WO2010050720A2 - Near infrared absorbent consisting of dithiol metal complex, method for preparing said dithiol metal complex, and optical filter and thermal infrared shielding filter containing same - Google Patents
Near infrared absorbent consisting of dithiol metal complex, method for preparing said dithiol metal complex, and optical filter and thermal infrared shielding filter containing same Download PDFInfo
- 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
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- WIPO (PCT)
- Prior art keywords
- dithiol
- metal complex
- formula
- based metal
- near infrared
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- -1 dithiol metal complex Chemical class 0.000 title claims abstract description 24
- 238000000034 method Methods 0.000 title claims abstract description 15
- 239000002250 absorbent Substances 0.000 title claims abstract description 14
- 230000002745 absorbent Effects 0.000 title claims abstract description 14
- 230000003287 optical effect Effects 0.000 title abstract description 26
- 239000002952 polymeric resin Substances 0.000 claims abstract description 21
- 229920003002 synthetic resin Polymers 0.000 claims abstract description 21
- 239000003960 organic solvent Substances 0.000 claims abstract description 13
- 238000004519 manufacturing process Methods 0.000 claims abstract description 11
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 81
- 150000004662 dithiols Chemical class 0.000 claims description 79
- 239000006096 absorbing agent Substances 0.000 claims description 49
- 150000001875 compounds Chemical class 0.000 claims description 40
- 150000004696 coordination complex Chemical class 0.000 claims description 40
- 229910052759 nickel Inorganic materials 0.000 claims description 40
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical group ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 36
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 33
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 31
- 239000000203 mixture Substances 0.000 claims description 19
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- 229910052739 hydrogen Inorganic materials 0.000 claims description 16
- 239000001257 hydrogen Substances 0.000 claims description 16
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 16
- 125000001033 ether group Chemical group 0.000 claims description 11
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 10
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 10
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 10
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- 229910052751 metal Inorganic materials 0.000 claims description 8
- 239000002184 metal Substances 0.000 claims description 8
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 7
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- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 claims description 5
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 claims description 5
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 claims description 5
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 5
- 238000005805 hydroxylation reaction Methods 0.000 claims description 5
- 229910052763 palladium Inorganic materials 0.000 claims description 5
- 229910052697 platinum Inorganic materials 0.000 claims description 5
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 5
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- 229910001510 metal chloride Inorganic materials 0.000 claims description 3
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- NAWXUBYGYWOOIX-SFHVURJKSA-N (2s)-2-[[4-[2-(2,4-diaminoquinazolin-6-yl)ethyl]benzoyl]amino]-4-methylidenepentanedioic acid Chemical compound C1=CC2=NC(N)=NC(N)=C2C=C1CCC1=CC=C(C(=O)N[C@@H](CC(=C)C(O)=O)C(O)=O)C=C1 NAWXUBYGYWOOIX-SFHVURJKSA-N 0.000 description 2
- LRRQSCPPOIUNGX-UHFFFAOYSA-N 2-hydroxy-1,2-bis(4-methoxyphenyl)ethanone Chemical compound C1=CC(OC)=CC=C1C(O)C(=O)C1=CC=C(OC)C=C1 LRRQSCPPOIUNGX-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 description 2
- ISAOCJYIOMOJEB-UHFFFAOYSA-N benzoin Chemical compound C=1C=CC=CC=1C(O)C(=O)C1=CC=CC=C1 ISAOCJYIOMOJEB-UHFFFAOYSA-N 0.000 description 2
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- 239000003054 catalyst Substances 0.000 description 2
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- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical compound ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
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- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
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- NNFCIKHAZHQZJG-UHFFFAOYSA-N potassium cyanide Chemical compound [K+].N#[C-] NNFCIKHAZHQZJG-UHFFFAOYSA-N 0.000 description 2
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- OIFKAYYDTOHLSS-UHFFFAOYSA-N 1,2-bis(3,4,5-trimethoxyphenyl)ethane-1,2-dione Chemical compound COC1=C(OC)C(OC)=CC(C(=O)C(=O)C=2C=C(OC)C(OC)=C(OC)C=2)=C1 OIFKAYYDTOHLSS-UHFFFAOYSA-N 0.000 description 1
- JIDNYUKRPUJZAL-UHFFFAOYSA-N 2-hydroxy-1,2-bis(3,4,5-trimethoxyphenyl)ethanone Chemical compound COC1=C(OC)C(OC)=CC(C(O)C(=O)C=2C=C(OC)C(OC)=C(OC)C=2)=C1 JIDNYUKRPUJZAL-UHFFFAOYSA-N 0.000 description 1
- JHUUPUMBZGWODW-UHFFFAOYSA-N 3,6-dihydro-1,2-dioxine Chemical compound C1OOCC=C1 JHUUPUMBZGWODW-UHFFFAOYSA-N 0.000 description 1
- DMHBUEWIMWWGIH-YJSPFGELSA-N CC/C(/I)=C/C=C(\C=C)/C(S1)=C(C2=CC=C=CC=C2)S[N]11SC(c2ccccc2)=C(/C(/C=C\C)=C/C=C)S1 Chemical compound CC/C(/I)=C/C=C(\C=C)/C(S1)=C(C2=CC=C=CC=C2)S[N]11SC(c2ccccc2)=C(/C(/C=C\C)=C/C=C)S1 DMHBUEWIMWWGIH-YJSPFGELSA-N 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
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- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
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- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 description 1
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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.
Abstract
The present invention relates to a near infrared absorbent consisting of a novel dithiol metal complex, a method for preparing said dithiol metal complex, and an optical filter and a thermal infrared shielding filter containing said near infrared absorbent. The near infrared absorbent of the present invention consists of a dithiol metal complex that selectively absorbs near infrared only, and as said dithiol metal complex has improved solubility with respect to organic solvents, efficient mixing is accomplished with organic materials including polymeric resin, etc., which are mixed when manufacturing an optical filter, so that sufficiently superior performance of rear infrared absorption of said dithiol metal complex is exhibited, and a novel near infrared absorbent is prepared, the near infrared absorption capability whereof does not deteriorate over a long period. Furthermore, the near infrared absorbent of the present invention is provided and manufactured either through a manufacturing process step or in a separate master batch form; thus, it may be usefully utilized for an optical filter, particularly a thermal infrared shielding filter using a near infrared absorption dye and having both selective near infrared shielding effects that are superior to existing coating-type films, and excellent high temperature stability.
Description
본 발명은 디티올계 금속 착화합물로 이루어진 근적외선 흡수제, 상기 디티올계 금속 착화합물의 제조방법, 그를 함유한 광학 필터 및 열적외선 차폐 필터에 관한 것으로서, 더욱 상세하게는 본 발명은 유기용매에 대한 용해성이 개선된 신규한 디티올계 니켈 착화합물로 이루어진 근적외선 흡수제를 제공함에 따라, 광학 필터 제조 시, 혼용되는 고분자 수지등의 유기재료와의 효율적으로 혼합하여, 상기 디티올계 니켈 착화합물의 우수한 근적외선 흡수성능이 충분히 발휘되어 장시간에 걸쳐 근적외선 흡수 능력이 저하되지 않는 광학 필터 및 열적외선 차폐 필터에 관한 것이다.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. By providing a novel near-infrared absorber composed of a novel dithiol-based nickel complex compound, 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.
최근, 많은 종류의 화상 표시 장치(디스플레이) 예를 들면, 액정 표시 장치(LCD), 플라즈마 디스플레이 패널(PDP), 전계 발광 디스플레이(ELD), 음극관 표시 장치(CRT), 형광 표시관, 전계 방사형 디스플레이의 개발과 이들을 포함하는 기기가 실용화되어 있다. 이들의 각종 화상 표시 장치 중에서도, 하이비젼용 대형 벽걸이 텔레비전, 멀티 미디어용 대화면 디스플레이로서 칼라 플라즈마 디스플레이(PDP)가 주목을 받고 있다.Recently, many kinds of image display devices (displays), for example, liquid crystal displays (LCDs), plasma display panels (PDPs), electroluminescent displays (ELDs), cathode ray display devices (CRTs), fluorescent displays, electroluminescent displays Has been put to practical use. Among these various image display apparatuses, color plasma display (PDP) is attracting attention as a large wall-mounted television for high-vision and a large-screen display for multimedia.
이들의 화상 표시 장치는 원칙으로서 적색, 청색, 녹색의 빛의 삼원색의 조합으로 칼라 화상을 표시한다. 그러나, 표시장치로부터는 불필요한 파장의 빛도 발해지고 있고, 주변 전자 기기의 오동작이나 표시 화상의 고품질화에 문제가 있다. 특히 플라즈마 디스플레이는 800 내지 1000nm 영역의 근적외선이나 전자파 등도 방출하는데, 상기 근적외선의 파장 영역은 근적외선 통신이나 다른 전자기기의 리모트 컨트롤러에 사용되는 파장 영역과 중복되기 때문에, 주변 전자기기의 오작동을 일으키는 원인이 된다. In principle, these image display devices display a color image in a combination of three primary colors of red, blue, and green light. However, 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. In particular, 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.
상기 문제에 대하여, 특정의 빛을 흡수하는 광흡수제를 함유한 광학 필터가 사용되고 있고, 예를 들면 근적외선을 흡수하는 광학 필터는 일본 특허공개 평9-230134호 공보, 일본 특허공개 평11-73115호 공보, 일본 특허공개 평11-12425호 공보, 일본 특허공개 2000-206322호 공보, 일본 특허공개 2000-212546호 공보 등에 방향족 디티올 니켈화합물을 광흡수제로서 이용한 광학 필터가 보고되어 있다.In response to the above problem, 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.
광학 필터용 근적외선 흡수제로서는 근적외선 영역의 파장광을 선택적으로 흡수하고, 가시광선 영역의 빛을 투과하는 것이 요구되고 있다. 그러나, 종래의 광흡수제는 가시광선 영역도 흡수하여, 광학 필터용의 광흡수제로서는 적합한 것이 아니었다.As 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. However, the conventional light absorbing agent also absorbs the visible light region and was not suitable as a light absorbing agent for optical filters.
종래 공지된 광흡수제 중, 800 내지 900nm 파장영역의 근적외선을 효과적으로 흡수하여 근적외선 흡습제로서 우수한 성능을 가진 일례로서, 하기 화학식 13으로 표시되는 디티올계 니켈 착화합물이 대표적이다.Among the conventionally known light absorbing agents, 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.
화학식 13 
Formula 13
상기 디티올계 니켈 착화합물은 근적외선 흡수제로서의 용도 이외에도 일중항 산소에 대하여 우수한 비활성화 작용을 가지므로, 폴리올레핀류 등의 산화방지제, 내후제 또는 칼라사진 등의 탈색 방지제로서 유용하다. 나아가, 상기 디티올계 니켈 착화합물은 물의 광분해반응과 탈수반응의 촉매 또는 액정재료로서 유용하게 활용될 수 있을 정도로 다분야에 적용가능한 우수한 성질을 가지고 있다. 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.
이러한 디티올계 니켈 착화합물의 성질을 충분히 발휘하기 위해서는 바인더 수지, 플라스틱, 이온 도료 또는 유기용제 등의 유기재료에 균일하게 최적의 함량으로 용해 또는 함유시켜야 한다. 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.
그러나, 상기 디티올계 니켈 착화합물은 유기재료에 대하여 용해성이 현저히 낮아 유기재료에 충분한 양을 함유시킬 수 없으므로 성능을 충분히 발휘하지 못하는 문제점이 있다. However, 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.
이에, 본 발명자들은 종래 광학 필터용의 광흡수제의 문제점을 해소하고자 노력한 결과, 종래의 디티올계 니켈 착화합물로부터 유기재료에 대한 용해성이 개선되고 선택적으로 근적외선만을 흡수하는 신규한 디티올계 니켈 착화합물을 얻고, 상기 디티올계 니켈 착화합물의 성능이 충분히 발휘되어 장시간에 걸쳐 근적외선 흡수 능력이 저하되지 않는 신규한 근적외선 흡수색소를 제조하고, 이를 이용한 광학 필터 및 열적외선 차폐 필터를 제공함으로써, 본 발명을 완성하였다.Accordingly, 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.
본 발명의 목적은 가시광선 영역의 흡수가 작고, 선택적으로 근적외선 영역의 파장광을 흡수하고 유기재료에 대한 용해성이 개선된 근적외선 흡수제를 제공하는 것이다.It is an object of the present invention to provide a near-infrared absorber having a low absorption in the visible region, selectively absorbing wavelength light in the near-infrared region, and improving solubility in organic materials.
본 발명의 다른 목적은 신규한 디티올계 니켈 착화합물의 제조방법을 제공하는 것이다.Another object of the present invention is to provide a novel method for producing a dithiol-based nickel complex.
본 발명의 또 다른 목적은 상기 디티올계 니켈 착화합물로 이루어진 근적외선 흡수제를 함유한 광학 필터, 열적외선 차폐 필터 및 이를 채용한 플라즈마 디스플레이 패널을 제공하는 것이다.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.
상기 목적을 달성하기 위하여, 본 발명은 유기재료에 대한 용해성이 개선된 디티올계 니켈 착화합물로 이루어진 근적외선 흡수제를 제공한다.In order to achieve the above object, the present invention provides a near-infrared absorber composed of a dithiol-based nickel complex compound with improved solubility in organic materials.
더욱 상세하게는, 하기 화학식 1로 표시되는 디티올계 금속 착화합물로 이루어진 근적외선 흡수제를 제공하는 것이다.More specifically, it is to provide a near-infrared absorber composed of a dithiol-based metal complex represented by the following formula (1).
화학식 1 
Formula 1
(상기에서, M은 니켈, 팔라듐 또는 백금이며, R은 수소, C1∼C6의 알킬기 또는 C1∼C6의 에테르기이고, X는 수소 또는 할로겐이고, m=1∼3이고, o, p, q, r, o', p', q' 및 r'는 0∼3이며, [o-o'], [p-p'], [q-q'] 및 [r-r']는 각각 0∼3이며 양의 정수이다.)(Wherein, 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.)
본 발명의 상기 디티올계 금속 착화합물은 벤젠고리에 하이드록시기가 1 내지 5개 치환되어 용해도가 개선된 것을 특징으로 하는 근적외선 흡수제를 제공한다. 이때, 본 발명의 근적외선 흡수제에서 디티올계 금속 착화합물 중, 금속 원소는 니켈이 바람직하다.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. At this time, in the near-infrared absorber of the present invention, nickel is preferably used as the metal element among the dithiol-based metal complex compounds.
본 발명의 디티올계 금속 착화합물은 디클로로메탄, 디클로로에탄, 메틸에틸케톤, 메틸이소부틸케톤, 톨루엔, 에틸렌글리콜모노에틸에테르, 에탄올, 자일렌, 테트라히드로푸란 및 1,4-디옥산으로 이루어진 군에서 선택되는 어느 하나의 유기용매에 대하여 용해성 개선 효과를 보인다.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.
또한, 본 발명은 용해도가 개선된 디티올계 금속 착화합물의 제조방법을 제공한다. The present invention also provides a method for producing a dithiol-based metal complex having improved solubility.
더욱 구체적으로는, 하기 화학식 10으로 표시되는 2-하이드록시기를 가진 화합물을 산화 반응하여, 화학식 11로 표시되는 디온 화합물을 합성하는 제1단계;More specifically, a first step of synthesizing the dione compound represented by the formula (11) by oxidizing the compound having a 2-hydroxy group represented by the formula (10);
화학식 11로 표시되는 디온 화합물과 금속염화물과 반응하여, 화학식 12로 표시되는 디티올계 금속 착화합물을 제조하는 제2단계; 및 A second step of preparing a dithiol-based metal complex compound represented by Chemical Formula 12 by reacting with a dione compound represented by Chemical Formula 11 and a metal chloride; And
상기 화학식 12로 표시되는 디티올계 금속 착화합물 함유 유기용액에 AlCl3, ZnCl2 및 BF3로 이루어진 군에서 선택되는 적어도 하나의 루이스 산을 정량적으로 첨가하여 부분적으로 하이드록실레이션 반응을 제어하여, 화학식 1로 표시되는 디티올계 금속 착화합물을 제조한다.By partially quantitatively 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, the reaction was partially controlled by Formula 1 To prepare a dithiol-based metal complex represented by.
반응식 1Scheme 1
(상기에서, M은 니켈, 팔라듐 또는 백금이며, R은 수소, C1∼C6의 알킬기 또는 C1∼C6의 에테르기이고, X는 수소 또는 할로겐이고, m=1∼3이고, o, p, q, r, o', p', q' 및 r'는 0∼3이며, [o-o'], [p-p'], [q-q'] 및 [r-r']는 각각 0∼3이며 양의 정수이다.)(Wherein, 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.)
본 발명의 제조방법 중 제3단계에서 AlCl3, ZnCl2 및 BF3로 이루어진 군에서 선택되는 적어도 하나의 루이스 산은 디티올계 금속 착화합물에 대하여, 2 내지 15몰%, 더욱 바람직하게는 2 내지 10몰%로 첨가되어 부분적 하이드록실레이션 반응을 수행하여, 대칭형 또는 비대칭형의 디티올계 금속 착화합물을 제조할 수 있다.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.
이때, 상기 디티올계 금속 착화합물은 하이드록시기 치환기가 2 내지 5개인 것이 바람직하며, 중심금속은 니켈이 바람직하다.In this case, the dithiol-based metal complex compound is preferably a hydroxyl group substituent of 2 to 5, the center metal is preferably nickel.
또한, 본 발명은 유리 또는 투명한 기재필름 상에, 화학식 1로 표시되는 디티올계 금속 착화합물로 이루어진 근적외선 흡수제와 고분자 수지를 함유한 조성물을 적용하여 필름 또는 패널 형상으로 제조된 광학 필터 특히, 열적외선 차폐 필터를 제공한다.In addition, 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.
이때, 상기 디티올계 금속 착화합물 중, 중심금속은 니켈이 바람직하며, 상기 고분자 수지는 아크릴계 수지, 폴리에스테르계 수지, 폴리카보네이트 수지, 우레탄계 수지, 셀룰로오스계 수지, 폴리이소시아네이트, 폴리아릴레이트 및 에폭시계 수지로 이루어진 군에서 선택 사용될 수 있다.At this time, in the dithiol-based metal complex compound, the central metal is preferably nickel, and 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.
또한 상기 조성물이 근적외선 흡수제 및 고분자 수지로 이루어지되, 고분자 수지에 대하여, 근적외선 흡수제 1 내지 3 중량%를 함유한다.In addition, 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.
나아가, 본 발명은 상기 광학 필터 또는 열적외선 차폐 필터를 화상 표시 장치에 이용되며, 특히 디티올계 금속 착화합물로 이루어진 근적외선 흡수제 1 내지 3 중량%와 아크릴계 수지, 폴리에스테르계 수지, 폴리카보네이트 수지, 우레탄계 수지, 셀룰로오스계 수지, 폴리이소시아네이트, 폴리아릴레이트 및 에폭시계 수지로 이루어진 군에서 선택되는 어느 하나의 고분자 수지 98 내지 99 중량%로 이루어진 조성물을 유리 또는 투명한 기재필름 상에 적용하여 제조된 광학 필터 또는 열적외선 차폐 필터가 채용된 플라즈마 디스플레이 패널을 제공한다.Furthermore, 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 Provided is a plasma display panel employing an infrared shielding filter.
본 발명에 따라, 가시광선 영역의 흡수가 작고, 선택적으로 근적외선 영역의 파장광을 흡수하고 유기재료에 대한 용해성이 개선된 디티올계 금속 착화합물로 이루어진 근적외선 흡수제를 제공할 수 있으며, 상기 용해성이 개선된 근적외선 흡수제를 함유하여 장시간에 걸쳐 근적외선 흡수 능력이 저하되지 않는 광학 필터, 열적외선 차폐 필터 및 이를 채용한 플라즈마 디스플레이 패널을 제공할 수 있다.According to the present invention, it is possible to provide 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.
도 1은 본 발명의 디티올계 니켈 착화합물의 자외선 분광기를 이용한 흡수스펙트럼이다. 1 is an absorption spectrum using ultraviolet spectroscopy of the dithiol-based nickel complex of the present invention.
이하, 본 발명을 상세히 설명하고자 한다.Hereinafter, the present invention will be described in detail.
본 발명은 종래 근적외선 흡수제로 공지된 화학식 5의 디티올계 금속 착화합물이 유기용매에 대하여 용해도가 낮은 문제점을 해소하고자 안출된 발명으로서, 화학식 1로 표시되는 디티올계 금속 착화합물로 이루어진 근적외선 흡수제를 제공한다.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).
화학식 1Formula 1
(상기에서, M은 니켈, 팔라듐 또는 백금이며, R은 수소, C1∼C6의 알킬기 또는 C1∼C6의 에테르기이고, X는 수소 또는 할로겐이고, m=1∼3이고, o, p, q, r, o', p', q' 및 r'는 0∼3이며, [o-o'], [p-p'], [q-q'] 및 [r-r']는 각각 0∼3이며 양의 정수이다.)(Wherein, 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.)
상기에서, 더욱 바람직하게는 금속 원자가 니켈이며, R의 알킬기는 메틸기, 에틸기, n-프로필기, iso-프로필기, n-부틸기, iso-부틸기, sec-부틸기, tert-부틸기, n-펜틸기, iso-펜틸기, sec-펜틸기, tert-펜틸기 및 n-헥실기로 이루어진 군에서 선택되는 어느 하나를 사용할 수 있으며, 더욱 바람직하게는 R의 알킬기가 메틸기 또는 에틸기인 것이다. In the above, more preferably, the metal atom is nickel, and 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. .
상기 디티올계 금속 착화합물은 하이드록시기(R=H)가 증가할수록 용해도가 개선되나, 바람직하게는 1 내지 5개, 더욱 바람직하게는 2 내지 5개가 치환될 때, 용해도 개선 효과를 보이는 동시에, 930 내지 960nm 파장영역의 근적외선을 선택적으로 흡수하여 PDP 광학필터용도에 적합하다. 이때, 하이드록시기가 5개를 초과하면, 용해도개선효과는 높으나, 장파장이동이 현저하여 원하는 파장범위를 벗어나고, 니켈 착화합물이 깨지는 부반응물 생성이 증가하여 분리정제가 어렵다.The dithiol-based metal complex compound improves the solubility as the hydroxyl group (R = H) increases, but when 1 to 5, more preferably 2 to 5 is substituted, it shows a solubility improving effect, 930 It selectively absorbs near infrared rays in the wavelength range from 960 nm to the PDP optical filter. At this time, when the number of hydroxyl groups is more than five, the solubility improvement effect is high, but the long wavelength shift is remarkable, out of the desired wavelength range, and the formation of side reactants in which the nickel complex compound is broken increases, making it difficult to separate and purify.
본 발명에서 용해도 개선이라 함은 본 발명의 디티올계 금속 착화합물은 케톤계와 할로겐계 용매뿐만 아니라, 에틸렌글리콜모노에틸에테르와 에탄올 등의 알코올류에서도 용해도가 개선된다. 더욱 구체적으로는, 디클로로메탄, 디클로로에탄, 메틸에틸케톤, 메틸이소부틸케톤, 톨루엔, 에틸렌글리콜모노에틸에테르, 에탄올, 자일렌, 테트라히드로푸란 및 1,4-디옥산로 이루어진 군에서 선택되는 어느 하나의 유기용매에 대하여 용해성능(soluble)을 가진다.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.
또한, 본 발명의 디티올계 금속 착화합물은 930 내지 960nm 파장영역의 근적외선을 선택적으로 흡수한다.In addition, the dithiol-based metal complex of the present invention selectively absorbs near infrared rays in the wavelength range of 930 to 960 nm.
본 발명의 바람직한 제1실시형태의 근적외선 흡수제는 하기 화학식 2 또는 화학식 3으로 표시되는 디티올계 니켈 착화합물을 함유하고, R=H가 2 내지 5개가 함유된 것이다.The near-infrared absorber of 1st Embodiment of this invention contains the dithiol type nickel complex compound represented by following formula (2) or (3), and R = H contains 2-5 pieces.
화학식 2 
Formula 2
화학식 3 
Formula 3
(상기에서, R은 수소, C1∼C6의 알킬기 또는 C1∼C6의 에테르기이다.)(Wherein, R is an ether group of hydrogen, C 1 ~C 6 alkyl group or a C 1 ~C 6 in.)
본 발명의 바람직한 제2실시형태로서 근적외선 흡수제는 하기 화학식 4 내지 화학식 6으로 표시되는 대칭형 디티올계 니켈 착화합물 중에서 선택되는 디티올계 니켈 착화합물을 함유하고, R=H가 2 내지 5개가 함유된 것이다.As a second preferred embodiment of the present invention, the near-infrared absorber contains a dithiol-based nickel complex compound selected from the symmetrical dithiol-based nickel complex compounds represented by the following formulas (4) to (6), and R = H contains 2-5.
화학식 4 
Formula 4
화학식 5 
Formula 5
화학식 6 
Formula 6
(상기에서, R은 수소, C1∼C6의 알킬기 또는 C1∼C6의 에테르기이다.)(Wherein, R is an ether group of hydrogen, C 1 ~C 6 alkyl group or a C 1 ~C 6 in.)
또한, 본 발명의 바람직한 제3실시형태의 근적외선 흡수제는 하기 화학식 7 내지 화학식 9로 표시되는 비대칭형 디티올계 니켈 착화합물 중에서 선택되는 디티올계 니켈 착화합물을 함유하고, R=H가 2 내지 5개가 함유된 것이다.In addition, the near-infrared absorber of the third preferred embodiment of the present invention contains a dithiol-based nickel complex compound selected from the asymmetric dithiol-based nickel complex compounds represented by the following formulas (7) to (9), wherein R = H contains 2-5. will be.
화학식 7 
Formula 7
화학식 8 
Formula 8
화학식 9 
Formula 9
(상기에서, R은 수소, C1∼C6의 알킬기 또는 C1∼C6의 에테르기이다.)(Wherein, R is an ether group of hydrogen, C 1 ~C 6 alkyl group or a C 1 ~C 6 in.)
본 발명은 상기 근적외선 흡수제에 함유되며, 용해도가 개선된 디티올계 금속 착화합물의 제조방법을 제공한다.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.
더욱 구체적으로는, 하기 화학식 10으로 표시되는 2-하이드록시기를 가진 화합물을 산화 반응하여, 화학식 11로 표시되는 디온 화합물을 합성하는 제1단계;More specifically, a first step of synthesizing the dione compound represented by the formula (11) by oxidizing the compound having a 2-hydroxy group represented by the formula (10);
화학식 11로 표시되는 디온 화합물과 금속염화물과 반응하여, 화학식 12로 표시되는 디티올계 금속 착화합물을 제조하는 제2단계; 및 A second step of preparing a dithiol-based metal complex compound represented by Chemical Formula 12 by reacting with a dione compound represented by Chemical Formula 11 and a metal chloride; And
상기 화학식 12로 표시되는 디티올계 금속 착화합물 함유 유기용액에 AlCl3, ZnCl2 및 BF3로 이루어진 군에서 선택되는 적어도 하나의 루이스 산을 첨가하여 부분적으로 하이드록실레이션 반응을 제어하여, 화학식 1로 표시되는 디티올계 금속 착화합물을 제조하는 제3단계로 이루어진다.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.
반응식 1Scheme 1
(상기에서, M, R, X, m, o, p, q, r, o', p', q' 및 r'는 상기에서 정의한 바와 같다.)(In the above, M, R, X, m, o, p, q, r, o ', p', q 'and r' are as defined above.)
본 발명의 제조방법은 제3단계에서 AlCl3, ZnCl2 및 BF3로 이루어진 군에서 선택되는 적어도 하나의 루이스 산이 디티올계 금속 착화합물에 대하여, 2 내지 15몰%, 더욱 바람직하게는 2 내지 10몰%로 첨가되어 부분적 하이드록실레이션 반응을 수행할 수 있다. 이때, 선택된 루이스 산의 당량에 따라, 흡수파장의 변화, 용해도 변화 및 수율에 영향을 미친다. AlCl3을 선택사용할 경우, 2 내지 10몰%이 바람직하고, ZnCl2를 사용할 경우, 2 내지 15몰%까지 원하는 흡수파장의 변화, 용해도 변화 및 수율을 얻을 수 있다. 다만, 루이스 산의 당량이 15몰%을 초과하면, 용해도는 현저히 개선되나, 장파장이동이 현저하고, 니켈 착화합물이 깨지는 부반응물 생성이 증가하여 전체수율을 낮춘다[표 3 및 표 4].In the preparation method of the present invention, at least one Lewis acid selected from the group consisting of AlCl 3 , ZnCl 2 and BF 3 in the third step is 2 to 15 mol%, more preferably 2 to 10 mol relative to the dithiol-based metal complex compound. % May be added to effect partial hydroxylation reaction. At this time, depending on the equivalent of the selected Lewis acid, it affects the change in absorption wavelength, solubility change and yield. When AlCl 3 is optionally used, 2 to 10 mol% is preferable, and when ZnCl 2 is used, desired change in absorption wavelength, solubility change and yield can be obtained up to 2 to 15 mol%. However, when the equivalent of Lewis acid exceeds 15 mol%, the solubility is remarkably improved, but the long wavelength shift is remarkable, and the formation of side reactants in which the nickel complex compound is broken increases, lowering the overall yield [ Table 3 and Table 4 ].
본 발명의 디티올계 금속 착화합물은 상기 하이드록시기 치환기가 1 내지 5개, 더욱 바람직하게는 2 내지 5개인 경우, 유기용매에 대한 우수한 용해성을 구현한다. 상기 하이드록시 치환기가 5개를 초과하면, 용해성은 우수하나, 장파장이동이 현저하여 원하는 파장범위를 벗어나고, 목적하는 니켈 착화합물의 분리정제에 어려움이 있다. 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.
상기 유기용매는 클로로메탄, 디클로로에탄, 메틸에틸케톤, 메틸이소부틸케톤, 톨루엔, 에틸렌글리콜모노에틸에테르, 에탄올, 자일렌, 테트라히드로푸란 및 1,4-디옥산로 이루어진 군에서 선택되는 어느 하나이며, 종래 거의 용해되지 않는 용해성(insoluble)에 대하여 우수한 용해성(soluble)을 발휘한다.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.
또한, 본 발명의 제조방법의 제3단계는 R=CH3로만 치환된 대칭 또는 비대칭의 디티올계 금속 화합물을 출발물질로 하고, 하이드록실레이션 반응을 통해, 정량적으로 R=H(하이드록시기) 치환반응을 제어한다. 이에, 유기용매에 대한 용해도가 개선된 동시에 930 내지 960nm 파장영역의 근적외선을 선택적으로 흡수하는 대칭형[화학식 4 내지 6으로 표기되는 화합물] 또는 비대칭형[화학식 7 내지 9로 표기되는 화합물]의 디티올계 금속 착화합물을 제조할 수 있다.In addition, the third step of the production method of the present invention is a symmetrical or asymmetric dithiol-based metal compound substituted only with R = CH 3 as a starting material, and through the hydroxylation reaction, R = H (hydroxy group) quantitatively Control the substitution reaction. Thus, 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.
본 발명은 유리 또는 투명한 기재필름 상에, 상기 화학식 1로 표시되는 디티올계 금속 착화합물로 이루어진 근적외선 흡수제와 고분자 수지를 함유한 조성물을 적용하여 필름 또는 패널 형상으로 제조된 광학 필터 및 열적외선 차폐 필터를 제공한다.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.
이때, 상기 디티올계 금속 착화합물 중, 중심금속은 니켈이 바람직하며, 상기 고분자 수지는 아크릴계 수지, 폴리에스테르계 수지, 폴리카보네이트 수지, 우레탄계 수지, 셀룰로오스계 수지, 폴리이소시아네이트, 폴리아릴레이트 및 에폭시계 수지로 이루어진 군에서 선택 사용될 수 있다. At this time, in the dithiol-based metal complex compound, the central metal is preferably nickel, and 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.
본 발명에서 사용되는 투명한 기재필름은 폴리에스테르 또는 폴리카보네이트를 사용하는 것이 바람직하다.As the transparent base film used in the present invention, it is preferable to use polyester or polycarbonate.
본 발명의 근적외선 흡수제 및 고분자 수지로 이루어진 조성물은 그 조성의 함량에 따라, 근적외선 흡수율을 조절할 수 있다. 이에, 바람직하게는 고분자 수지에 대하여, 디티올계 금속 착화합물로 이루어진 근적외선 흡수제 1 내지 3 중량%를 함유하는 것이다. 이때, 근적외선 흡수제의 함량이 1 중량% 미만이면, 근적외선 흡수 능력이 불충분하고, 3 중량%를 초과하면, 가시광선의 투과율이 저하된다.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. Thus, 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.
본 발명의 조성물은 습식 방식에 의해 유리 또는 투명한 기재필름 상에 적용하여 필름 또는 패널 형상으로 제조되며, 이때, 습식방식은 근적외선 흡수제와 고분자 수지를 유기용매에 용해 또는 분산시켜 제조된 코팅액을 유리 또는 투명한 기재필름 상에 도포하여 건조하고, 필름 또는 패널 상으로 제조하는 것으로, 본 발명에 특별히 한정되는 것을 아니나, 롤러코팅법, 스핀코트법, 캐스트법 또는 용융 압출법을 이용한다.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 | coated on a transparent base film, it dries, and it manufactures in a film or a panel, It does not specifically limit to this invention, The roller coating method, a spin coat method, the cast method, or the melt extrusion method is used.
이때, 유기용매는 디클로로메탄, 디클로로에탄(DME), 메틸에틸케톤, 메틸이소부틸케톤, 톨루엔, 에틸렌글리콜모노에틸에테르, 에탄올, 자일렌, 테트라히드로푸란 및 1,4-디옥산로 이루어진 군에서 선택되는 단독 또는 그 혼합형태가 사용될 수 있으며, 본 발명의 디티올계 금속 착화합물이 상기 유기용매에 쉽게 용해됨으로써, 아크릴계 수지, 폴리에스테르계 수지, 폴리카보네이트 수지, 우레탄계 수지, 셀룰로오스계 수지, 폴리이소시아네이트, 폴리아릴레이트 및 에폭시계 수지로 이루어진 군에서 선택되는 고분자 수지와 효율적으로 혼합될 수 있다.At this time, 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.
특히, 본 발명의 디티올계 금속 착화합물은 케톤계와 할로겐계 용매뿐만 아니라, 에틸렌글리콜모노에틸에테르와 에탄올 등의 알코올류에서도 용해도가 현저히 개선된다[표 2].In particular, 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 ].
한편, 용융 압출법을 적용하여 본 발명의 근적외선 차단 필터를 제조하기 위해서는, 본 발명의 근적외선 흡수제를 고분자 수지 중에 용해 또는 혼련시킨 후, 압출 성형에 의해 필름 또는 패널 상으로 성형한다.On the other hand, in order to manufacture the near-infrared cut off filter of this invention by applying the melt-extruding method, the near-infrared absorber of this invention is melt | dissolved or kneaded in a polymeric resin, and is shape | molded on a film or panel by extrusion molding.
또한, 본 발명은 근적외선 흡수제와 고분자 수지를 혼합하여 제조된 마스터 배치를 혼합하여 필름을 제조하는 방법으로 광학 필터 및 열적외선 차폐 필터를 제공할 수 있다.In addition, 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.
이때, 상기 마스터배치의 원료조성물에 있어서, 필요에 따라 산화방지제, 열안정제, 점도조정제, 가소제, 색상개량제, 윤활제, 핵제, 자외선 안정제, 대전방지제, 산화방지제, 바인더 및 촉매 등의 첨가제를 더 사용할 수 있으며, 근적외선 흡수제 1 내지 3 중량%를 유지하는 범위이내에서 첨가제의 함량은 조절될 수 있다.In this case, 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.
상기 근적외선 흡수제 함유 마스터 배치 형태로 적용됨으로써, 열 차폐필름에 근적외선 흡수제의 분산성이 우수하여 염색의 얼룩이 생기지 않고 열 차폐 효율을 향상시킬 수 있다. 따라서, 균일한 품질의 열 차폐필름을 제공할 수 있고, 종래의 염색공정보다 공정이 단순하여 경제적인 효과를 구현할 수 있다. By being applied in the form of the near-infrared absorber-containing master batch, 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.
나아가, 본 발명은 상기 광학 필터 또는 열적외선 차폐 필터를 화상 표시 장치에 이용되며, 특히 디티올계 금속 착화합물로 이루어진 근적외선 흡수제 1 내지 3 중량%와 아크릴계 수지, 폴리에스테르계 수지, 폴리카보네이트 수지, 우레탄계 수지, 셀룰로오스계 수지, 폴리이소시아네이트, 폴리아릴레이트 및 에폭시계 수지로 이루어진 군에서 선택되는 어느 하나의 고분자 수지 98 내지 99 중량%로 이루어진 조성물을 유리 또는 투명한 기재필름 상에 적용하여 제조된 광학 필터 또는 열적외선 차폐 필터가 채용된 플라즈마 디스플레이 패널을 제공한다.Furthermore, 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 Provided is a plasma display panel employing an infrared shielding filter.
이하, 본 발명을 실시예에 의하여 상세히 설명한다.Hereinafter, the present invention will be described in detail by way of examples.
하기 실시예는 본 발명을 예시하는 것일 뿐, 본 발명의 범위가 하기 실시예에 한정되는 것은 아니다. The following examples are merely illustrative of the present invention, but the scope of the present invention is not limited to the following examples.
<실시예 1> <Example 1>
단계 1: 13.5g의 3,4,5-트리메톡시벤자알데하이드를 50㎖ 에탄올에 용해시킨 후, 4.5g의 시안화칼륨을 녹인 20㎖ 증류수를 천천히 첨가하였다. 1시간 동안 환류한 후 냉각한 다음 150㎖의 증류수를 첨가하여 침전물을 형성시킨 후 감압 여과하고 증류수로 여러번 씻어준 후 건조하여 노란색의 목적물 8.2g을 수득하였다. 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.
단계 2: 48g의 2-하이드록시-1,2-비스(3,4,5-트리메톡시페닐)에탄논을 피리딘 150g에 용해시킨 후 50g의 CuSO4ㆍ5H2O을 녹인 100㎖ 증류수를 천천히 첨가하였다. 10시간 동안 환류한 후, 냉각한 다음 500㎖의 증류수를 첨가하여 침전물을 형성시킨 후 감압 여과하고 증류수로 여러번 씻어준 후 건조하여 연한 노란색의 목적물 40g을 수득하였다. 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.
단계 3: 32g의 1,2-비스(3,4,5-트리메톡시페닐)에탄-1,2-디온과 P2S5 18g을 1,4-다이옥산 150㎖에 넣고 교반하였다. 5시간동안 환류한 후 냉각하여 여과하여 여액을 500㎖ 반응기로 옮긴 후 여기에 증류수 100㎖에 11g의 NiCl2ㆍH2O을 녹인 용액을 1시간에 걸쳐 천천히 첨가하였다. 첨가 완료 후 30시간 동안 환류하고 냉각하였다. 냉각된 반응물에 에탄올 100㎖를 투입한 후 감압 여과하고 아세톤으로 여러번 씻어준 후 건조하여 진한 녹색의 목적물 14g을 수득하였다. 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.
단계 4: 14.7g(0.11몰)의 AlCl3을 디클로로메탄 30㎖에서 30분 동안 교반한 후, 단계 3에서 제조된 12-메톡시-Ni-착화합물 10g(0.011몰)을 디클로로메탄 50㎖에 희석해서 천천히 첨가하였다. 실온에서 1시간 30분간 반응 후 아이스 챔버 하에서 증류수 600㎖를 천천히 첨가하면서 교반한 후 형성된 침전을 감압 여과하고 증류수로 여러번 씻어준 후 정제하였다. 이때, 정제방법은 출발물질인 12-메톡시-Ni-착화합물 중, 최대 12개의 메톡시기에서 하이드록시 치환기가 많을수록 메탄올에 용이하게 용해되므로 소량의 메탄올로 세척하여 불순물을 제거하였다. 침전물을 건조한 다음 에틸메틸케톤에 녹여 감압 여과한 용액을 감압 농축 건조하여 진한 녹색의 목적물 2.3g을 수득하였다. 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. At this time, 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.
<실험예 1>Experimental Example 1
1. 물질분석1. Material analysis
상기 실시예 1에서 제조된 목적화합물을 HPLC 및 질량분석기[LC-Mass 분광기,VG BIO TECH, 모델명: VG BIO TECH]를 이용하여 분석한 결과를 하기 표 1 및 표 2에 기재하였다. 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 .
상기 결과로부터, 실시예 1에서 제조된 목적화합물은 하이드록시기(R=H)가 1 내지 5개가 치환된 화합물이 혼재되어 있음을 확인하였다.From the above results, it was confirmed that the target compound prepared in Example 1 contains a compound in which 1 to 5 hydroxy groups (R = H) are substituted.
또한, 열중량분석기(TGA)를 이용하여 분해온도 281.26℃에서 측정한 결과, mp 258.71, 320.59 및 342.82℃ 피크를 확인하였으며, 시차주차열량계(DSC)를 이용한 결과, 3개 이상의 물질이 혼재되어 있음을 확인하였다. In addition, using a thermogravimetric analyzer (TGA) at the decomposition temperature of 281.26 ℃, mp 258.71, 320.59 and 342.82 ℃ peaks were confirmed, using a differential parking calorimeter (DSC), three or more substances are mixed It was confirmed.
또한, 상기 화합물을 메틸에틸케톤에 용해시킨 후 UV 분광기를 통해 측정한 결과, 최대흡수파장(λmax)이 960nm(ε= 2.9×104 L/cmㆍg)로 관찰됨[도 1]에 따라, 플라즈마 디스플레이 패널(PDP)용도에 적합한 근적외선 흡수제로 사용할 수 있다.In addition, after dissolving the compound in methyl ethyl ketone measured by UV spectroscopy, the maximum absorption wavelength (λ max ) is observed at 960nm (ε = 2.9 × 10 4 L / cm · g) [ Fig. 1 ] Therefore, it can be used as a near infrared absorber suitable for plasma display panel (PDP) use.
2. AlCl2. AlCl
33
당량에 따른 파장변화 Wavelength change according to equivalent weight
상기 실시예 1의 단계 4에서 사용된 AlCl3 당량을 하기 표 3과 같이 변화하여 제조된 화합물을 메틸에틸케톤 용매 조건하에서 UV 분광기를 이용하여 최대흡수파장(λmax)을 측정하였다. The maximum absorption wavelength (λ max ) 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.
그 측정결과, 상기 실시예 1의 단계 3에서 제조된 12개의 메톡시로 치환된 Ni 착화합물(비교예 1)은 최대흡수파장(λmax)이 930nm을 보인 반면에, 단계 4에서 AlCl3의 당량에 따라, 하이드록시(R=H) 치환기수가 증가하고, 최대흡수파장(λmax)이 정량적으로 장파장이동함을 확인하였다. As a result, the 12 methoxy-substituted Ni complex compound prepared in step 3 of Example 1 (Comparative Example 1) showed a maximum absorption wavelength (λ max ) of 930 nm, whereas the equivalent of AlCl 3 in step 4 As a result, it was confirmed that the number of hydroxy (R = H) substituents increased and the maximum absorption wavelength (λ max ) shifted quantitatively.
반면에, AlCl3 과량(10당량 이상)을 사용할 때, 니켈 착화합물이 깨지는 부산물이 과량 생산되어 생산성이 떨어지면, 분리 정제가 어렵다.On the other hand, when an excess of AlCl 3 (10 equivalents or more) is used, if the byproducts in which the nickel complex compound is broken are excessively produced and the productivity decreases, separation and purification are difficult.
3. AlCl3. AlCl
33
당량에 따른 용해도 변화 Change in solubility with equivalent weight
상기 실시예 1의 단계 4에서 사용된 AlCl3 당량을 하기 표 3과 같이 변화하여 제조된 화합물을 메틸에틸케톤 용매 조건 하에서 UV 분광기를 이용하여 용해도를 측정하여 그 결과를 표 3에 기재하였다.The solubility of the compound prepared by changing the AlCl 3 equivalent used in Step 4 of Example 1 as shown in Table 3 was measured using a UV spectrometer under methyl ethyl ketone solvent conditions, and the results are shown in Table 3.
그 결과, AlCl3 당량이 높을수록 하이드록시(R=H) 치환기수가 증가하고, 그에 따라 용해도가 현저히 증가한다. 다만, 10 당량 이상 사용 시, 니켈금속이 깨어지는 비율이 더 높아진다.As a result, the higher the AlCl 3 equivalent, the more the number of hydroxy (R = H) substituents increases, so that the solubility significantly increases. However, when more than 10 equivalents are used, the rate at which nickel metal is broken is higher.
4. AlCl4. AlCl
33
당량에 따른 수율 변화 Yield change according to equivalent weight
상기 실시예 1의 단계 4에서 출발물질인 12개의 메톡시기가 치환된 니켈 착화합물 100g 반응을 전제 하에, AlCl3 당량에 따른 수율을 조사하였다. 그 결과를 하기 표 4에 기재하였다. The yield of AlCl 3 equivalent was investigated under the premise of 100 g reaction of nickel complex substituted with 12 methoxy groups as starting materials in Step 4 of Example 1. The results are shown in Table 4 below.
5. 용해성 측정5. Solubility measurement
상기 실시예 1의 디티올계 니켈 착화합물을 에탄올, 메틸에틸케톤, 에틸아세테이트 및 톨루엔 용매 100g에 대한 각각의 용해성(g/g)을 측정하였다. 그 결과를 표 5에 기재하였다. The solubility (g / g) of the dithiol-based nickel complex of Example 1 in 100 g of ethanol, methyl ethyl ketone, ethyl acetate and toluene solvent was measured. The results are shown in Table 5 .
상기 표 5의 결과로부터, 실시예 1에서 제조된 디티올계 니켈 착화합물은 메톡기로 치환된 디티올계 니켈 착화합물보다 케톤계 및 할로겐계 용매뿐만 아니라, 에탄올 등의 알코올류에서도 용해도가 월등히 개선되었다. From the results of Table 5, 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.
<실시예 4> <Example 4>
단계 1: 40g의 p-아니사알데하이드(anisaldehye)를 40㎖ 에탄올에 용해시킨 후, 22g의 시안화칼륨을 녹인 20㎖ 증류수를 천천히 첨가하였다. 1시간 동안 환류한 후 냉각한 다음 350㎖의 증류수 첨가하여 침전물을 형성시킨 후 감압 여과하고, 침전물을 40㎖ 에탄올로 20분간 교반한 후 여과하고 에탄올로 여러번 씻어준 후 건조하여 연한 노란색의 목적물 28g을 수득하였다. 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.
단계 2: 19g의 2-하이드록시-1,2-bis(4-메톡시페닐)에탄논과 P2S5 14g을 1,4-다이옥산 100㎖에 넣고 교반하였다. 28시간동안 환류한 후 냉각하고 여과하여 여액을 500㎖ 반응기로 옮긴 후 여기에 증류수 30㎖에 9g의 NiCl2ㆍH2O을 녹인 용액을 2시간에 걸쳐 천천히 첨가한다. 첨가 완료 후 30시간 동안 환류하고 냉각하였다. 냉각된 반응물에 아세톤 200㎖를 투입한 후 감압 여과하고 아세톤으로 여러번 씻어준 후 건조하여 진한 녹색의 목적물 12g을 수득하였다. 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.
단계 3: 22g의 AlCl3을 디클로로메탄 50㎖에서 30분 동안 교반한 후 12-메톡시-Ni-착화합물 21g을 디클로로메탄 60㎖에 희석해서 천천히 첨가하였다. 실온에서 30분간 반응 후 아이스 챔버 하에서 증류수 200㎖를 천천히 첨가한 후 형성된 침전을 감압 여과하고 증류수로 여러번 씻어준 후 소량의 메탄올로 세척하였다. 건조하여 진한 녹색의 목적물 19g을 수득하였다. 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.
<실시예 5> Example 5
단계 1: 50g의 벤자알데하이드를 80㎖ 에탄올에 용해시킨 후 8g의 시안화나트륨을 녹인 70㎖ 증류수를 천천히 첨가하였다. 3시간 동안 환류한 후 냉각하여 형성된 침전물을 감압 여과하고 침전물을 에탄올로 여러번 씻어준 후 건조하여 연한 노란색의 목적물 35g을 수득하였다. 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.
단계 2: 2-하이드록시-1,2-디페닐에탄논 8.6g과 2-하이드록시-1,2-bis(4-메톡시페닐)에탄논 11.8g을 P2S5 18g와 함께 1,4-다이옥산 100㎖에 넣고 교반하였다. 4시간동안 환류한 후 냉각하고 여과하여 여액을 500㎖ 반응기로 옮긴 후 아이스 배스를 사용하여 0℃로 낮춘 후, 여기에 증류수 30㎖에 10g의 NiCl2ㆍH2O을 녹인 용액을 1시간에 걸쳐 천천히 첨가하였다. 첨가 완료 후 28시간 동안 환류하고 냉각하였다. 냉각된 반응물에 아세톤 50㎖를 투입한 후 감압 여과하고 아세톤으로 여러번 씻어준 후 건조하여 진한 녹색의 목적물 16g을 수득하였다. 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.
단계 3: 20g의 AlCl3을 디클로로메탄 60㎖에서 30분 동안 교반한 후 12-메톡시-Ni-착화합물 30g을 디클로로메탄 50㎖에 희석해서 천천히 첨가하였다. 실온에서 30분간 반응 후 아이스 배스 하에서 증류수 200㎖를 천천히 첨가한 후 형성된 침전을 감압 여과하고 증류수로 여러번 씻어준 후 소량의 메탄올로 세척하였다. 건조하여 진한 녹색의 목적물 17g을 수득하였다. 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.
<실시예 6><Example 6>
상기 실시예 1의 단계 3에서 제조된 12-메톡시-Ni-착화합물 10g(0.011몰)을 디클로로메탄 50㎖에 희석하여 준비하고, 16.1g(0.11몰)의 ZnCl2를 디클로로메탄 30㎖에서 30분 동안 교반하여 준비한 용액에 천천히 첨가하였다. 6시간동안 환류반응한 후 아이스 챔버 하에서 증류수 600㎖를 천천히 첨가하면서 교반한 후 형성된 침전을 감압 여과하고 증류수로 여러번 씻어준 후 정제하였다. 이때, 정제방법은 출발물질인 12-메톡시-Ni-착화합물 중, 최대 12개의 메톡시기에서 하이드록시 치환기가 많을수록 메탄올에 용이하게 용해되므로 소량의 메탄올로 세척하여 불순물을 제거하였다. 침전물을 건조한 다음 에틸메틸케톤에 녹여 감압 여과한 용액을 감압 농축 건조하여 진한 녹색의 목적물 4.8g을 수득하였다. 10 g (0.011 mol) of 12-methoxy-Ni-complex compound prepared in step 3 of Example 1 was prepared by diluting in 50 ml of dichloromethane, and 16.1 g (0.11 mol) of ZnCl 2 was dissolved in 30 ml of dichloromethane. It was slowly added to the prepared solution by stirring for minutes. After refluxing for 6 hours and stirring while slowly adding 600ml of distilled water under an ice chamber, the precipitate formed was filtered under reduced pressure, washed several times with distilled water and purified. At this time, 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.
<실시예 7> <Example 7>
ZnCl2를 24.12g(0.165몰, 15eq)을 사용하는 것을 제외하고는, 상기 실시예 6과 동일하게 수행하였다. 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.
상기에서 살펴본 바와 같이, 본 발명은 As described above, the present invention
첫째, 케톤계 및 할로겐계 용매뿐만 아니라, 알코올류의 유기용매에서 용해도가 개선된 신규한 디티올계 금속 착화합물로 이루어진 근적외선 흡수제를 제공하였다. First, there was provided 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.
둘째, 용해성이 개선된 근적외선 흡수제는 고분자 수지등의 유기재료와의 효율적인 혼합이 실현됨에 따라, 상기 디티올계 금속 착화합물의 우수한 근적외선 흡수성능이 충분히 발휘되어 장시간에 걸쳐 근적외선 흡수 능력이 저하되지 않는 광학 필터 또는 열적외선 차폐 필터를 제공할 수 있다.Second, as the near-infrared absorbent with improved solubility is realized with efficient mixing with organic materials such as polymer resins, 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. Or a thermal infrared shielding filter can be provided.
셋째, 본 발명의 근적외선 흡수제가 제조공정 단계 또는 별도의 마스터 배치 형태로 제공하여 제조함으로써, 종래 코팅방식의 필름보다 선택적 근적외선 차폐효과가 우수하고, 고온 안정성이 우수한 근적외선 흡수제를 이를 이용한 광학 필터 특히, 열적외선 차폐 필터에 유용하게 활용될 수 있다.Third, by providing the near-infrared absorber of the present invention in the manufacturing process step or in the form of a separate master batch, an optical filter using the near-infrared absorber excellent in selective near-infrared shielding effect and excellent high-temperature stability than the conventional coating film, in particular, It can be usefully used in thermal infrared shielding filter.
이상에서 본 발명은 기재된 구체예에 대해서만 상세히 설명되었지만, 본 발명의 범위 내에서 다양한 변형 및 수정이 가능함은 당업자에게 명백한 것이며, 이러한 변형 및 수정이 첨부된 특허 청구 범위에 속함은 당연한 것이다.While the invention has been described in detail only with respect to the described embodiments, it will be apparent to those skilled in the art that various modifications and variations are possible within the scope of the invention, and such modifications and variations belong to the appended claims.
Claims (14)
- 하기 화학식 1로 표시되는 용해도가 개선된 디티올계 금속 착화합물로 이루어진 것을 특징으로 하는 근적외선 흡수제.Near-infrared absorber, characterized in that made of a dithiol-based metal complex with improved solubility represented by the formula (1).화학식 1Formula 1
(상기에서, M은 니켈, 팔라듐 또는 백금이며, R은 수소, C1∼C6의 알킬기 또는 C1∼C6의 에테르기이고, X는 수소 또는 할로겐이고, m=1∼3이고, o, p, q, r, o', p', q' 및 r'는 0∼3이며, [o-o'], [p-p'], [q-q'] 및 [r-r']는 각각 0∼3이며 양의 정수이다.)(Wherein, 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.) - 제1항에 있어서, 상기 디티올계 금속 착화합물이 하이드록시기(R=H)가 1 내지 5개 치환된 것을 특징으로 하는 것을 특징으로 하는 상기 근적외선 흡수제.The near-infrared absorber according to claim 1, wherein the dithiol-based metal complex is substituted with 1 to 5 hydroxyl groups (R = H).
- 제1항에 있어서, 상기 디티올계 금속 착화합물이 디클로로메탄, 디클로로에탄, 메틸에틸케톤, 메틸이소부틸케톤, 톨루엔, 에틸렌글리콜모노에틸에테르, 에탄올, 자일렌, 테트라히드로푸란 및 1,4-디옥산로 이루어진 군에서 선택되는 어느 하나의 유기용매에 대하여, 0.05 내지 7g/g의 용해성질을 가지는 것을 특징으로 하는 상기 근적외선 흡수제.The dithiol-based metal complex is a dichloromethane, dichloroethane, methyl ethyl ketone, methyl isobutyl ketone, toluene, ethylene glycol monoethyl ether, ethanol, xylene, tetrahydrofuran and 1,4-dioxane The near-infrared absorbent, characterized in that it has a solubility of 0.05 to 7g / g with respect to any one organic solvent selected from the group consisting of.
- 제1항에 있어서, 상기 디티올계 금속 착화합물이 930 내지 960 nm 파장영역의 근적외선을 선택적으로 흡수하는 것을 특징으로 하는 상기 근적외선 흡수제.The near-infrared absorber according to claim 1, wherein the dithiol-based metal complex selectively absorbs near infrared rays in a wavelength region of 930 to 960 nm.
- 제1항에 있어서, 상기 디티올계 금속 착화합물이 하기 화학식 2 또는 화학식 3으로 표시되는 디티올계 니켈 착화합물이고, R=H가 2 내지 5개 함유된 것을 특징으로 하는 상기 근적외선 흡수제.The near-infrared absorber according to claim 1, wherein the dithiol-based metal complex is a dithiol-based nickel complex represented by the following Formula (2) or (3), and contains 2 to 5 R = H.화학식 2Formula 2
화학식 3Formula 3
(상기에서, R은 수소, C1∼C6의 알킬기또는 C1∼C6의 에테르기이다.)(Wherein, R is an ether group of hydrogen, C 1 ~C 6 alkyl group or a C 1 ~C 6 in.) - 제1항에 있어서, 상기 디티올계 금속 착화합물이 하기 화학식 4 내지 화학식 6으로 표시되는 대칭형 디티올계 니켈 착화합물 중에서 선택되는 어느 하나이고, R=H가 2 내지 5개 함유된 것을 특징으로 하는 상기 근적외선 흡수제.The near-infrared absorber of claim 1, wherein the dithiol-based metal complex is any one selected from symmetrical dithiol-based nickel complexes represented by the following Chemical Formulas 4 to 6, wherein R = H is contained in 2 to 5. .화학식 4Formula 4
화학식 5Formula 5
화학식 6Formula 6
(상기에서, R은 수소, C1∼C6의 알킬기 또는 C1∼C6의 에테르기이다.)(Wherein, R is an ether group of hydrogen, C 1 ~C 6 alkyl group or a C 1 ~C 6 in.) - 제1항에 있어서, 상기 디티올계 금속 착화합물이 하기 화학식 7 내지 화학식 9로 표시되는 비대칭형 디티올계 니켈 착화합물 중에서 선택되는 어느 하나이고, R=H가 2 내지 5개 함유된 것을 특징으로 하는 상기 근적외선 흡수제.The near-infrared ray of claim 1, wherein the dithiol-based metal complex is any one selected from asymmetric dithiol-based nickel complexes represented by the following Chemical Formulas 7 to 9. Absorbent.화학식 7Formula 7
화학식 8Formula 8화학식 9Formula 9
(상기에서, R은 수소, C1∼C6의 알킬기또는 C1∼C6의 에테르기이다.)(Wherein, R is an ether group of hydrogen, C 1 ~C 6 alkyl group or a C 1 ~C 6 in.) - 하기 화학식 10으로 표시되는 2-하이드록시기를 가진 화합물을 산화 반응하여, 화학식 11로 표시되는 디온 화합물을 합성하는 제1단계;A first step of oxidizing a compound having a 2-hydroxy group represented by Formula 10 to synthesize a dione compound represented by Formula 11;화학식 11로 표시되는 디온 화합물과 금속염화물과 반응하여, 화학식 12로 표시되는 디티올계 금속 착화합물을 제조하는 제2단계; 및 A second step of preparing a dithiol-based metal complex compound represented by Chemical Formula 12 by reacting with a dione compound represented by Chemical Formula 11 and a metal chloride; And상기 화학식 12로 표시되는 디티올계 금속 착화합물 함유 유기용액에 AlCl3, ZnCl2 및 BF3로 이루어진 군에서 선택되는 적어도 하나의 루이스 산을 첨가하여 부분적으로 하이드록실레이션 반응을 제어하여, 화학식 1로 표시되는 디티올계 금속 착화합물을 제조하는 제3단계로 이루어지는 것을 특징으로 하는 화학식 1로 표시되는 디티올계 금속 착화합물의 제조방법.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 Method for producing a dithiol-based metal complex represented by the formula (1), characterized in that consisting of a third step of producing a dithiol-based metal complex.반응식 1Scheme 1
(상기에서, M은 니켈, 팔라듐 또는 백금이며, R은 수소, C1∼C6의 알킬기 또는 C1∼C6의 에테르기이고, X는 수소 또는 할로겐이고, m=1∼3이고, o, p, q, r, o', p', q' 및 r'는 0∼3이며, [o-o'], [p-p'], [q-q'] 및 [r-r']는 각각 0∼3이며 양의 정수이다.)(Wherein, 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.) - 제8항에 있어서, 상기 제3단계에서 AlCl3, ZnCl2 및 BF3로 이루어진 군에서 선택되는 적어도 하나의 루이스 산이 디티올계 금속 착화합물에 대하여, 2 내지 15몰%로 첨가되는 것을 특징으로 하는 상기 디티올계 금속 착화합물의 제조방법.The method according to claim 8, wherein in the third step, at least one Lewis acid selected from the group consisting of AlCl 3 , ZnCl 2 and BF 3 is added in an amount of 2 to 15 mol% based on the dithiol metal complex. Method for producing a dithiol-based metal complex.
- 제8항에 있어서, 상기 디티올계 금속 착화합물이 하이드록시기 치환기가 1 내지 5개인 것을 특징으로 하는 상기 디티올계 금속 착화합물의 제조방법.The method for producing the dithiol-based metal complex according to claim 8, wherein the dithiol-based metal complex has 1 to 5 hydroxyl group substituents.
- 유리 또는 투명한 기재필름 상에,On glass or transparent base film,제1항 내지 제7항 중 어느 한 항의 디티올계 금속 착화합물로 이루어진 근적외선 흡수제와 고분자 수지를 함유한 조성물을 적용하여 필름 또는 패널 형상으로 제조된 것을 특징으로 하는 열적외선 차폐 필터.A thermal infrared shielding filter, which is manufactured in the form of a film or a panel by applying a composition containing a near-infrared absorbent and a polymer resin, wherein the dithiol-based metal complex of any one of claims 1 to 7 is used.
- 제11항에 있어서, 상기 디티올계 금속 착화합물에 있어서, 중심금속이 니켈인 것을 특징으로 하는 상기 열적외선 차폐 필터.12. The thermal infrared shielding filter according to claim 11, wherein in the dithiol-based metal complex, the central metal is nickel.
- 제11항에 있어서, 상기 조성물이 근적외선 흡수제 및 고분자 수지로 이루어지되, 고분자 수지에 대하여, 근적외선 흡수제 1 내지 3 중량%를 함유하는 것을 특징으로 하는 상기 열적외선 차폐 필터.The thermal infrared shielding filter according to claim 11, wherein the composition is composed of a near infrared absorber and a polymer resin, and contains 1 to 3 wt% of a near infrared absorber with respect to the polymer resin.
- 제1항 내지 제7항 중 어느 한 항의 디티올계 금속 착화합물로 이루어진 근적외선 흡수제 1 내지 3 중량% 및 1-3 weight% of near-infrared absorbers which consist of the dithiol type metal complex of any one of Claims 1-7, and아크릴계 수지, 폴리에스테르계 수지, 폴리카보네이트 수지, 우레탄계 수지, 셀룰로오스계 수지, 폴리이소시아네이트, 폴리아릴레이트 및 에폭시계 수지로 이루어진 군에서 선택되는 어느 하나의 고분자 수지 98 내지 99 중량%로 이루어진 조성물을 유리 또는 투명한 기재필름 상에 적용하여 제조된 열적외선 차폐 필터가 채용된 것을 특징으로 하는 플라즈마 디스플레이 패널.Glass composition comprising 98 to 99% by weight of any one polymer resin selected from the group consisting of acrylic resin, polyester resin, polycarbonate resin, urethane resin, cellulose resin, polyisocyanate, polyarylate and epoxy resin Or a heat infrared ray shielding filter manufactured by applying on a transparent base film.
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| KR10-2008-0105189 | 2008-10-27 | ||
| KR1020080105189A KR20100046373A (en) | 2008-10-27 | 2008-10-27 | Near infrared ray absorber containing dithiol metal complex, manufacturing method of dithiol metal complex, optical filter comprising them and sun protection filter containing near infrared ray absorber |
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| WO2010050720A2 true WO2010050720A2 (en) | 2010-05-06 |
| WO2010050720A3 WO2010050720A3 (en) | 2010-08-05 |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103502222A (en) * | 2011-05-06 | 2014-01-08 | 巴斯夫欧洲公司 | Chromophores with perfluoroalkyl substituents |
| CN104177238A (en) * | 2014-07-25 | 2014-12-03 | 山东大学 | Method for synthesizing 3, 4-di(3, 4, 5-trimethoxy phenyl)-2, 5-diphenyl cyclopentadienone |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6217796B1 (en) * | 1998-11-17 | 2001-04-17 | Nisshinbo Industries, Inc. | Near infrared absorption composition |
| JP2001138623A (en) * | 1999-11-12 | 2001-05-22 | Canon Inc | Medium to be recorded |
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| JPH1112425A (en) * | 1997-06-23 | 1999-01-19 | Mitsubishi Rayon Co Ltd | Optical filter for plasma display |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6217796B1 (en) * | 1998-11-17 | 2001-04-17 | Nisshinbo Industries, Inc. | Near infrared absorption composition |
| JP2001138623A (en) * | 1999-11-12 | 2001-05-22 | Canon Inc | Medium to be recorded |
Non-Patent Citations (1)
| Title |
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| CHO; JIAN-YANG ET AL.: 'High electron mobility in nickel bis(dithiolene) complexes' JOURNAL OF MATERIALS CHEMISTRY vol. 17, no. 25, 2007, pages 2642 - 2647 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103502222A (en) * | 2011-05-06 | 2014-01-08 | 巴斯夫欧洲公司 | Chromophores with perfluoroalkyl substituents |
| CN103502222B (en) * | 2011-05-06 | 2016-08-17 | 巴斯夫欧洲公司 | There is the chromophore of perfluoroalkyl substituents |
| CN104177238A (en) * | 2014-07-25 | 2014-12-03 | 山东大学 | Method for synthesizing 3, 4-di(3, 4, 5-trimethoxy phenyl)-2, 5-diphenyl cyclopentadienone |
| CN104177238B (en) * | 2014-07-25 | 2016-05-25 | 山东大学 | Synthetic 3,4-bis-(3,4,5-trimethoxyphenyl)-2, the method for 5-diphenyl cyclopentadienone |
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| WO2010050720A3 (en) | 2010-08-05 |
| KR20100046373A (en) | 2010-05-07 |
| WO2010050720A4 (en) | 2010-09-30 |
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