resin such as thiourethane, ARTON (registered trademark, manufactured by Nippon Synthetic Rubber Co., Ltd.), ZEONEX (registered trademark, manufactured by Nippon Zeon Co., Ltd.), OPTPOREZ (Hitachi) Adult Ltd.) It is also preferable to use O-PET (Kanebo Ltd.) optical resin such.

  As a method for producing a filter for a plasma display panel of the present invention, the processing temperature, filming conditions and the like are slightly different depending on the base resin to be used. After being heated and dissolved at 150 to 350 ° C., a method of forming a resin plate by molding, (II) a method of forming a film with an extruder, and (III) a raw material with an extruder, Examples thereof include a method of stretching a film uniaxially or biaxially at 30 to 120 ° C. 2 to 5 times to form a film having a thickness of 10 to 200 μm. 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 phthalocyanine compound of the present invention varies depending on the thickness of the resin to be produced, the target absorption strength, the target visible light transmittance, etc., but is usually 0.0005 to 20% by mass, preferably 0, based on the resin. .0010 to 10% by mass. Moreover, the resin board and resin film which used the casting method by block polymerization of the phthalocyanine compound of this invention, methyl methacrylate, etc. can also be produced.

  Next, as a method of (2) coating and coating, the phthalocyanine compound of the present invention is dissolved in a binder resin and an organic solvent to form a coating, and the phthalocyanine compound is atomized to several μm or less in an acrylic emulsion. There is a method of dispersing in 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 (registered trademark, manufactured by Nippon Synthetic Rubber Co., Ltd.), ZEONEX (registered trademark, manufactured by Nippon Zeon Co., Ltd.), OPTPOREZ (manufactured by Hitachi Chemical Co., Ltd.), O-PET (manufactured by Kanebo Co., Ltd.), etc. 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.

  Although the density | concentration of the phthalocyanine compound of this invention changes with thickness of a coating, the target absorption intensity, the target visible light transmittance, etc., it is 0.1-30% normally with respect to the mass of binder resin. Moreover, binder resin density | concentration is 1-50% normally with respect to the whole coating material. Similarly, in the case of an acrylic emulsion water-based paint, it can be obtained by dispersing a finely pulverized phthalocyanine compound of the present invention in an uncolored acrylic emulsion paint. In the coating material, additives such as ultraviolet absorbers, antioxidants and the like used in normal 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., and the plasma display of the present invention Panel filters 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.

  Further, in the method of (3) for producing a laminated resin plate, a laminated resin film, a laminated glass, etc. by containing the phthalocyanine compound in the pressure-sensitive adhesive, as the pressure-sensitive adhesive, general silicon-based, urethane-based, acrylic-based , SBR-based resin or laminated glass polyvinyl butyral pressure-sensitive adhesive (PVA), ethylene-vinyl acetate copolymer pressure-sensitive adhesive (EVA), carboxylated polyolefin, chlorinated polyolefin and other laminated glass A known transparent adhesive can be used. More specific adhesives include polymers obtained by polymerizing ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, n-octyl acrylate, or the like as a main component. The pressure-sensitive adhesive may be synthesized or a commercially available product may be used. As an example of the latter, there is ACRYSET AST (Nippon Catalyst). At this time, Tg of the pressure-sensitive adhesive is not particularly limited, but is preferably −80 ° C. or higher and 0 ° C. or lower. Within this range, deterioration in the composition during kneading of the phthalocyanine compound of the present invention and the pressure-sensitive adhesive can be suppressed, and the composition can be used for bonding with other functional films. And can be economical.

  The phthalocyanine compound of the present invention is preferably a transparent resin using the added adhesive in an amount of 0.01 to 30% by mass, more preferably 0.1 to 10% by mass, based on the resin solid content. A filter is manufactured by bonding plates, resin plate and resin film, resin plate and glass, resin films, resin film and glass, and glass. 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.

  When the phthalocyanine compound of the present invention is used as a near-infrared absorption filter (malfunction prevention filter) for a plasma display panel, it is placed on the front of the display to cut off near-infrared light emitted from the display. When the transmittance is low, the sharpness of the image decreases. For this reason, the higher the visible light transmittance of the filter, the better, and the phthalocyanine compound is preferably at least 65%, preferably 70% or more. Moreover, since the cut region of near-infrared light is 800 to 1100 nm, preferably 850 to 1000 nm, which is used for remote control and transmission optical communication, the average light transmittance of the region of the phthalocyanine compound of the present invention is 30 % Or less, preferably 15% or less. Therefore, if necessary, two or more phthalocyanine compounds represented by the general formula (1) may be combined. 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 manufacturing method is not particularly limited. For example, a sputtering method such as a metal oxide can be used for the electromagnetic wave cut layer, but usually In ₂ O ₃ (ITO) to which Sn is added is common. Further, by laminating the dielectric layer and the metal layer alternately on the base material by sputtering or the like, it is possible to cut light of 1100 nm or more 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 the phthalocyanine compound of the present invention is excellent in the heat ray shielding effect, and therefore can further improve the heat resistance effect. As the substrate, the filter containing the phthalocyanine compound of the present invention may be used as it is, or may be bonded to the filter containing the phthalocyanine compound after sputtering on a resin film or glass. 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, in a single layer or a multilayer. 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 a filter containing a near infrared absorbing compound, and if necessary, a non-glare layer is provided on the opposite side of the antireflection layer. In addition, when combining an electromagnetic wave cut layer, a filter containing a near infrared ray absorbing compound is used as a base material, and an electromagnetic wave cut layer is provided thereon, or a filter containing a near infrared ray absorbing compound and a filter having an electromagnetic wave cutting ability are provided. Can be made by pasting together. In that case, an antireflection layer can be 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. Since the filter for a plasma display panel of the present invention can specifically transmit near-infrared light in the wavelength range of 800 to 1100 nm, particularly 850 to 1000 nm, in addition to improving the color reproducibility of the display, peripheral electronic equipment The wavelength used by the remote controller, transmission optical communication, etc. is not adversely affected, and malfunctions thereof can be prevented.

  Examples will be described below. However, the technical scope of the present invention is not limited only to the following examples.

  In the following Examples, the maximum absorption wavelength (λmax) of the phthalocyanine compound was evaluated according to the following method.

<Measurement of maximum absorption wavelength (λmax)>
The maximum absorption wavelength (λmax (nm)) of the phthalocyanine compound is a value obtained by measuring the maximum absorption wavelength (λmax) of the phthalocyanine compound in chloroform using a spectrophotometer (manufactured by Shimadzu Corporation: UV-1650PC). Is nm.

Synthesis Example 1-1: Synthesis of 3,5,6-trifluoro-4-phenylthiophthalonitrile 3,5,6-trifluoro-4-phenylthiophthalonitrile was synthesized according to the following reaction formula.

  Specifically, a 300 ml reaction vessel equipped with a dropping funnel was charged with 25.01 g (124.99 mmol) of tetrafluorophthalonitrile, 7.41 g (127.54 mmol) of potassium carbonate, and 100 g of methyl ethyl ketone. Cooled to ° C. After cooling, a solution obtained by dissolving 14.45 g (131.15 mmol) of thiophenol in 58 g of methyl ethyl ketone was charged into a dropping funnel and slowly dropped and added to the reaction vessel. After completion of dropping, the mixture was stirred at 25 ° C. for 12 hours.

  After completion of the reaction, the reaction solution was filtered to remove inorganic salts, and concentrated with an evaporator. The concentrate was recrystallized from ethyl acetate / hexane to remove impurities 3,6-difluoro-4,5-bisphenylthiophthalonitrile, and the filtrate was concentrated using an evaporator. This recrystallization operation was performed once again, and then purified by Shaw and silica gel column chromatography (solvent chloroform) to obtain 22.12 g (76.21 mmol, yield) of 3,5,6-trifluoro-4-phenylthiophthalonitrile. : 61% with respect to tetrafluorophthalonitrile).

Synthesis Example 1-2: Synthesis of 3,5,6-trifluoro-4- (2,6-dimethylphenoxy) phthalonitrile According to the following reaction formula, 3,5,6-trifluoro-4- (2,6- Dimethylphenoxy) phthalonitrile was synthesized.

  Specifically, tetrafluorophthalonitrile 16.01 g (80.01 mol), potassium fluoride (KF) 5.54 g (95.35 mmol), and acetonitrile 50 mL were added to a 100 mL three-necked flask and stirred at 0 ° C. Until cooled. After cooling, a solution prepared by dissolving 9.77 g (79.98 mmol) of 2,6-dimethylphenol in 50 mL of acetonitrile was added dropwise from above, followed by stirring for 7 hours.

  After returning this reaction liquid to room temperature, chloroform was added, the organic component was dissolved, and KF was separated by filtration. After concentrating the filtrate, this concentrated solution was dissolved in acetone, and water was added to precipitate the solid content again. When this solid content was dried at 60 ° C. under reduced pressure, 13.8 g (45.60 mmol, yield: tetrafluoro) of the desired 3,5,6-trifluoro-4- (2,6-dimethylphenoxy) phthalonitrile was obtained. 57% relative to phthalonitrile).

Synthesis Example 1-3: Synthesis of 3,5,6-trifluoro-4- (4-methoxyphenylthio) phthalonitrile According to the following reaction formula, 3,5,6-trifluoro-4- (4-methoxyphenylthio) ) Phthalonitrile was synthesized.

  Specifically, tetrafluorophthalonitrile 100.03 g (499.93 mmol), potassium carbonate 29.9 g (514.63 mmol), and methyl ethyl ketone 620 ml were charged into a 1 L reaction vessel equipped with a dropping funnel, and the reaction vessel was kept at -5 ° C. Until cooled. After cooling, a solution obtained by dissolving 73.57 g (524.75 mmol) of 4-methoxythiophenol in 180 ml of methyl ethyl ketone was charged into a dropping funnel and slowly dropped and added to the reaction vessel. After completion of dropping, the mixture was kept at −3 ° C. for 3 hours, and then the cooling bath was removed and the mixture was stirred as it was for 12 hours.

  After completion of the reaction, the mixture was filtered to remove inorganic salts, and concentrated using an evaporator. This concentrate was recrystallized twice with chloroform / methanol to give 109.21 g (340.97 mmol, yield: tetrafluoro) of the desired 3,5,6-trifluoro-4- (4-methoxyphenylthio) phthalonitrile. 68% relative to phthalonitrile).

Synthesis Example 1-4: Synthesis of 3,5,6-trifluoro-4- (4-methylphenyl) phthalonitrile 3,5,6-trifluoro-4- (4-methylphenyl) phthalonitrile 2007-230999 gazette It synthesize | combined by the method as described in Example 2. FIG. That is, 3,5,6-trifluoro-4- (4-methylphenyl) phthalonitrile was synthesized according to the following reaction formula.

  Magnesium 3.86 g (134.9 mmol) was added to a 200 ml three-necked flask equipped with a dropping funnel and a reflux tube, and the inside of the reaction vessel was purged with nitrogen, and then 100 ml of tetrahydrofuran (THF) was added. Subsequently, 19.24 g (112.5 mmol) of p-bromotoluene was slowly added dropwise from the dropping funnel at room temperature (25 ° C.). Bromide) was synthesized. Next, 4.77 g (112.5 mmol) of lithium chloride was added to prepare a homogeneous Grignard reagent solution containing lithium chloride.

  Separately from the synthesis of the Grignard reagent, a 300 ml three-necked flask equipped with a thermometer and a dropping funnel was prepared, and tetrafluorophthalonitrile 15.00 g (75 mmol) and lithium chloride 4.77 g (112.5 mmol) were prepared. The reaction vessel was purged with nitrogen, and 150 ml of THF was added to prepare a substrate solution. After cooling this substrate solution to 0 ° C., the previously prepared Grignard reagent solution was transferred to a dropping funnel with a syringe, and the Grignard reagent solution was added dropwise while taking care that the reaction solution did not exceed 5 ° C.

  After completion of the dropwise addition of the Grignard reagent solution, the mixture was stirred at 0 ° C. for 24 hours, and then a 1M aqueous hydrochloric acid solution was added to terminate the reaction. The organic phase was taken out from this, the remaining aqueous phase was extracted three times with diethyl ether, and the organic phase combined with diethyl ether used in the extraction was washed with saturated brine and dehydrated with magnesium sulfate. Subsequently, magnesium sulfate is removed by filtration, the solvent of the organic phase is distilled off with an evaporator, and the obtained residue is purified by sublimation to obtain the desired 3,5,6-trifluoro-4- (4-methylphenyl). ) 9.60 g (35.25 mmol, yield: 47% based on tetrafluorophthalonitrile) of phthalonitrile was obtained.

  The raw materials, target products, and yields of Synthesis Examples 1-1 to 1-5 are summarized in Table 1 below.

Synthesis Example 2-1 Synthesis of Phthalonitrile (a) Phthalonitrile (a) was synthesized according to the following reaction formula.

  In a 50 ml reaction vessel, 1.50 g (4.97 mmol) of 3,5,6-trifluoro-4- (2,6-dimethylphenoxy) phthalonitrile produced in the same manner as in Synthesis Example 1-2, fluoride 0.74 g (12.74 mmol) of potassium and 15 g of methyl ethyl ketone were charged, and the temperature was raised to 50 ° C. Subsequently, a solution prepared by dissolving 0.825 g (4.96 mmol) of 4-tert-butyl-benzene-1,2-diol in 8.3 g of methyl ethyl ketone was slowly added to the reaction solution.

  After reacting for 3 hours, 10 ml of ethyl acetate was added to dissolve the precipitated organic matter, followed by filtration to remove inorganic salts. Once the organic solvent is removed using an evaporator, it is dissolved again in ethyl acetate and transferred to a separatory funnel. The organic layer is washed three times with water and once with a saturated saline solution, dried over anhydrous sodium sulfate, and then on an evaporator. Concentrated. The concentrate was recrystallized from chloroform / hexane, and 1.45 g (3.39 mmol, yield: 3,5,6-trifluoro-4- (2,6-dimethylphenoxy) phthaloide of the desired phthalonitrile (a). 68% relative to the nitrile).

Synthesis Example 2-2: Synthesis of phthalonitrile (b) According to the following reaction formula, phthalonitrile (b) was synthesized.

  In a 100 ml reaction vessel, 3.66 g (12.61 mmol) of 3,5,6-trifluoro-4-phenylthiophthalonitrile prepared in the same manner as in Synthesis Example 1-1, 1.87 g of potassium fluoride (32 .19 mmol) and 27.6 g of methyl ethyl ketone were charged, and the temperature was raised to 50 ° C. Subsequently, a solution prepared by dissolving 2.1 g (12.63 mmol) of 4-tert-butyl-benzene-1,2-diol in 17.1 g of methyl ethyl ketone was slowly added to the reaction solution.

  After reacting for 3 hours, 10 ml of ethyl acetate was added to dissolve the precipitated organic matter, followed by filtration to remove inorganic salts. Once the organic solvent is removed using an evaporator, it is dissolved again in ethyl acetate and transferred to a separatory funnel. The organic layer is washed three times with water and once with a saturated saline solution, dried over anhydrous sodium sulfate, and then on an evaporator. Concentrated. The concentrate was recrystallized from chloroform / hexane, and 3.02 g (7.24 mmol, yield: 57% of 3,5,6-trifluoro-4-phenylthiophthalonitrile) of the desired phthalonitrile (b). )Obtained.

Synthesis Example 2-3: Synthesis of phthalonitrile (c) According to the following reaction formula, phthalonitrile (c) was synthesized.

  In a 100 ml reaction vessel, 3.89 g (13.4 mmol) of 3,5,6-trifluoro-4-phenylthiophthalonitrile prepared in the same manner as in Synthesis Example 1-1, 1.97 g (33 .91 mmol) and 29.3 g of methyl ethyl ketone were charged, and the temperature was raised to 50 ° C. Subsequently, a solution prepared by dissolving 1.48 g (13.44 mmol) of benzene-1,2-diol in 11.5 g of methyl ethyl ketone was slowly added to the reaction solution.

  After reacting for 3 hours, chloroform was added to dissolve the precipitated organic matter, followed by filtration to remove inorganic salts. Once the organic solvent is removed using an evaporator, it is dissolved again in chloroform and transferred to a separatory funnel. The organic layer is washed three times with water and once with a saturated saline solution, dried over anhydrous sodium sulfate, and then concentrated with an evaporator. did. The concentrate was recrystallized from chloroform / hexane, and 3.94 g (10.94 mmol, yield: 82% of 3,5,6-trifluoro-4-phenylthiophthalonitrile) of the desired phthalonitrile (c). )Obtained.

Synthesis Example 2-4: Synthesis of phthalonitrile (d) According to the following reaction formula, phthalonitrile (d) was synthesized.

  In a 100 ml reaction vessel, 5.247 g (18.08 mmol) of 3,5,6-trifluoro-4-phenylthiophthalonitrile prepared in the same manner as in Synthesis Example 1-1, 3.2 g of potassium fluoride (55 0.08 mmol) and 39.5 g of methyl ethyl ketone were charged, and the temperature was raised to 50 ° C. Subsequently, a solution prepared by dissolving 2.90 g (18.09 mmol) of 2,3-dihydroxynaphthalene in 22 g of methyl ethyl ketone was slowly added to the reaction solution. After completion of the dropwise addition, the temperature was raised to 65 ° C. and reacted for 5 hours.

  After completion of the reaction, the reaction solution was concentrated, chloroform was added, washed with water in a suspension state, and further washed with saturated brine. The organic layer was concentrated to obtain 4.81 g (11.72 mmol, yield: 65% based on 3,5,6-trifluoro-4-phenylthiophthalonitrile) of the desired phthalonitrile (d).

Synthesis Example 2-5: Synthesis of phthalonitrile (e) According to the following reaction formula, phthalonitrile (e) was synthesized.

  In a 300 ml reaction vessel, 15.28 g (47.71 mmol) of 3,5,6-trifluoro-4- (4-methoxyphenylthio) phthalonitrile produced in the same manner as in Synthesis Example 1-3, potassium fluoride 9.51 g (163.68 mmol) and 115 g of methyl ethyl ketone were charged, and the temperature was raised to 50 ° C. Subsequently, a solution prepared by dissolving 7.94 g (47.77 mmol) of 4-tert-butyl-benzene-1,2-diol in 60 g of methyl ethyl ketone was slowly added dropwise to the reaction solution. After completion of the dropwise addition, the reaction solution was heated to 65 ° C. and reacted for 9 hours.

  After completion of the reaction, the reaction solution was concentrated once, chloroform was added and insolubles were removed by filtration, washed with water and saturated brine, further dried over anhydrous sodium sulfate, and then concentrated with an evaporator. The concentrate was recrystallized from chloroform / methanol and 17.26 g (81.03 mmol, yield: 3,5,6-trifluoro-4- (4-methoxyphenylthio) phthalonitrile of the desired phthalonitrile (e). 81%).

Synthesis Example 2-6: Synthesis of phthalonitrile (f) According to the following reaction formula, phthalonitrile (f) was synthesized.

  In a 50 ml reaction vessel, 0.85 g (2.98 mmol) of 3,5,6-trifluoro-4- (4-methylphenyl) phthalonitrile produced in the same manner as in Synthesis Example 1-4, potassium fluoride 0 .45 g (7.75 mmol) and methyl ethyl ketone 8 g were charged and the temperature was raised to 40 ° C. Subsequently, a solution prepared by dissolving 4.2 g (29.53 mmol) of 1,2-benzenedithiol in 4.2 g of methyl ethyl ketone was slowly added to the reaction solution.

  After reacting for 3 hours, the mixture was concentrated once, washed with chloroform, washed with water and saturated brine, dried over anhydrous sodium sulfate, and concentrated with an evaporator. The concentrate was recrystallized from chloroform / hexane, and 0.82 g (2.19 mmol, yield: 3,5,6-trifluoro-4- (4-methylphenyl) phthalonitrile of the desired phthalonitrile (f) was obtained. 74%).

Synthesis Example 2-7: Synthesis of phthalonitrile (g) Phthalonitrile (g) was synthesized according to the following reaction formula.

  In a 50 ml reaction vessel, 0.50 g (1.83 mmol) of 3,5,6-trifluoro-4- (4-methylphenyl) phthalonitrile produced in the same manner as in Synthesis Example 1-4, potassium fluoride 0 .27 g (4.65 mmol) and 7 g of methyl ethyl ketone were charged, and the temperature was raised to 50 ° C. Subsequently, a solution prepared by dissolving 0.20 g (1.82 mmol) of benzene-1,2-diol in 4 g of methyl ethyl ketone was slowly added to the reaction solution.

  After reacting for 3 hours, ethyl acetate was added to dissolve the precipitated organic matter, followed by filtration to remove inorganic salts. Once the organic solvent is removed using an evaporator, it is dissolved again in ethyl acetate and transferred to a separatory funnel. The organic layer is washed three times with water and once with a saturated saline solution, dried over anhydrous sodium sulfate, and then on an evaporator. Concentrated. The concentrate was recrystallized from chloroform / hexane to give 0.59 g (1.72 mmol, yield: 3,5,6-trifluoro-4- (4-methylphenyl) phthalonitrile of the desired phthalonitrile (g). 95%).

Synthesis Example 2-8: Synthesis of phthalonitrile (h) Phthalonitrile (h) was synthesized according to the following reaction formula.

  In a 50 ml reaction vessel, 0.71 g (2.61 mmol) of 3,5,6-trifluoro-4- (4-methylphenyl) phthalonitrile produced in the same manner as in Synthesis Example 1-4, potassium fluoride 0 .38 g (6.54 mmol) and methyl ethyl ketone 7.1 g were charged, and the temperature was raised to 50 ° C. Subsequently, a solution prepared by dissolving 0.43 g (2.59 mmol) of 4-tert-butyl-benzene-1,2-diol in 4.3 g of methyl ethyl ketone was slowly added to the reaction solution.

  After reacting for 3 hours, ethyl acetate was added to dissolve the precipitated organic matter, followed by filtration to remove inorganic salts. Once the organic solvent is removed using an evaporator, it is dissolved again in ethyl acetate and transferred to a separatory funnel. The organic layer is washed three times with water and once with a saturated saline solution, dried over anhydrous sodium sulfate, and then on an evaporator. Concentrated. The concentrate was recrystallized from chloroform / hexane, and 1.01 g (2.53 mmol, yield: 3,5,6-trifluoro-4- (4-methylphenyl) phthalonitrile of the desired phthalonitrile (h) was obtained. 98%).

Synthesis Example 2-9: Synthesis of phthalonitrile (i) According to the following reaction formula, phthalonitrile (i) was synthesized.

  In a 300 ml reaction vessel, 10.00 g (33.09 mmol) of 3,5,6-trifluoro-4- (2,6-dimethylphenoxy) phthalonitrile produced in the same manner as in Synthesis Example 1-5, fluoride 4.54 g (78.14 mmol) of potassium and 74.9 g of methyl ethyl ketone were charged, and the temperature was raised to 50 ° C. Subsequently, a solution prepared by dissolving 3.44 g (31.21 mmol) of 1,2-benzenediol in 33.2 g of methyl ethyl ketone was slowly added dropwise to the reaction solution. The reaction was continued for 7 hours. After completion of the reaction, the product was washed off by filtering and filtering the filtrate with chloroform to remove inorganic salts. The filtrate was concentrated once, dissolved by adding chloroform, and purified by short silica gel column chromatography (solvent chloroform) and recrystallization (chloroform / hexane) to obtain 8.62 g (23.16 mmol, Yield: 70% based on 3,5,6-trifluoro-4- (2,6-dimethylphenoxy) phthalonitrile).

Synthesis Example 2-9: Synthesis of phthalonitrile (j) According to the following reaction formula, phthalonitrile (j) was synthesized.

  In a 300 ml reaction vessel, 10.00 g (31.22 mmol) of 3,5,6-trifluoro-4- (4-methoxyphenylthio) phthalonitrile produced in the same manner as in Synthesis Example 1-3, potassium fluoride 4.54 g (78.14 mmol) and 74.9 g of methyl ethyl ketone were charged, and the temperature was raised to 50 ° C. Subsequently, a solution prepared by dissolving 4.44 g (31.21 mmol) of 1,2-benzenedithiol in 33.2 g of methyl ethyl ketone was slowly added dropwise to the reaction solution. The reaction was continued for 7 hours.

  After completion of the reaction, the product was washed off by filtering and filtering the filtrate with chloroform to remove inorganic salts. The filtrate was concentrated once, then dissolved by adding chloroform, and purified by short silica gel column chromatography (solvent chloroform) and recrystallization (chloroform / hexane) to obtain 11.32 g (26.79 mmol, 26.79 mmol, Yield: 86% with respect to 3,5,6-trifluoro-4- (4-methoxyphenylthio) phthalonitrile).

  The raw materials, target products (phthalonitrile (a) to (j)) and yields of Synthesis Examples 2-1 to 2-9 are summarized in Tables 2-1 and 2-2 below.

Synthesis Example 3-1 Synthesis of Phthalocyanine (1) Phthalocyanine (1) was synthesized according to the following reaction formula.

  In a reaction vessel equipped with a reflux condenser, 0.426 g (1.02 mmol) of phthalonitrile (b) synthesized in the same manner as in Synthesis Example 2-2, 0.0578 g (0.37 mmol) of vanadium trichloride, benzo 0.92 g of nitrile and 0.055 g of n-octanol were charged, and the temperature was raised to 180 ° C. After reacting for 4 hours, the mixture was allowed to cool, and 7.5 g of methanol was added to the reaction solution to precipitate the target product. After filtration, the residue was vacuum dried at 100 ° C. to obtain 0.38 g (0.22 mmol, yield: 86% based on phthalonitrile (b)) of the desired phthalocyanine (1).

Synthesis Example 3-2: Synthesis of phthalocyanine (2) Phthalocyanine (2) was synthesized according to the following reaction formula.

  In a reaction vessel equipped with a reflux condenser, 0.107 g (0.25 mmol) of phthalonitrile (a) synthesized in the same manner as in Synthesis Example 2-1 above, 0.008 g (0.08 mmol) of copper (I) chloride , 0.27 g of benzonitrile was charged, and the temperature was raised to 180 ° C. After reacting for 4 hours, the mixture was allowed to cool, and a mixed solution of isopropanol / water was added to precipitate the target product. After filtration, the residue was vacuum dried at 80 ° C. to obtain 0.102 g (0.06 mmol, yield: 92% with respect to phthalonitrile (a)) of the desired phthalocyanine (2).

Synthesis Example 3-3: Synthesis of phthalocyanine (3) Phthalocyanine (3) was synthesized according to the following reaction formula.

  In a reaction vessel equipped with a reflux condenser, 0.239 g (0.56 mmol) of phthalonitrile (a) synthesized in the same manner as in Synthesis Example 2-1 above, 0.028 g (0.18 mmol) of vanadium trichloride, Nitrile 0.6g and n-octanol 0.03g were prepared, and it heated up at 180 degreeC. After reacting for 4 hours, the mixture was allowed to cool, and 20 g of methanol and 3 g of water were added to the reaction solution to precipitate the desired product. After filtration, the residue was vacuum dried at 100 ° C. to obtain 0.07 g (0.04 mmol, yield: 28% based on phthalonitrile (a)) of the desired phthalocyanine (3).

Synthesis Example 3-4: Synthesis of phthalocyanine (4) Phthalocyanine (4) was synthesized according to the following reaction formula.

  In a reaction vessel equipped with a reflux condenser, 0.387 g (1.07 mmol) of phthalonitrile (c) synthesized in the same manner as in Synthesis Example 2-3, 0.054 (0.35 mmol) of vanadium trichloride, benzo Nitrile 0.88 g and n-octanol 0.06 g were charged and heated to 180 ° C. After reacting for 4 hours, the mixture was allowed to cool, and 7 g of methanol and 1 g of water were added to the reaction solution to precipitate the desired product. After filtration, the residue was vacuum dried at 100 ° C. to obtain 0.39 g (0.26 mmol, yield: 96% based on phthalonitrile (c)) of the desired phthalocyanine (4).

Synthesis Example 3-5: Synthesis of phthalocyanine (5) According to the following reaction formula, phthalocyanine (5) was synthesized.

  In a reaction vessel equipped with a reflux condenser, 0.10 g (0.23 mmol) of phthalonitrile (a) synthesized in the same manner as in Synthesis Example 2-1 above, 0.02 g (0.06 mmol) of zinc iodide, benzoic acid 1.05 g of nitrile was charged and the temperature was raised to 180 ° C. After reacting for 3.5 hours, the mixture was allowed to cool, and isopropanol / water was added to precipitate the target product. After filtration, the residue was vacuum dried at 80 ° C. to obtain 0.079 g (0.04 mmol, yield: 76% based on phthalonitrile (a)) of the desired phthalocyanine (5).

Synthesis Example 3-6: Synthesis of phthalocyanine (6) Phthalocyanine (6) was synthesized according to the following reaction formula.

  In a reaction vessel equipped with a reflux condenser, 0.10 mg (0.30 mmol) of phthalonitrile (g) synthesized in the same manner as in Synthesis Example 2-8, 0.07 g (0.22 mmol) of zinc iodide, benzoic acid Nitrile 1.61g was prepared and it heated up at 160 degreeC. After reacting for 3 hours, the mixture was allowed to cool, and isopropanol / water was added to precipitate the target product. After filtration, the residue was vacuum dried at 80 ° C. to obtain 0.07 g (0.05 mmol, yield: 69% with respect to phthalonitrile (g)) of the desired phthalocyanine (6).

Synthesis Example 3-7: Synthesis of phthalocyanine (7) According to the following reaction formula, phthalocyanine (7) was synthesized.

  In a reaction vessel equipped with a reflux condenser, 0.10 g (0.26 mmol) of phthalonitrile (h) synthesized in the same manner as in Synthesis Example 2-9, 0.045 g (0.14 mmol) of zinc iodide, Nitrile 1.2g was prepared, and it heated up at 170 degreeC. After reacting for 5 hours, the mixture was allowed to cool, and isopropanol / water was added to precipitate the target product. After filtration, the residue was vacuum-dried at 80 ° C. to obtain 0.08 g (0.5 mmol, yield: 79% with respect to phthalonitrile (h)) of the desired phthalocyanine (7).

Synthesis Example 3-8: Synthesis of phthalocyanine (8) According to the following reaction formula, phthalocyanine (8) was synthesized.

  In a reaction vessel equipped with a reflux condenser, 0.10 g (0.26 mmol) of phthalonitrile (f) synthesized in the same manner as in Synthesis Example 2-7, 0.04 g (0.13 mmol) of zinc iodide, benzoate Nitrile 1.0g was prepared and it heated up at 180 degreeC. After reacting for 3 hours, the mixture was allowed to cool, and isopropanol / water was added to precipitate the target product. After filtration, the residue was vacuum-dried at 80 ° C. to obtain 0.10 g (0.06 mmol, yield: 93% based on phthalonitrile (f)) of the desired phthalocyanine (8).

Synthesis Example 3-9: Synthesis of phthalocyanine (9) According to the following reaction formula, phthalocyanine (9) was synthesized.

  In a reaction vessel equipped with a reflux condenser, 0.105 g (0.26 mmol) of phthalonitrile (h) synthesized in the same manner as in Synthesis Example 2-8, 0.015 g (0.10 mmol) of vanadium trichloride, Nitrile 0.24g and n-octanol 0.0016g were prepared, and it heated up at 180 degreeC. After reacting for 3.5 hours, the mixture was allowed to cool, and isopropanol / methanol / water was added to precipitate the target product. After filtration, the residue was vacuum dried at 80 ° C. to obtain 0.089 g (0.05 mmol, yield: 81% with respect to phthalonitrile (h)) of the desired phthalocyanine (9).

  The raw materials, target products (phthalocyanines (1) to (9)), yields, and maximum absorption wavelength (λmax) of Synthesis Examples 3-1 to 3-9 are summarized in Table 3 below. In the table below, “PN” means phthalonitrile.

Example 4-1 Synthesis of Phthalocyanine (112) Phthalocyanine (112) was synthesized according to the following reaction formula.

  In a reaction vessel equipped with a reflux condenser, 0.219 g (0.13 mmol) of phthalocyanine (1) obtained in Synthesis Example 3-1, 0.68 g (5.26 mmol) of 2-ethylhexylamine, and 0.67 g of benzonitrile were added. The temperature was raised to 120 ° C. After reacting for 2 hours, the reaction solution was cooled, the reaction solution was filtered to remove a trace amount of insoluble matter, and then poured into methanol. The precipitate was filtered, and the filtrate was washed with methanol and then vacuum dried at 100 ° C. to obtain 0.142 g (0.07 mmol) of the desired phthalocyanine (112). At this time, the yield based on phthalocyanine (1) was 52%.

Example 4-2: Synthesis of phthalocyanine (113) Phthalocyanine (113) was synthesized according to the following reaction formula.

  In a reaction vessel equipped with a reflux condenser, 0.03 g (0.02 mmol) of phthalocyanine (6) obtained in Synthesis Example 3-6, 0.24 g (1.87 mmol) of 2-ethylhexylamine, and 0.4 g of benzonitrile were added. The temperature was raised to 140 ° C. After reacting for 4 hours, the reaction solution was cooled, the reaction solution was filtered to remove a small amount of insoluble matter, and then poured into methanol. The precipitate was filtered, and the filtrate was washed with methanol and then vacuum dried at 100 ° C. to obtain 0.012 g (0.006 mmol) of the desired phthalocyanine (113). At this time, the yield based on phthalocyanine (6) was 31%.

Example 4-3: Synthesis of phthalocyanine (114) Phthalocyanine (114) was synthesized according to the following reaction formula.

  In a reaction vessel equipped with a reflux condenser, 0.03 g (0.02 mmol) of phthalocyanine (9) obtained in Synthesis Example 3-9, 0.097 g (0.96 mmol) of n-hexylamine, and 0.31 g of benzonitrile were added. The temperature was raised to 120 ° C. After reacting for 5 hours, the reaction solution was cooled, the reaction solution was filtered to remove a small amount of insoluble matter, and then added dropwise to a mixed solution of 5 g of methanol and 1 g of water. The precipitate was filtered, and the filtrate was washed with methanol and then vacuum dried at 100 ° C. to obtain 0.020 g (0.01 mmol) of the desired phthalocyanine (114). At this time, the yield based on phthalocyanine (9) was 54%.

  The raw materials, target products (phthalocyanines (112) to (114)), yields, and maximum absorption wavelength (λmax) of Synthesis Examples 4-1 to 4-3 are summarized in Table 4 below. In the table below, “Ph” means phthalocyanine.

Synthesis Example 5-1 Synthesis of Phthalocyanine (101) Phthalocyanine (101) was synthesized according to the following reaction formula.

  In a 50 mL three-necked flask equipped with a reflux condenser and a gas blowing bottle, 4.47 g (9.66 mmol) of phthalonitrile (e) synthesized in the same manner as in Synthesis Example 2-5 and 0.51 g of vanadium trichloride were synthesized. (3.24 mmol), 5.4 g of 1,2,4-trimethylbenzene, and 0.6 g of benzonitrile were charged. While a mixed gas (oxygen 6.8% / nitrogen balance) was blown into the liquid at a flow rate of 0.8 mL per minute, the mixture was stirred at 160 ° C. for 7 hours to cause a cyclization reaction.

  After completion of the cyclization reaction, 12 g of 1,2,4-trimethylbenzene was added to stop the flow of the mixed gas, and the internal temperature was set to 70 ° C. Next, 10.34 g (80.0 mmol) of 2-ethylhexylamine was added, and nucleophilic substitution reaction was performed by stirring at 70 ° C. for 7 hours while blowing into the liquid at a flow rate of 0.8 mL per minute.

  The reaction solution was cooled to 35 ° C. under a nitrogen stream, filtered using Kiriyama filter paper (No. 4) having a diameter of 40 mm, and washed with 5 g of 1,2,4-trimethylbenzene. As a result, there was almost no residue on the filter paper. The washing liquid was added to the first filtrate to obtain 36.1 g of filtrate.

  In a 500 mL separable flask, 290 g of methanol was added, and the filtrate was added dropwise over 30 minutes while stirring at 55 ° C. After the completion of the dropwise addition, the mixture was kept at 55 ° C. for 20 minutes, and then cooled to 30 ° C. at a cooling rate of 15 ° C./hour while continuing stirring, and further allowed to cool for 1 hour to lower the temperature to 24 ° C. Filtered. The crystals on the obtained filter paper were washed with 5 g of methanol.

  The obtained crystal was vacuum-dried at 60 ° C. to obtain 3.84 g (1.68 mmol) of phthalocyanine (101). The yield based on phthalonitrile (e) was 69%.

  Moreover, the transmittance | permeability in 400-1100 nm was measured about the phthalocyanine (101) obtained in this way, and the result is shown in FIG.

Example 5-2: Synthesis of phthalocyanine (101) According to the following reaction formula, phthalocyanine (101) was synthesized.

  In a reaction vessel equipped with a reflux condenser, 0.512 g (1.15 mmol) of phthalonitrile (e) synthesized in the same manner as in Synthesis Example 2-5, 0.062 g (0.39 mmol) of vanadium trichloride, Nitrile 1.2 g and n-octanol 0.06 g were charged and heated to 180 ° C. After reacting for 5 hours, 1.9 g of benzonitrile was added and cooled to 130 ° C., and then 4.9 g (37.91 mmol) of 2-ethylhexylamine was added and reacted for 2 hours. After cooling the reaction solution, the reaction solution was filtered to remove a small amount of insoluble matter, and 130 g of methanol was put into a beaker, and the filtrate was slowly added dropwise while stirring at room temperature. After completion of the dropwise addition, the solution was allowed to stand for a while and then filtered, and the residue was vacuum dried at 100 ° C. to obtain 0.258 g (0.11 mmol) of the desired phthalocyanine (101). At this time, the yield based on phthalonitrile (e) was 39%.

Example 5-3: Synthesis of phthalocyanine (102) Phthalocyanine (102) was synthesized according to the following reaction formula.

  In a reaction vessel equipped with a reflux condenser, 0.208 g (0.49 mmol) of phthalonitrile (a) synthesized in the same manner as in Synthesis Example 2-1 above, 0.021 g (0.13 mmol) of vanadium trichloride, benzo Nitrile (5.9 g) and n-octanol (0.024 g) were charged and heated to 180 ° C. After reacting for 4 hours, 0.94 g of benzonitrile was added and cooled to 120 ° C., and then 2.0 g (15.48 mmol) of 2-ethylhexylamine was added and reacted for 5 hours. After cooling the reaction solution, the reaction solution was filtered to remove a small amount of insoluble matter, and 49.5 g of methanol was placed in a beaker, and the filtrate was slowly added dropwise while stirring at room temperature. After completion of the dropwise addition, the solution was allowed to stand for a while and then filtered. The residue was vacuum-dried at 100 ° C. to obtain 0.131 g (0.60 mmol) of the desired phthalocyanine (102). At this time, the yield based on phthalonitrile (a) was 49%.

Example 5-4: Synthesis of phthalocyanine (103) Phthalocyanine (103) was synthesized according to the following reaction formula.

  In a reaction vessel equipped with a reflux condenser, 0.342 g (0.95 mmol) of phthalonitrile (c) synthesized in the same manner as in Synthesis Example 2-3, 0.052 g (0.33 mmol) of vanadium trichloride, benzo Nitrile 0.82g and n-octanol 0.056g were charged and heated to 180 ° C. After reacting for 4 hours, 1.25 g of benzonitrile was added and cooled to 120 ° C., and then 3.95 g (30.56 mmol) of 2-ethylhexylamine was added and reacted for 2 hours. After cooling the reaction solution, the reaction solution was filtered to remove a small amount of insoluble matter, and 45.5 g of methanol was put into a beaker, and the filtrate was slowly added dropwise while stirring at room temperature. After completion of the dropwise addition, the solution was allowed to stand for a while and then filtered, and the residue was vacuum dried at 100 ° C. to obtain 0.256 g (0.13 mmol) of the desired phthalocyanine (103). At this time, the yield based on phthalonitrile (c) was 55%.

Example 5-5: Synthesis of phthalocyanine (104) Phthalocyanine (104) was synthesized according to the following reaction formula.

  In a reaction vessel equipped with a reflux condenser, 0.30 g (0.72 mmol) of phthalonitrile (b) synthesized in the same manner as in Synthesis Example 2-2, 0.023 g (0.23 mmol) of copper (I) chloride , 0.61 g of benzonitrile was charged and heated to 180 ° C. After reacting for 3.5 hours, 1.13 g of benzonitrile was added and cooled to 120 ° C., and then 2.98 g (23.05 mmol) of 2-ethylhexylamine was added and reacted for 2 hours. After cooling the reaction solution, the reaction solution was filtered to remove a small amount of insoluble matter, and 50 g of methanol was put into a beaker, and the filtrate was slowly added dropwise while stirring at room temperature. After completion of the dropwise addition, the solution was allowed to stand for a while and then filtered. The residue was vacuum dried at 100 ° C. to obtain 0.14 g (0.065 mmol) of the desired phthalocyanine (104). At this time, the yield based on phthalonitrile (b) was 36%.

Example 5-6: Synthesis of phthalocyanine (105) Phthalocyanine (105) was synthesized according to the following reaction formula.

  In a reaction vessel equipped with a reflux condenser, 0.198 g (0.48 mmol) of phthalonitrile (b) synthesized in the same manner as in Synthesis Example 2-2, 0.028 g (0.18 mmol) of vanadium trichloride, Nitrile 0.066g, pseudocumene 0.41g, n-octanol 0.024g was prepared, and it heated to 180 degreeC. After reacting for 5 hours, 0.6 g of benzonitrile was added and cooled to 130 ° C., and then 1.54 g (15.22 mmol) of n-hexylamine was added and reacted for 2 hours. After cooling the reaction solution, the reaction solution was filtered to remove a small amount of insoluble matter, and 35 g of methanol was put into a beaker, and the filtrate was slowly added dropwise while stirring at room temperature. After completion of the dropwise addition, the solution was allowed to stand for a while and then filtered, and the residue was vacuum dried at 100 ° C. to obtain 0.101 g (0.047 mmol) of the desired phthalocyanine (105). At this time, the yield based on phthalonitrile (b) was 41%.

Example 5-7: Synthesis of phthalocyanine (106) Phthalocyanine (106) was synthesized according to the following reaction formula.

  In a reaction vessel equipped with a reflux condenser, 0.228 g (0.56 mmol) of phthalonitrile (d) synthesized in the same manner as in Synthesis Example 2-4, 0.029 g (0.18 mmol) of vanadium trichloride, Nitrile 0.56 g and n-octanol 0.036 g were charged and heated to 180 ° C. After reacting for 4.5 hours, 0.8 g of benzonitrile was added and cooled to 140 ° C., then 2.31 g (17.87 mmol) of 2-ethylhexylamine was added and reacted for 2.5 hours. After cooling the reaction solution, the reaction solution was filtered to remove a small amount of insoluble matter, and 50.2 g of methanol and 5.3 g of isopropanol were placed in a beaker, and the filtrate was slowly added dropwise while stirring at room temperature. After completion of the dropwise addition, the solution was allowed to stand for a while and then filtered. The residue was vacuum-dried at 100 ° C. to obtain 0.158 g (0.074 mmol) of the desired phthalocyanine (106). At this time, the yield based on phthalonitrile (d) was 53%.

Example 5-8: Synthesis of phthalocyanine (107) According to the following reaction formula, phthalocyanine (107) was synthesized.

  In a reaction vessel equipped with a reflux condenser, 0.115 g (0.56 mmol) of phthalonitrile (h) synthesized in the same manner as in Synthesis Example 2-8, 0.016 g (0.18 mmol) of vanadium trichloride, Nitrile 0.23g and n-octanol 0.016g were prepared, and it heated to 180 degreeC. After reacting for 4 hours, 0.41 g of benzonitrile was added and cooled to 100 ° C., and then 1.21 g (9.36 mmol) of 2-ethylhexylamine was added, followed by raising the temperature to 140 ° C. for 2 hours. I let you. After cooling the reaction solution to room temperature, the reaction solution was filtered to remove a small amount of insoluble matter, and 15 g of methanol and 3 g of water were put into a beaker, and the filtrate was slowly added dropwise while stirring at room temperature. After completion of the dropwise addition, the solution was allowed to stand for a while and then filtered, and the residue was vacuum dried at 100 ° C. to obtain 0.128 g (0.061 mmol) of the desired phthalocyanine (107). At this time, the yield based on phthalonitrile (h) was 85%.

Example 5-9: Synthesis of phthalocyanine (108) Phthalocyanine (108) was synthesized according to the following reaction formula.

  In a reaction vessel equipped with a reflux condenser, 0.157 g (0.42 mmol) of phthalonitrile (f) synthesized in the same manner as in Synthesis Example 2-6, 0.021 g (0.18 mmol) of vanadium trichloride, Nitrile 0.36 g and n-octanol 0.024 g were charged and heated to 180 ° C. After reacting for 3.5 hours, 0.59 g of benzonitrile was added and cooled to 140 ° C., and then 1.75 g (13.54 mmol) of 2-ethylhexylamine was added, followed by reaction for 2.5 hours. After cooling the reaction solution to room temperature, the reaction solution was filtered to remove a small amount of insoluble matter, and 42.5 g of methanol was put into a beaker, and the filtrate was slowly added dropwise while stirring at room temperature. After completion of the dropwise addition, the solution was left standing for a while and then filtered, and the residue was vacuum dried at 100 ° C. to obtain 0.09 g (0.045 mmol) of the desired phthalocyanine (108). At this time, the yield based on phthalonitrile (f) was 43%.

Example 5-10: Synthesis of phthalocyanine (109) Phthalocyanine (109) was synthesized according to the following reaction formula.

  In a reaction vessel equipped with a reflux condenser, 0.30 g (0.71 mmol) of phthalonitrile (j) synthesized in the same manner as in Synthesis Example 2-10, 0.023 g (0.23 mmol) of vanadium trichloride, 1 , 2,4-trimethylbenzene 0.45 g and benzonitrile 0.05 g were charged and heated to 160 ° C. under nitrogen-oxygen mixed gas (oxygen component 7%). After reacting for 20 hours, 1.13 g of benzonitrile was added and cooled to 80 ° C., then 1.03 g (8.52 mmol) of 2-ethylhexylamine was added and reacted for 4 hours. After cooling the reaction solution, the reaction solution was filtered to remove a small amount of insoluble matter, and 50 g of methanol was put into a beaker, and the filtrate was slowly added dropwise while stirring at room temperature. After completion of the dropwise addition, the solution was left standing for a while and then filtered, and the residue was vacuum dried at 100 ° C. to obtain 0.16 g (0.071 mmol) of the desired phthalocyanine (109). At this time, the yield based on phthalonitrile (j) was 40%.

Example 5-11: Synthesis of phthalocyanine (110) Phthalocyanine (110) was synthesized according to the following reaction formula.

  In a reaction vessel equipped with a reflux condenser, 0.30 g (0.81 mmol) of phthalonitrile (i) synthesized in the same manner as in Synthesis Example 2-9, 0.023 g (0.23 mmol) of vanadium trichloride, 1 , 2,4-trimethylbenzene 0.45 g and benzonitrile 0.05 g were charged and heated to 160 ° C. under nitrogen-oxygen mixed gas (oxygen component 7%). After reacting for 20 hours, 1.13 g of benzonitrile was added and cooled to 130 ° C., then 1.78 g (9.72 mmol) of benzhydrylamine was added and reacted for 40 hours. After cooling the reaction solution, the reaction solution was filtered to remove a small amount of insoluble matter, and 50 g of methanol was put into a beaker, and the filtrate was slowly added dropwise while stirring at room temperature. After completion of the dropwise addition, the solution was allowed to stand for a while and then filtered, and the residue was vacuum dried at 100 ° C. to obtain 0.30 g (0.071 mmol) of the desired phthalocyanine (110). At this time, the yield based on phthalonitrile (i) was 66%.

Example 5-12: Synthesis of phthalocyanine (111) Phthalocyanine (111) was synthesized according to the following reaction formula.

  In a reaction vessel equipped with a reflux condenser, 0.30 g (0.70 mmol) of phthalonitrile (a) synthesized in the same manner as in Synthesis Example 2-1 above, 0.023 g (0.23 mmol) of vanadium trichloride, 1 , 2,4-trimethylbenzene 0.45 g and benzonitrile 0.05 g were charged and heated to 160 ° C. under nitrogen-oxygen mixed gas (oxygen component 7%). After reacting for 20 hours, 1.13 g of benzonitrile was added and cooled to 80 ° C., then 1.08 g (8.40 mmol) of 2-ethylhexylamine was added and reacted for 4 hours. After cooling the reaction solution, the reaction solution was filtered to remove a small amount of insoluble matter, and 50 g of methanol was put into a beaker, and the filtrate was slowly added dropwise while stirring at room temperature. After completion of the dropwise addition, the solution was allowed to stand for a while and filtered, and the residue was vacuum dried at 100 ° C. to obtain 0.28 g (0.071 mmol) of the desired phthalocyanine (111). At this time, the yield based on phthalonitrile (a) was 72%.

  The raw materials, target products (phthalocyanines (101) to (111)), yield and maximum absorption wavelength (λmax) of Synthesis Examples 5-1 to 5-12 are summarized in Tables 5-1 and 5-2 below. . In the table below, “PN” means phthalonitrile.

Comparative Example 1
In a 100 ml four-necked flask, 10.00 g (20.7 mmol) of 3- (2,6-dimethylphenoxy) -4,5-bisphenylthio-6-fluorophthalonitrile, 0.978 g of vanadium trichloride (6 0.22 mmol), 0.81 g of n-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 after cooling to 60 ° C., 13.29 g (124 mmol) of benzylamine 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 methanol, and further washed once with methanol and once with acetonitrile. Vacuum drying yielded 8.31 g of comparative phthalocyanine (A) (yield: 68.5 mol%).

  Moreover, the transmittance | permeability in 400-1100 nm was measured about the comparison phthalocyanine (A) obtained in this way, and the result is shown in FIG.

Comparative Example 2
In a 100 ml four-necked flask, 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 n-octanol and 14.19 g of benzonitrile were charged and then kept under reflux for about 4 hours with stirring. Then, 30 g of benzonitrile was added, and after cooling to 60 ° C., 16.05 g (124 mmol) of 2-ethylhexylamine was added, and the mixture was kept at 60 ° C. for about 6 hours with stirring. After cooling, the reaction solution was filtered, the filtrate was crystallized dropwise in methanol, and further washed once with methanol and once with acetonitrile. 9.18 g of comparative phthalocyanine (B) was obtained by vacuum drying (yield: 66.3 mol%).

  Moreover, the transmittance | permeability in 400-1100 nm was measured about the comparison phthalocyanine (B) obtained in this way, and the result is shown in FIG.

Example 6
About the phthalocyanines (101) and (109) to (111) obtained in Synthesis Examples 5-1 and 5-10 to 12 and the comparative phthalocyanines (A) and (B) obtained in Comparative Examples 1 and 2, As shown in FIG. 3, the weather resistance test is performed.

  FIG. 3 shows that the phthalocyanine compound of the present invention is significantly superior in light resistance in the adhesive layer as compared with the conventional phthalocyanine compound.

<Weather resistance test>
First, each dye is adjusted to 5% solid content with toluene to prepare a dye solution. About 0.8 parts of the dye solution thus prepared is added to 100 parts of the pressure-sensitive adhesive (solid content: about 44.4%). Next, it adjusts by MEK so that solid content of each said solution may be 30%. The addition amount of the dye solution was adjusted as appropriate according to the absorbance, and specifically, the following composition was used. Moreover, the compound manufactured by the following method was used for the adhesive used in this test.

(Resin synthesis example)
As the monomer, 264.6 g of 2-ethylhexyl acrylate, 150 g of butyl acrylate, 180 g of cyclohexyl methacrylate and 5.4 g of hydroxyethyl acrylate were weighed and mixed well to obtain a polymerizable monomer mixture.

  160 g of ethyl acetate and 300 g of the polymerizable monomer mixture were placed in a flask equipped with a thermometer, a stirrer, an inert gas introduction tube, a reflux condenser and a dropping funnel. In addition, 300 g of a polymerizable monomer mixture, 16 g of ethyl acetate and 0.15 g of Nyper BMT-K40 (polymerization initiator, manufactured by NOF Corporation) were added to the dropping funnel and mixed well to obtain a mixture for dropping. While flowing nitrogen gas at a rate of 20 ml / min, the internal temperature of the flask was raised to 95 ° C., and Niper BMT-K40 (0.15 g) as a polymerization initiator was charged into the flask to initiate the polymerization reaction. 30 minutes after the introduction of the polymerization initiator, the dropping of the dropping mixture from the dropping funnel was started. The mixture for dripping was dripped uniformly over 90 minutes. After completion of the dropping, the mixture was aged for 6 hours while maintaining the reflux temperature while diluting with ethyl acetate as the viscosity increased. After completion of the reaction, the ethyl acetate reaction solution is diluted so that the nonvolatile content is about 45%, and a resin having a calculated glass transition temperature (Tg) of −35.0 ° C. and a calculated solubility parameter of 9.6 is obtained. Obtained. This resin had a weight average molecular weight (Mw) of 440,000 and an acid value of 0.

  Further, each of the above mixtures is stirred for about 15 minutes with a paint shaker to obtain an adhesive dye solution. Place the applicator (6.3 mil) on the left side of the PET film (Toyobo Cosmo Shine A4300) and place the adhesive dye solution on the right side of the applicator. Apply so that it is straight. Cut the film with non-uniform film pressure with a cutter to make it about A4 size. The film obtained as described above is placed on a SUS plate, stopped in four directions with a clip, and then dried at 100 ° C. for 2 minutes. Next, the dried test piece is cut into an appropriate size (2 cm × 2 cm) and attached to the glass surface so that air does not enter as much as possible with a roller (ignoring some bubbles).

  The test piece thus obtained was subjected to a weather resistance test. Here, the weather resistance is evaluated by observing a change in absorbance with time by irradiating the test piece with artificial sunlight as shown in FIG. 1 using a weather resistance tester (manufactured by Shimadzu Corporation, UNTESTER XF-180CPS). During the above test, the number of bubbles increased with irradiation, but the absorbance was measured while avoiding the bubbles.

Claims (4)

Following formula (1):
Wherein, X and X 'represents an acid atom (-O-) or a sulfur atom (-S-); Ar each independently may have a substituent group o- phenylene group or a substituted An o-naphthylene group which may have a group, wherein the substituent is an alkyl group having 1 to 8 carbon atoms ; A is independently an oxygen atom (—O—), sulfur; Represents an atom (—S—) or a single bond (—); each R independently represents an optionally substituted phenyl group or naphthyl group , wherein the substituent is the number of carbon atoms A linear or branched alkyl group of 1 to 8 or a linear or branched alkoxyl group of 1 to 8 carbon atoms ; one of R ′ and R ″ is a hydrogen atom, and the other is a substituent have a phenyl group have a good carbon atoms 1-8C alkyl group; M , Copper, represent vanadyl or zinc,
Or a positional isomer thereof. One of R ′ and R ″ is a hydrogen atom, and the other is an n-octyl group, 2-ethylhexyl group, n-hexyl group; having 1 to 3 aryl groups as substituents, and having 1 to 3 carbon atoms The phthalocyanine compound according to claim 1, which is an alkyl group, or a positional isomer thereof. The following groups:
The phthalocyanine compound according to claim 1 or 2, or a positional isomer thereof, selected from the group consisting of:   The near-infrared absorption filter containing the phthalocyanine compound of any one of Claims 1-3, or its positional isomer.