[go: up one dir, main page]

WO2010050720A2 - Absorbant de proche infrarouge constitué de complexe métallique de dithiol, procédé de préparation dudit complexe métallique de dithiol, et filtre optique et filtre de protection contre l’infrarouge thermique contenant un tel absorbant - Google Patents

Absorbant de proche infrarouge constitué de complexe métallique de dithiol, procédé de préparation dudit complexe métallique de dithiol, et filtre optique et filtre de protection contre l’infrarouge thermique contenant un tel absorbant Download PDF

Info

Publication number
WO2010050720A2
WO2010050720A2 PCT/KR2009/006216 KR2009006216W WO2010050720A2 WO 2010050720 A2 WO2010050720 A2 WO 2010050720A2 KR 2009006216 W KR2009006216 W KR 2009006216W WO 2010050720 A2 WO2010050720 A2 WO 2010050720A2
Authority
WO
WIPO (PCT)
Prior art keywords
dithiol
metal complex
formula
based metal
near infrared
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/KR2009/006216
Other languages
English (en)
Korean (ko)
Other versions
WO2010050720A3 (fr
WO2010050720A4 (fr
Inventor
손세모
김태훈
김광식
이태훈
강봉구
서동원
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
ICB CO Ltd
Original Assignee
ICB CO Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by ICB CO Ltd filed Critical ICB CO Ltd
Publication of WO2010050720A2 publication Critical patent/WO2010050720A2/fr
Publication of WO2010050720A3 publication Critical patent/WO2010050720A3/fr
Publication of WO2010050720A4 publication Critical patent/WO2010050720A4/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C323/00—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups
    • C07C323/10—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and singly-bound oxygen atoms bound to the same carbon skeleton
    • C07C323/11—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and singly-bound oxygen atoms bound to the same carbon skeleton having the sulfur atoms of the thio groups bound to acyclic carbon atoms of the carbon skeleton
    • C07C323/16—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and singly-bound oxygen atoms bound to the same carbon skeleton having the sulfur atoms of the thio groups bound to acyclic carbon atoms of the carbon skeleton the carbon skeleton containing six-membered aromatic rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C321/00—Thiols, sulfides, hydropolysulfides or polysulfides
    • C07C321/02—Thiols having mercapto groups bound to acyclic carbon atoms
    • C07C321/10—Thiols having mercapto groups bound to acyclic carbon atoms of an unsaturated carbon skeleton containing rings
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • G02B5/208—Filters for use with infrared or ultraviolet radiation, e.g. for separating visible light from infrared and/or ultraviolet radiation

Definitions

  • the present invention relates to a near-infrared absorber composed of a dithiol-based metal complex, a method for preparing the dithiol-based metal complex, an optical filter and a thermal infrared shielding filter containing the same, and more particularly, the present invention provides improved solubility in organic solvents.
  • the optical filter is efficiently mixed with organic materials such as a polymer resin to be mixed, and the excellent near-infrared absorption performance of the dithiol-based nickel complex compound is sufficiently exhibited for a long time.
  • the present invention relates to an optical filter and a thermal infrared shielding filter in which the near infrared absorptive capacity is not degraded.
  • LCDs liquid crystal displays
  • PDPs plasma display panels
  • ELDs electroluminescent displays
  • CRTs cathode ray display devices
  • fluorescent displays electroluminescent displays
  • LCDs liquid crystal displays
  • ELDs electroluminescent displays
  • CRTs cathode ray display devices
  • fluorescent displays electroluminescent displays
  • electroluminescent displays has been put to practical use.
  • color plasma display (PDP) is attracting attention as a large wall-mounted television for high-vision and a large-screen display for multimedia.
  • these image display devices display a color image in a combination of three primary colors of red, blue, and green light.
  • light of an unnecessary wavelength is also emitted from the display device, and there is a problem in the malfunction of peripheral electronic devices and the quality of the display image.
  • the plasma display also emits near-infrared rays or electromagnetic waves in the 800-1000 nm region. Since the wavelength region of the near-infrared rays overlaps with the wavelength region used in the near-infrared communication or the remote controller of another electronic apparatus, it causes malfunction of the peripheral electronic apparatus. do.
  • an optical filter containing a light absorbing agent that absorbs specific light is used, and for example, an optical filter that absorbs near infrared rays is disclosed in Japanese Patent Laid-Open No. 9-230134 and Japanese Patent Laid-Open No. 11-73115 Japanese Patent Laid-Open No. 11-12425, Japanese Patent Laid-Open No. 2000-206322, Japanese Patent Laid-Open No. 2000-212546 and the like have reported optical filters using an aromatic dithiol nickel compound as a light absorbing agent.
  • the near-infrared absorber for an optical filter it is desired to selectively absorb the wavelength light of a near-infrared region, and to transmit the light of visible region.
  • the conventional light absorbing agent also absorbs the visible light region and was not suitable as a light absorbing agent for optical filters.
  • dithiol-based nickel complex compounds represented by the following general formula (13) are representative as an example of effectively absorbing near infrared rays in the 800 to 900 nm wavelength region and having excellent performance as a near infrared absorbent.
  • the dithiol-based nickel complex compound Since the dithiol-based nickel complex compound has excellent deactivation effect against singlet oxygen in addition to its use as a near-infrared absorber, it is useful as an antioxidant such as polyolefins, a weathering agent, or a decoloring inhibitor such as color photograph. Furthermore, the dithiol-based nickel complex compound has excellent properties that can be applied to a wide range of fields so that it can be usefully used as a catalyst or liquid crystal material for water photolysis and dehydration.
  • the dithiol-based nickel complex compound In order to fully exhibit the properties of the dithiol-based nickel complex compound, it must be dissolved or contained in an organic material such as binder resin, plastic, ion paint or organic solvent in an optimal content uniformly.
  • the dithiol-based nickel complex compound has a problem in that the solubility of the organic material is significantly low so that it cannot contain a sufficient amount of the organic material, so that the performance cannot be sufficiently exhibited.
  • the present inventors have tried to solve the problem of the light absorbing agent for the conventional optical filter, and as a result, to obtain a novel dithiol-based nickel complex that improves the solubility in organic materials and selectively absorbs only near infrared rays from the conventional dithiol-based nickel complex,
  • the present invention has been completed by producing a novel near-infrared absorbing pigment, in which the performance of the dithiol-based nickel complex compound is sufficiently exhibited and the near-infrared absorbing ability is not lowered over a long period of time, and an optical filter and a thermal infrared shielding filter using the same are provided.
  • Another object of the present invention is to provide a novel method for producing a dithiol-based nickel complex.
  • Still another object of the present invention is to provide an optical filter containing a near infrared absorber composed of the dithiol-based nickel complex compound, a thermal infrared shielding filter, and a plasma display panel employing the same.
  • the present invention provides a near-infrared absorber composed of a dithiol-based nickel complex compound with improved solubility in organic materials.
  • a near-infrared absorber composed of a dithiol-based metal complex represented by the following formula (1).
  • M is a nickel, palladium or platinum
  • R is an ether group of hydrogen, C 1 ⁇ C 6 alkyl group or a C 1 ⁇ C 6
  • X is hydrogen or halogen
  • m 1 ⁇ 3, o , p, q, r, o ', p', q 'and r' are 0 to 3, [o-o '], [p-p'], [q-q '] and [r-r' ] Are 0 to 3, respectively, and are positive integers.
  • the dithiol-based metal complex of the present invention provides a near-infrared absorber, characterized in that the solubility is improved by replacing 1 to 5 hydroxyl groups in the benzene ring.
  • nickel is preferably used as the metal element among the dithiol-based metal complex compounds.
  • the dithiol metal complex of the present invention is dichloromethane, dichloroethane, methyl ethyl ketone, methyl isobutyl ketone, toluene, ethylene glycol monoethyl ether, ethanol, xylene, tetrahydrofuran and 1,4-dioxane
  • the solubility improvement effect is shown with respect to any one organic solvent selected.
  • the present invention also provides a method for producing a dithiol-based metal complex having improved solubility.
  • M is a nickel, palladium or platinum
  • R is an ether group of hydrogen, C 1 ⁇ C 6 alkyl group or a C 1 ⁇ C 6
  • X is hydrogen or halogen
  • m 1 ⁇ 3, o , p, q, r, o ', p', q 'and r' are 0 to 3, [o-o '], [p-p'], [q-q '] and [r-r' ] Are 0 to 3, respectively, and are positive integers.
  • At least one Lewis acid selected from the group consisting of AlCl 3 , ZnCl 2 and BF 3 in the third step of the preparation method of the present invention is 2 to 15 mol%, more preferably 2 to 10 mol relative to the dithiol-based metal complex It can be added in% to perform a partial hydroxylation reaction to prepare a symmetric or asymmetric dithiol-based metal complex.
  • the dithiol-based metal complex compound is preferably a hydroxyl group substituent of 2 to 5, the center metal is preferably nickel.
  • the present invention is applied to a glass or transparent base film, in particular, an optical filter manufactured in the form of a film or a panel by applying a composition containing a near-infrared absorber composed of a dithiol-based metal complex represented by the formula (1) and a polymer resin, in particular, thermal infrared shielding Provide a filter.
  • the central metal is preferably nickel
  • the polymer resin is acrylic resin, polyester resin, polycarbonate resin, urethane resin, cellulose resin, polyisocyanate, polyarylate and epoxy resin. It can be used selected from the group consisting of.
  • the composition is composed of a near infrared absorber and a polymer resin, but contains 1 to 3% by weight of a near infrared absorber, based on the polymer resin.
  • the present invention uses the optical filter or the thermal infrared shielding filter in an image display device, in particular, 1 to 3% by weight of a near infrared absorber made of a dithiol-based metal complex, an acrylic resin, a polyester resin, a polycarbonate resin, and a urethane resin.
  • Optical filter or heat prepared by applying a composition consisting of 98 to 99% by weight of any one polymer resin selected from the group consisting of cellulose resin, polyisocyanate, polyarylate and epoxy resin on a glass or transparent base film
  • a plasma display panel employing an infrared shielding filter.
  • a near-infrared absorber composed of a dithiol-based metal complex having a low absorption in the visible region, selectively absorbing wavelength light in the near infrared region, and improved solubility in organic materials. It is possible to provide an optical filter, a thermal infrared shielding filter, and a plasma display panel employing the same, which contain a near infrared absorber and which do not degrade the near infrared absorbing ability for a long time.
  • 1 is an absorption spectrum using ultraviolet spectroscopy of the dithiol-based nickel complex of the present invention.
  • the present invention has been made to solve the problem of the low solubility of the dithiol-based metal complex of formula (5) known as a conventional near-infrared absorber, and provides a near-infrared absorber consisting of a dithiol-based metal complex represented by the formula (1).
  • M is a nickel, palladium or platinum
  • R is an ether group of hydrogen, C 1 ⁇ C 6 alkyl group or a C 1 ⁇ C 6
  • X is hydrogen or halogen
  • m 1 ⁇ 3, o , p, q, r, o ', p', q 'and r' are 0 to 3, [o-o '], [p-p'], [q-q '] and [r-r' ] Are 0 to 3, respectively, and are positive integers.
  • the metal atom is nickel
  • the alkyl group of R is methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl, tert-butyl, Any one selected from the group consisting of n-pentyl group, iso-pentyl group, sec-pentyl group, tert-pentyl group and n-hexyl group may be used, and more preferably, the alkyl group of R is a methyl group or an ethyl group. .
  • the solubility improvement in the present invention is that the dithiol-based metal complex of the present invention improves solubility not only in ketone and halogen solvents but also in alcohols such as ethylene glycol monoethyl ether and ethanol. More specifically, any one selected from the group consisting of dichloromethane, dichloroethane, methyl ethyl ketone, methyl isobutyl ketone, toluene, ethylene glycol monoethyl ether, ethanol, xylene, tetrahydrofuran and 1,4-dioxane It has solubility in one organic solvent.
  • the dithiol-based metal complex of the present invention selectively absorbs near infrared rays in the wavelength range of 930 to 960 nm.
  • R is an ether group of hydrogen, C 1 ⁇ C 6 alkyl group or a C 1 ⁇ C 6 in.
  • R is an ether group of hydrogen, C 1 ⁇ C 6 alkyl group or a C 1 ⁇ C 6 in.
  • R is an ether group of hydrogen, C 1 ⁇ C 6 alkyl group or a C 1 ⁇ C 6 in.
  • the present invention provides a method for producing a dithiol-based metal complex compound which is contained in the near-infrared absorber and has improved solubility.
  • the hydroxylation reaction is partially controlled by adding at least one Lewis acid selected from the group consisting of AlCl 3 , ZnCl 2 and BF 3 to the dithiol-based metal complex-containing organic solution represented by Formula 12, and is represented by Formula 1
  • the third step is to prepare a dithiol-based metal complex compound.
  • the dithiol-based metal complex of the present invention implements excellent solubility in organic solvents when the hydroxyl group substituent is 1 to 5, more preferably 2 to 5. When the hydroxy substituent exceeds 5, the solubility is excellent, but the long wavelength shift is remarkable, out of the desired wavelength range, there is a difficulty in the separation and purification of the desired nickel complex compound.
  • the organic solvent is any one selected from the group consisting of chloromethane, dichloroethane, methyl ethyl ketone, methyl isobutyl ketone, toluene, ethylene glycol monoethyl ether, ethanol, xylene, tetrahydrofuran and 1,4-dioxane It exhibits excellent solubility with respect to the insoluble which is hardly dissolved conventionally.
  • R CH 3 as a starting material
  • R H (hydroxy group) quantitatively Control the substitution reaction.
  • the dithiol system of the symmetrical type [compound represented by Formulas 4 to 6] or the asymmetrical type [compound represented by Formulas 7 to 9] which has improved solubility in organic solvents and selectively absorbs near infrared rays in the 930 to 960 nm wavelength range.
  • Metal complexes can be prepared.
  • the present invention is applied to a glass or transparent substrate film, the optical filter and thermal infrared shielding filter prepared in the form of a film or panel by applying a composition containing a near-infrared absorber and a polymer resin made of a dithiol-based metal complex represented by the formula (1) to provide.
  • the central metal is preferably nickel
  • the polymer resin is acrylic resin, polyester resin, polycarbonate resin, urethane resin, cellulose resin, polyisocyanate, polyarylate and epoxy resin. It can be used selected from the group consisting of.
  • polyester or polycarbonate As the transparent base film used in the present invention, it is preferable to use polyester or polycarbonate.
  • the composition consisting of the near-infrared absorbent and the polymer resin of the present invention can adjust the near-infrared absorption rate according to the content of the composition.
  • the polymer resin preferably contains 1 to 3% by weight of a near infrared absorber made of a dithiol-based metal complex compound. At this time, when the content of the near infrared absorber is less than 1% by weight, the near infrared absorption capacity is insufficient, and when the content of the near infrared absorber exceeds 3% by weight, the transmittance of visible light is reduced.
  • the composition of the present invention is applied to a glass or transparent base film by a wet method to produce a film or panel shape, wherein the wet method is a glass or a coating solution prepared by dissolving or dispersing a near infrared absorber and a polymer resin in an organic solvent. It is apply
  • the organic solvent in the group consisting of dichloromethane, dichloroethane (DME), methyl ethyl ketone, methyl isobutyl ketone, toluene, ethylene glycol monoethyl ether, ethanol, xylene, tetrahydrofuran and 1,4-dioxane Selected single or mixed forms thereof may be used, and the dithiol-based metal complex of the present invention is easily dissolved in the organic solvent, such as acrylic resin, polyester resin, polycarbonate resin, urethane resin, cellulose resin, polyisocyanate, It can be efficiently mixed with a polymer resin selected from the group consisting of polyarylate and epoxy resin.
  • the dithiol-based metal complex of the present invention is significantly improved in solubility not only in ketone and halogen solvents but also in alcohols such as ethylene glycol monoethyl ether and ethanol [ Table 2 ].
  • the near-infrared absorber of this invention is melt
  • the present invention may provide an optical filter and a thermal infrared shielding filter by a method of preparing a film by mixing a master batch prepared by mixing a near infrared absorber and a polymer resin.
  • additives such as antioxidants, heat stabilizers, viscosity adjusters, plasticizers, color improvers, lubricants, nucleating agents, UV stabilizers, antistatic agents, antioxidants, binders, and catalysts may be further used in the raw material composition of the master batch.
  • the content of the additive may be controlled within a range of maintaining 1 to 3% by weight of the near infrared absorbent.
  • the heat shielding film can be excellent in dispersibility of the near-infrared absorbent, thereby improving heat shielding efficiency without causing staining of the dye. Therefore, it is possible to provide a heat shield film having a uniform quality, and the process is simpler than the conventional dyeing process it can implement an economic effect.
  • the present invention uses the optical filter or the thermal infrared shielding filter in an image display device, in particular, 1 to 3% by weight of a near infrared absorber made of a dithiol-based metal complex, an acrylic resin, a polyester resin, a polycarbonate resin, and a urethane resin.
  • Optical filter or heat prepared by applying a composition consisting of 98 to 99% by weight of any one polymer resin selected from the group consisting of cellulose resin, polyisocyanate, polyarylate and epoxy resin on a glass or transparent base film
  • a plasma display panel employing an infrared shielding filter.
  • Step 1 After dissolving 13.5 g of 3,4,5-trimethoxybenzaaldehyde in 50 ml ethanol, 20 ml distilled water dissolved in 4.5 g of potassium cyanide was slowly added. After refluxing for 1 hour, the mixture was cooled, and 150 ml of distilled water was added to form a precipitate. The precipitate was filtered under reduced pressure, washed several times with distilled water, and dried to obtain 8.2 g of a yellow target product.
  • Step 2 After dissolving 48 g of 2-hydroxy-1,2-bis (3,4,5-trimethoxyphenyl) ethanone in 150 g of pyridine, 100 ml of distilled water dissolved in 50 g of CuSO 4 .5H 2 O was added. Added slowly. After refluxing for 10 hours, the mixture was cooled and 500 mL of distilled water was added to form a precipitate. The precipitate was filtered under reduced pressure, washed several times with distilled water and dried to obtain 40 g of a pale yellow target product.
  • Step 3 32 g of 1,2-bis (3,4,5-trimethoxyphenyl) ethane-1,2-dione and P 2 S 5 18 g were added to 150 ml of 1,4-dioxane and stirred. After refluxing for 5 hours, the mixture was cooled, filtered, and the filtrate was transferred to a 500 ml reactor, where a solution of 11 g of NiCl 2 ⁇ H 2 O dissolved in 100 ml of distilled water was slowly added over 1 hour. It was refluxed and cooled for 30 hours after the addition was completed. 100 ml of ethanol was added to the cooled reaction product, filtered under reduced pressure, washed several times with acetone, and dried to obtain 14 g of a dark green target product.
  • Step 4 14.7 g (0.11 mol) of AlCl 3 was stirred in 30 ml of dichloromethane for 30 minutes, and then 10 g (0.011 mol) of 12-methoxy-Ni-complex prepared in Step 3 was diluted in 50 ml of dichloromethane. And slowly added. After the reaction at room temperature for 1 hour and 30 minutes, the solution was stirred while slowly adding 600 ml of distilled water under an ice chamber, and the formed precipitate was filtered under reduced pressure, washed several times with distilled water, and then purified.
  • the purification method of the 12-methoxy-Ni-complex compound as a starting material the more hydroxy substituents in the maximum 12 methoxy groups are more easily dissolved in methanol to remove impurities by washing with a small amount of methanol.
  • the precipitate was dried and then dissolved in ethyl methyl ketone, and the solution filtered under reduced pressure was concentrated under reduced pressure to give 2.3 g of a dark green target product.
  • Example 1 The target compound prepared in Example 1 was analyzed using an HPLC and a mass spectrometer [LC-Mass spectrometer, VG BIO TECH, model name: VG BIO TECH] are shown in Table 1 and Table 2 .
  • thermogravimetric analyzer TGA
  • mp 258.71, 320.59 and 342.82 °C peaks were confirmed, using a differential parking calorimeter (DSC), three or more substances are mixed It was confirmed.
  • ⁇ max The maximum absorption wavelength of the compound prepared by changing the AlCl 3 equivalent used in Step 4 of Example 1 as shown in Table 3 below using a UV spectrometer under methyl ethyl ketone solvent conditions was measured.
  • the dithiol-based nickel complex prepared in Example 1 was significantly improved in solubility not only in the ketone-based and halogen-based solvents, but also in alcohols such as ethanol than the dithiol-based nickel complex substituted with methoxyl.
  • Step 1 After 40 g of p-anisaldehye was dissolved in 40 mL of ethanol, 20 mL of distilled water dissolved in 22 g of potassium cyanide was slowly added thereto. After refluxing for 1 hour, the mixture was cooled, and then 350 ml of distilled water was added to form a precipitate. The precipitate was filtered under reduced pressure. The precipitate was stirred with 40 ml of ethanol for 20 minutes, filtered, washed several times with ethanol, and dried to give a pale yellow target. 28 g. Obtained.
  • Step 2 19 g of 2-hydroxy-1,2-bis (4-methoxyphenyl) ethanone and 14 g of P 2 S 5 were added to 100 ml of 1,4-dioxane and stirred. After refluxing for 28 hours, the mixture was cooled, filtered, and the filtrate was transferred to a 500 ml reactor, where a solution of 9 g of NiCl 2 H 2 O dissolved in 30 ml of distilled water was slowly added over 2 hours. It was refluxed and cooled for 30 hours after the addition was completed. 200 ml of acetone was added to the cooled reaction, and the mixture was filtered under reduced pressure, washed several times with acetone, and dried to obtain 12 g of a dark green target product.
  • Step 3 22 g of AlCl 3 was stirred in 50 ml of dichloromethane for 30 minutes, and then 21 g of 12-methoxy-Ni-complex was diluted in 60 ml of dichloromethane and added slowly. After the reaction at room temperature for 30 minutes, 200ml of distilled water was slowly added under an ice chamber, and the precipitate formed was filtered under reduced pressure, washed several times with distilled water, and washed with a small amount of methanol. Drying gave 19 g of the dark green target product.
  • Step 1 50 g of benzaldehyde was dissolved in 80 ml of ethanol, and 70 ml of distilled water dissolved in 8 g of sodium cyanide was slowly added thereto. After refluxing for 3 hours, the precipitate formed by cooling was filtered under reduced pressure, and the precipitate was washed several times with ethanol and dried to obtain 35 g of a pale yellow target product.
  • Step 2 8.6 g of 2-hydroxy-1,2-diphenylethanone and 11.8 g of 2-hydroxy-1,2-bis (4-methoxyphenyl) ethanone together with 18 g of P 2 S 5 100 ml of 4-dioxane was added and stirred. The mixture was refluxed for 4 hours, cooled, filtered, and the filtrate was transferred to a 500 ml reactor, and then cooled to 0 ° C. using an ice bath. A solution of 10 g of NiCl 2 H 2 O in 30 ml of distilled water was added thereto for 1 hour. Added slowly over time. It was refluxed and cooled for 28 hours after the addition was completed. 50 ml of acetone was added to the cooled reaction product, filtered under reduced pressure, washed several times with acetone and dried to obtain 16 g of a dark green target product.
  • Step 3 20 g of AlCl 3 was stirred in 60 ml of dichloromethane for 30 minutes, and then 30 g of 12-methoxy-Ni-complex was diluted in 50 ml of dichloromethane and added slowly. After the reaction at room temperature for 30 minutes, 200 ml of distilled water was slowly added under an ice bath, and the precipitate formed was filtered under reduced pressure, washed several times with distilled water, and then washed with a small amount of methanol. Drying gave 17 g of the dark green target product.
  • the purification method of the 12-methoxy-Ni-complex compound as a starting material the more hydroxy substituents in the maximum 12 methoxy groups are more easily dissolved in methanol to remove impurities by washing with a small amount of methanol.
  • the precipitate was dried and then dissolved in ethyl methyl ketone, and the solution which was filtered under reduced pressure was concentrated under reduced pressure to give 4.8 g of a dark green target product.
  • ZnCl 2 was carried out in the same manner as in Example 6, except that 24.12 g (0.165 mol, 15 eq) was used.
  • a near-infrared absorber composed of a novel dithiol-based metal complex with improved solubility in ketone and halogen solvents as well as in organic solvents of alcohols.
  • the optical filter with excellent near-infrared absorption ability of the dithiol-based metal complex is sufficiently exhibited so that the near-infrared absorption ability is not degraded for a long time.
  • a thermal infrared shielding filter can be provided.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Engineering & Computer Science (AREA)
  • Health & Medical Sciences (AREA)
  • Toxicology (AREA)
  • Optical Filters (AREA)
  • Plasma & Fusion (AREA)
  • Microelectronics & Electronic Packaging (AREA)

Abstract

La présente invention concerne un absorbant de proche infrarouge constitué de complexe métallique de dithiol, un procédé de préparation dudit complexe métallique de dithiol, et un filtre optique et filtre de protection contre l’infrarouge thermique contenant ledit absorbant de proche infrarouge. L’absorbant de proche infrarouge est constitué d’un complexe métallique de dithiol qui réalise une absorption sélective du seul proche infrarouge, et étant donné que ledit complexe métallique de dithiol présente une solubilité améliorée par rapport aux solvants organiques, un mélange efficace est obtenu avec des matériaux organiques comprenant de la résine polymérique et analogue, qui sont mélangés lors de la fabrication d’un filtre optique, de sorte qu’une performance suffisamment supérieure d’absorption de proche infrarouge dudit complexe métallique de dithiol est assurée, et permet la préparation d’un nouvel absorbant de proche infrarouge dont la capacité d’absorption de proche infrarouge ne se détériore pas sur une longue période. En outre, l’absorbant de proche infrarouge selon la présente invention est préparé et obtenu soit par une étape de procédé de fabrication soit sous une forme de mélange maître; ainsi il peut être utilisé avantageusement pour un filtre optique, particulièrement un filtre de protection contre l’infrarouge thermique par l’utilisation d’un colorant d’absorption de proche infrarouge et présentant à la fois des effets de protection sélective contre le proche infrarouge qui sont supérieurs aux films de revêtement existants, et également une excellente stabilité à des températures élevées.
PCT/KR2009/006216 2008-10-27 2009-10-27 Absorbant de proche infrarouge constitué de complexe métallique de dithiol, procédé de préparation dudit complexe métallique de dithiol, et filtre optique et filtre de protection contre l’infrarouge thermique contenant un tel absorbant Ceased WO2010050720A2 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
KR1020080105189A KR20100046373A (ko) 2008-10-27 2008-10-27 디티올계 금속 착화합물로 이루어진 근적외선 흡수제, 상기디티올계 금속 착화합물의 제조방법, 그를 함유한 광학 필터 및 열적외선 차폐 필터
KR10-2008-0105189 2008-10-27

Publications (3)

Publication Number Publication Date
WO2010050720A2 true WO2010050720A2 (fr) 2010-05-06
WO2010050720A3 WO2010050720A3 (fr) 2010-08-05
WO2010050720A4 WO2010050720A4 (fr) 2010-09-30

Family

ID=42129444

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/KR2009/006216 Ceased WO2010050720A2 (fr) 2008-10-27 2009-10-27 Absorbant de proche infrarouge constitué de complexe métallique de dithiol, procédé de préparation dudit complexe métallique de dithiol, et filtre optique et filtre de protection contre l’infrarouge thermique contenant un tel absorbant

Country Status (2)

Country Link
KR (1) KR20100046373A (fr)
WO (1) WO2010050720A2 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103502222A (zh) * 2011-05-06 2014-01-08 巴斯夫欧洲公司 具有全氟烷基取代基的发色团
CN104177238A (zh) * 2014-07-25 2014-12-03 山东大学 合成3,4-二(3,4,5-三甲氧基苯基)-2,5-二苯基环戊二烯酮的方法

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN118005543B (zh) * 2024-04-10 2024-07-09 蜂巢能源科技股份有限公司 一种电解液添加剂及其制备方法和应用

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH1112425A (ja) * 1997-06-23 1999-01-19 Mitsubishi Rayon Co Ltd プラズマディスプレイ用光学フィルタ
US6217796B1 (en) * 1998-11-17 2001-04-17 Nisshinbo Industries, Inc. Near infrared absorption composition
JP2001138623A (ja) * 1999-11-12 2001-05-22 Canon Inc 被記録媒体

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103502222A (zh) * 2011-05-06 2014-01-08 巴斯夫欧洲公司 具有全氟烷基取代基的发色团
CN103502222B (zh) * 2011-05-06 2016-08-17 巴斯夫欧洲公司 具有全氟烷基取代基的发色团
CN104177238A (zh) * 2014-07-25 2014-12-03 山东大学 合成3,4-二(3,4,5-三甲氧基苯基)-2,5-二苯基环戊二烯酮的方法
CN104177238B (zh) * 2014-07-25 2016-05-25 山东大学 合成3,4-二(3,4,5-三甲氧基苯基)-2,5-二苯基环戊二烯酮的方法

Also Published As

Publication number Publication date
WO2010050720A3 (fr) 2010-08-05
WO2010050720A4 (fr) 2010-09-30
KR20100046373A (ko) 2010-05-07

Similar Documents

Publication Publication Date Title
WO2016108411A1 (fr) Complexe métallique et film de conversion de couleur le comprenant
CN110494502B (zh) 着色剂化合物和包含其的着色组合物
WO2011096643A1 (fr) Matière photochrome
WO2009139579A9 (fr) Préparation de dérivés d'anthracène asymétriques et dispositif électroluminescent organique utilisant lesdits dérivés
EP3848357B1 (fr) Absorbeur reactive d'uv de type benzotriazole et son utilisation
WO2010050720A2 (fr) Absorbant de proche infrarouge constitué de complexe métallique de dithiol, procédé de préparation dudit complexe métallique de dithiol, et filtre optique et filtre de protection contre l’infrarouge thermique contenant un tel absorbant
US6846934B2 (en) Photochromic diarylethene substituted with isoxazole group
KR101525542B1 (ko) 크산텐 염료 화합물 및 이의 제조방법
KR20160129385A (ko) 컬러필터용 착색 염료 및 이를 포함하는 감광성 수지 조성물
WO2023195774A1 (fr) Sel de diphényliodonium pour photoinitiateur et son procédé de préparation
WO2011102599A1 (fr) Matériau photochrome
WO2017052279A1 (fr) Composé cyclique contenant de l'azote et film de conversion de couleur comprenant celui-ci
CN108473782B (zh) 着色剂化合物、及包含该着色剂化合物的着色剂材料
CN121013888A (zh) 喹酞酮化合物、着色组合物及固化物
WO2013147443A1 (fr) Composition de résine contenant un polymère de silsesquioxane de type échelle pour film optique
WO2019093806A2 (fr) Composé et film de conversion de couleur comprenant celui-ci
WO2013176325A1 (fr) Nouveau procédé de préparation d'un composé hétérocyclique condensé faisant appel à un réactif de gilman
WO2018190679A1 (fr) Composé cyclique contenant de l'azote et film changeant de couleur comprenant celui-ci
CN120842877B (zh) 一种高溶解度光刻胶用绿色酞菁染料及其合成方法
KR101793681B1 (ko) 페릴렌 계열의 광차단막용 안료 및 그를 이용한 광경화성 조성물
CN118184523B (zh) 二胺化合物、其中间体及聚酰亚胺薄膜
KR20010067047A (ko) 아릴아미노히드록시안트라퀴논의 제조방법
KR101163656B1 (ko) 디이모늄염 올리고머, 이의 제조방법 및 용도
WO2024111793A1 (fr) Composé pour filtre d'absorption dans le proche infrarouge, composition le comprenant, et film d'absorption dans le proche infrarouge comprenant un produit durci de celui-ci
WO2019212219A1 (fr) Composé et film de conversion de couleur le comprenant, unité de rétroéclairage et dispositif d'affichage

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 09823800

Country of ref document: EP

Kind code of ref document: A2

NENP Non-entry into the national phase

Ref country code: DE

32PN Ep: public notification in the ep bulletin as address of the adressee cannot be established

Free format text: NOTING OF LOSS OF RIGHTS PURSUANT TO RULE 112(1) EPC (EPO FORMS 1205A DATED 06.07.11 AND 01.08.11)

122 Ep: pct application non-entry in european phase

Ref document number: 09823800

Country of ref document: EP

Kind code of ref document: A2