WO2010050720A4 - 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
- WO2010050720A4 WO2010050720A4 PCT/KR2009/006216 KR2009006216W WO2010050720A4 WO 2010050720 A4 WO2010050720 A4 WO 2010050720A4 KR 2009006216 W KR2009006216 W KR 2009006216W WO 2010050720 A4 WO2010050720 A4 WO 2010050720A4
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- WIPO (PCT)
- Prior art keywords
- dithiol
- metal complex
- near infrared
- based metal
- formula
- Prior art date
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- 239000002250 absorbent Substances 0.000 title claims abstract description 26
- 230000002745 absorbent Effects 0.000 title claims abstract description 26
- -1 dithiol metal complex Chemical class 0.000 title claims abstract description 19
- 238000000034 method Methods 0.000 title claims abstract description 18
- 230000003287 optical effect Effects 0.000 title abstract description 22
- 239000002952 polymeric resin Substances 0.000 claims abstract description 20
- 229920003002 synthetic resin Polymers 0.000 claims abstract description 20
- 239000003960 organic solvent Substances 0.000 claims abstract description 13
- 238000004519 manufacturing process Methods 0.000 claims abstract description 11
- 150000004662 dithiols Chemical class 0.000 claims description 74
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 58
- 150000004696 coordination complex Chemical class 0.000 claims description 41
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical group ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 36
- 239000006096 absorbing agent Substances 0.000 claims description 34
- 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
- 229910052759 nickel Inorganic materials 0.000 claims description 28
- 150000001875 compounds Chemical class 0.000 claims description 19
- 239000000203 mixture Substances 0.000 claims description 19
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 16
- 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
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 11
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 10
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- 150000002815 nickel Chemical class 0.000 claims description 10
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 10
- 229910052751 metal Inorganic materials 0.000 claims description 9
- 239000002184 metal Substances 0.000 claims description 9
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- 238000005805 hydroxylation reaction Methods 0.000 claims description 6
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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
- 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
- 239000008096 xylene Substances 0.000 claims description 5
- 229920002803 thermoplastic polyurethane Polymers 0.000 claims description 4
- 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 claims description 3
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- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 18
- 239000002244 precipitate Substances 0.000 description 13
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 10
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- 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
- OPHQOIGEOHXOGX-UHFFFAOYSA-N 3,4,5-trimethoxybenzaldehyde Chemical compound COC1=CC(C=O)=CC(OC)=C1OC OPHQOIGEOHXOGX-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
- 239000011230 binding agent Substances 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical compound ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 description 2
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- ZRSNZINYAWTAHE-UHFFFAOYSA-N p-methoxybenzaldehyde Chemical compound COC1=CC=C(C=O)C=C1 ZRSNZINYAWTAHE-UHFFFAOYSA-N 0.000 description 2
- 229920000647 polyepoxide Polymers 0.000 description 2
- 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
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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
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
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- 239000002667 nucleating agent Substances 0.000 description 1
- 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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- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
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- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 125000003548 sec-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
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- FWQHRZXEQNUCSY-UHFFFAOYSA-N tert-butyl N-[2-(ethoxycarbonylamino)-5-[(4-fluorophenyl)methyl-prop-2-ynylamino]phenyl]carbamate Chemical compound CCOC(=O)NC1=C(C=C(C=C1)N(CC#C)CC2=CC=C(C=C2)F)NC(=O)OC(C)(C)C FWQHRZXEQNUCSY-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 made of a dithiol-based metal complex, a method for producing the dithiol-based metal complex, an optical filter containing the same and an infrared ray shielding filter. More particularly, By providing a near infrared ray absorbent made of a novel ditol-based nickel complex, it is possible to efficiently mix with an organic material such as a polymer resin mixed in the production of an optical filter, thereby exhibiting excellent near infrared absorption performance of the ditol- Which does not deteriorate the near infrared absorbing ability.
- These image display devices display a color image by a combination of three primary colors of red, blue, and green light.
- light of unnecessary wavelength is emitted from the display device, and there is a problem in malfunction of the peripheral electronic device and high quality of the display image.
- the plasma display also emits near-infrared rays or electromagnetic waves in the 800 to 1000 nm range. Since the wavelength range of the near-infrared rays overlaps with the wavelength range used in near-infrared communication or remote controllers of other electronic apparatuses, do.
- An optical filter containing a specific light absorbing agent is used for the above problem.
- an optical filter for absorbing near infrared rays is disclosed in Japanese Patent Application Laid-Open Nos. 9-230134 and 11-73115
- An optical filter using an aromatic dithiol nickel compound as a light absorber has been reported in JP-A-11-12425, JP-A 2000-206322, and JP-A 2000-212546.
- the near infrared absorber for optical filters it is required to selectively absorb wavelength light in the near infrared region and transmit light in the visible light region.
- the conventional light absorbing agent absorbs the visible light region and is not suitable as the light absorbing agent for the optical filter.
- dithiol-based nickel complexes represented by the following formula (13) are typical examples of those having excellent performance as a near-infrared absorbing agent by effectively absorbing near-infrared rays in a wavelength region of 800 to 900 nm.
- the dithiol-based nickel complex is useful as an antioxidant such as polyolefins, an anti-discoloration agent such as an anti-fouling agent or a color photograph since it has a good inactivating action against singlet oxygen in addition to its use as a near infrared absorber. Furthermore, the dithiol-based nickel complexes have excellent properties applicable to various fields such that they can be usefully utilized as catalysts or liquid crystal materials for photodecomposition and dehydration of water.
- the organic material such as a binder resin, a plastic, an ionic coating or an organic solvent should be dissolved or contained in an optimal amount uniformly.
- the dithiol-based nickel complex has a low solubility with respect to an organic material, so that it can not contain a sufficient amount in an organic material, so that the performance can not be sufficiently exhibited.
- the present inventors have made efforts to solve the problems of the conventional light absorbents for optical filters. As a result, they have found that a novel dithiol-based nickel complex compound having improved solubility in an organic material and absorbing only near- The present inventors have completed the present invention by producing a novel near infrared absorbing dye in which the performance of the dithiol-based nickel complex is sufficiently exhibited and the near infrared absorbing ability is not deteriorated for a long time, and an optical filter and a thermal infrared ray shielding filter using the same.
- Another object of the present invention is to provide a novel method for preparing a dithiol-based nickel complex.
- Still another object of the present invention is to provide an optical filter, a thermal infrared ray shielding filter, and a plasma display panel employing the infrared filter, which contain a near infrared absorbent composed of the dithiol-based nickel complex.
- the present invention provides a near infrared ray absorbent made of a dithiol-based nickel complex having improved solubility in an organic material.
- the present invention provides a near infrared ray absorbent comprising 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
- X is hydrogen or halogen
- m 1 ⁇ 3
- o q-r ', p', q 'and r' are 0 to 3
- [o-o '], [p- ] 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 benzene ring is substituted with 1 to 5 hydroxy groups to improve solubility.
- the metal element is preferably nickel.
- the dithiol-based metal complexes of the present invention can be obtained by reacting a compound represented by the general formula (1) in a group consisting of dichloromethane, dichloroethane, methyl ethyl ketone, methyl isobutyl ketone, toluene, ethylene glycol monoethyl ether, ethanol, xylene, tetrahydrofuran and 1,4- And exhibit solubility-improving effects on any one of the selected organic solvents.
- the present invention also provides a process for preparing a dithiol-based metal complex having improved solubility.
- M is a nickel, palladium or platinum
- R is an ether group of hydrogen
- X is hydrogen or halogen
- m 1 ⁇ 3
- o q-r ', p', q 'and r' are 0 to 3
- [o-o '], [p- ] 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 is used in an amount of 2 to 15 mol%, more preferably 2 to 10 mol %
- a partial hydroxylation reaction to prepare a symmetrical or asymmetric dithiol-based metal complex.
- the dithiol-based metal complex preferably has 2 to 5 hydroxyl group substituents, and the central metal is preferably nickel.
- the present invention also relates to an optical filter manufactured in the form of a film or a panel by applying a composition containing a near infrared absorber and a polymer resin composed of a dithiol-based metal complex represented by Chemical Formula 1 on a glass or transparent base film, Filter.
- the central metal is preferably nickel
- the polymer resin may be at least one selected from the group consisting of an acrylic resin, a polyester resin, a polycarbonate resin, a urethane resin, a cellulose resin, a polyisocyanate, a polyarylate, May be used.
- the composition further comprises a near infrared absorbing agent and a polymer resin, and the polymer resin contains 1 to 3% by weight of a near infrared absorbing agent.
- the present invention is characterized in that the optical filter or the thermal infrared ray shielding filter is used for an image display device, and in particular, 1 to 3% by weight of a near infrared absorbent composed of a dithiol-based metal complex and an acrylic resin, a polyester resin, a polycarbonate resin, , 98 to 99% by weight of a polymeric resin selected from the group consisting of an acrylic resin, a polyester resin, a cellulose resin, a polyisocyanate, a polyarylate, and an epoxy resin is applied on a glass or transparent base film, A plasma display panel employing an infrared shielding filter is provided.
- a near infrared ray absorbent made of a dithiol-based metal complex having a small absorption in the visible ray region, selectively absorbing the wavelength light in the near infrared ray region and improving the solubility in an organic material
- an optical filter, a thermal infrared ray shielding filter and a plasma display panel employing the same that do not deteriorate the near infrared ray absorption ability for a long time by containing a near infrared ray absorbent.
- 1 is an absorption spectrum of a dithiol-based nickel complex of the present invention using an ultraviolet spectrometer.
- the present invention provides a near infrared ray absorbent comprising a dithiol-based metal complex represented by Chemical Formula (1), which is a conventional dithiol-based metal complex compound known as a near infrared absorber to solve the problem of low solubility in an organic solvent.
- a dithiol-based metal complex represented by Chemical Formula (1) which is a conventional dithiol-based metal complex compound known as a near infrared absorber to solve the problem of low solubility in an organic solvent.
- M is a nickel, palladium or platinum
- R is an ether group of hydrogen
- X is hydrogen or halogen
- m 1 ⁇ 3
- o q-r ', p', q 'and r' are 0 to 3
- [o-o '], [p- ] Are 0 to 3, respectively, and are positive integers.
- the alkyl group of R is preferably a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec- an n-pentyl group, an iso-pentyl group, a sec-pentyl group, a tert-pentyl group and an n-hexyl group, and more preferably the alkyl group of R is a methyl group or an ethyl group .
- the solubility improvement in the present invention means that the dithiol-based metal complexes of the present invention are improved in solubility not only in ketone-based solvents and halogen-based solvents but also in alcohols such as ethylene glycol monoethyl ether and ethanol. More specifically, it is preferable to use a solvent 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- And has a solubility in one organic solvent.
- the dithiol-based metal complex of the present invention selectively absorbs near-infrared rays in the wavelength region 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.
- the near infrared absorber according to the third preferred embodiment of the present invention contains a dithiol-based nickel complex selected from the asymmetric dithiol-based nickel complexes represented by the following general formulas (7) to (9) will be.
- 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 preparing a dithiol-based metal complex contained in the near infrared absorber and having improved solubility.
- the production method of the present invention is characterized in that at least one Lewis acid selected from the group consisting of AlCl 3 , ZnCl 2 and BF 3 is added to the dithiol-based metal complex in an amount of 2 to 15 mol%, more preferably 2 to 10 mol % ≪ / RTI > to effect a partial hydroxylation reaction.
- at least one Lewis acid selected from the group consisting of AlCl 3 , ZnCl 2 and BF 3 is added to the dithiol-based metal complex in an amount of 2 to 15 mol%, more preferably 2 to 10 mol % ≪ / RTI > to effect a partial hydroxylation reaction.
- AlCl 3 it is preferably 2 to 10 mol%
- ZnCl 2 when ZnCl 2 is used, a change in the desired absorption wavelength, a change in solubility and yield can be obtained by 2 to 15 mol%.
- the dithiol-based metal complex of the present invention exhibits excellent solubility in an organic solvent when 1 to 5, more preferably 2 to 5, hydroxyl group substituents are present.
- the solubility is excellent, but the long-wavelength shift is remarkable, which is outside the desired wavelength range, and it is difficult to separate and purify the desired nickel complex.
- the organic solvent may be 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- And exhibits excellent solubility in insoluble which is hardly dissolved in the prior art.
- the present invention relates to an optical filter and a thermal infrared ray shielding filter manufactured in the form of a film or a panel by applying a composition containing a near infrared absorber made of a dithiol-based metal complex represented by the above formula (1) and a polymer resin on a glass or transparent base film to provide.
- the central metal is preferably nickel
- the polymer resin may be at least one selected from the group consisting of an acrylic resin, a polyester resin, a polycarbonate resin, a urethane resin, a cellulose resin, a polyisocyanate, a polyarylate, May be used.
- the transparent substrate film used in the present invention is preferably polyester or polycarbonate.
- the composition of the near infrared absorber and the polymer resin of the present invention can control the near infrared absorption ratio according to the content of the composition.
- the polymer resin contains 1 to 3% by weight of a near infrared ray absorbent composed of a dithiol-based metal complex compound. If the content of the near infrared absorbing agent is less than 1% by weight, the near infrared ray absorbing ability is insufficient. If the content is more than 3% by weight, the transmittance of the visible ray decreases.
- the composition of the present invention is applied to a glass or transparent base film by a wet process to produce a film or a panel.
- the coating solution prepared by dissolving or dispersing the near infrared absorber and the polymer resin in an organic solvent
- a roll coating method, a spin coating method, a casting method, or a melt extrusion method is used, though not limited to the present invention.
- the organic solvent is selected from the group consisting of dichloromethane, dichloroethane (DME), methyl ethyl ketone, methyl isobutyl ketone, toluene, ethylene glycol monoethyl ether, ethanol, xylene, tetrahydrofuran and 1,4-
- the dithiol-based metal complex of the present invention can be easily dissolved in the organic solvent.
- the dithiol-metal complex compound of the present invention is remarkably improved in solubility, as well as ketones and halogenated solvents, ethylene glycol monoethyl ether alcohols such as ethanol and the flow table 2.
- the near infrared ray absorbent of the present invention is dissolved or kneaded in the polymer resin, and then molded into a film or a panel by extrusion molding.
- the present invention can provide an optical filter and a thermal infrared ray shielding filter as a method for producing a film by mixing a master batch produced by mixing a near infrared absorber and a polymer resin.
- additives such as an antioxidant, a heat stabilizer, a viscosity adjuster, a plasticizer, a color improving agent, a lubricant, a nucleating agent, an ultraviolet stabilizer, an antistatic agent, an antioxidant, a binder and a catalyst may be further used in the masterbatch composition And the content of the additive can be adjusted within a range of 1 to 3% by weight of the near infrared absorber.
- the heat shielding film is excellent in the dispersibility of the near infrared absorber, so that unevenness of dyeing does not occur and heat shielding efficiency can be improved. Therefore, it is possible to provide a uniform quality heat shielding film, and it is possible to realize an economical effect by simplifying the process than the conventional dyeing process.
- the present invention is characterized in that the optical filter or the thermal infrared ray shielding filter is used for an image display device, and in particular, 1 to 3% by weight of a near infrared absorbent composed of a dithiol-based metal complex and an acrylic resin, a polyester resin, a polycarbonate resin, , 98 to 99% by weight of a polymeric resin selected from the group consisting of an acrylic resin, a polyester resin, a cellulose resin, a polyisocyanate, a polyarylate, and an epoxy resin is applied on a glass or transparent base film, A plasma display panel employing an infrared shielding filter is provided.
- Step 1 After dissolving 13.5 g of 3,4,5-trimethoxybenzaldehyde in 50 ml of ethanol, 20 ml of distilled water containing 4.5 g of potassium cyanide was slowly added. After refluxing for 1 hour and cooling, 150 ml of distilled water was added to form a precipitate, which was then filtered under reduced pressure, washed several times with distilled water, and dried to obtain 8.2 g of yellow object.
- Step 2 48 g of 2-hydroxy-1,2-bis (3,4,5-trimethoxyphenyl) ethanone was dissolved in 150 g of pyridine and 100 ml of distilled water containing 50 g of CuSO 4 .5H 2 O Slowly added. After cooling to reflux for 10 hours, 500 ml of distilled water was added to form a precipitate, which was then filtered under reduced pressure, washed several times with distilled water, and then dried to obtain 40 g of a pale yellow object.
- Step 3 32 g of 1,2-bis (3,4,5-trimethoxyphenyl) ethane-1,2-dione and 18 g of P 2 S 5 were placed in 150 ml of 1,4-dioxane and stirred. The solution was refluxed for 5 hours, cooled and filtered. The filtrate was transferred to a 500 ml reactor, and a solution of 11 g of NiCl 2 .H 2 O dissolved in 100 ml of distilled water was slowly added over 1 hour. After completion of the addition, the mixture was refluxed for 30 hours and cooled. 100 ml of ethanol was added to the cooled reactant, and the mixture was filtered under reduced pressure, washed several times with acetone, and then dried to obtain 14 g of a dark green object.
- Step 4 After stirring the AlCl 3 of 14.7g (0.11 mol) in dichloromethane 30ml for 30 minutes, diluted with 12-methoxy -Ni- complex compound 10g (0.011 mol) prepared in Step 3 in dichloromethane 50ml Lt; / RTI > After reacting for 1 hour and 30 minutes at room temperature, 600 ml of distilled water was slowly added while stirring in an ice chamber. The precipitate formed was filtered under reduced pressure, washed several times with distilled water, and then purified.
- Example 1 The target compounds prepared in Example 1 were analyzed by HPLC and mass spectrometer (LC-Mass spectrometer, VG BIO TECH, model name: VG BIO TECH), and the results are shown in Tables 1 and 2 below.
- thermogravimetric analyzer TGA
- mp 258.71, 320.59 and 342.82 ° C peaks were confirmed.
- DSC differential pressure calorimeter
- the search observe the compound as a result, the maximum absorption wavelength ( ⁇ max) is 960nm ( ⁇ 2.9 ⁇ 10 4 L / cm and g) was measured by a UV spectrometer was dissolved in methyl ethyl ketone [1] Accordingly, it can be used as a near-infrared absorbing agent suitable for use in a plasma display panel (PDP).
- ⁇ max the maximum absorption wavelength
- solubilities (g / g) of the dithiol-based nickel complexes of Example 1 were measured for each of 100 g of ethanol, methyl ethyl ketone, ethyl acetate and toluene solvent. The results are shown in Table 5 .
- the dithiol-based nickel complexes prepared in Example 1 were significantly improved in solubility not only in ketone-based and halogen-based solvents but also in alcohols such as ethanol, compared with dithiol-based nickel complexes substituted with methoxy groups.
- Step 1 After 40 g of p-anisaldehyde was dissolved in 40 ml of ethanol, 20 ml of distilled water containing 22 g of potassium cyanide was slowly added. The mixture was refluxed for 1 hour, cooled, and then 350 ml of distilled water was added to form a precipitate. The precipitate was filtered under reduced pressure, and the precipitate was stirred with 40 ml of ethanol for 20 minutes. After filtration, washed several times with ethanol and dried, ≪ / RTI >
- Step 2 19 g of 2-hydroxy-1,2-bis (4-methoxyphenyl) ethanone and 14 g of P 2 S 5 were placed in 100 ml of 1,4-dioxane and stirred. The solution was refluxed for 28 hours, cooled and filtered. The filtrate was transferred to a 500 ml reactor. A solution of 9 g of NiCl 2 .H 2 O dissolved in 30 ml of distilled water was slowly added over 2 hours. After completion of the addition, the mixture was refluxed for 30 hours and cooled. 200 ml of acetone was added to the cooled reaction product, which was then filtered under reduced pressure, washed several times with acetone, and then dried to obtain 12 g of a dark green object.
- Step 3 A stirring 22g of AlCl 3 in dichloromethane 50ml for 30 minutes and then diluted 12-methoxy -Ni- complex 21g 60ml in dichloromethane was added slowly. After reacting for 30 minutes at room temperature, 200 ml of distilled water was added slowly under ice chamber. The precipitate formed was filtered under reduced pressure, washed several times with distilled water, and washed with a small amount of methanol. And dried to obtain 19 g of a dark green object.
- Step 1 After 50 g of benzaldehyde was dissolved in 80 ml of ethanol, 70 ml of distilled water containing 8 g of sodium cyanide was slowly added. The mixture was refluxed for 3 hours and then cooled. The precipitate thus formed was filtered under reduced pressure. The precipitate was washed several times with ethanol and then dried to obtain 35 g of a pale yellow object.
- Step 2 8.6 g of 2-hydroxy-1,2-diphenylethanone and 11.8 g of 2-hydroxy-1,2-bis (4-methoxyphenyl) ethanone were mixed with 18 g of P 2 S 5 , Was added to 100 ml of 4-dioxane and stirred. After refluxing for 4 hours, the reaction solution was cooled and filtered. 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 dissolved in distilled water Lt; / RTI > After the addition was complete, the mixture was refluxed for 28 hours and cooled. 50 ml of acetone was added to the cooled reactant, the mixture was filtered under reduced pressure, washed several times with acetone, and then dried to obtain 16 g of a dark green object.
- Step 3 After stirring the 20g of AlCl 3 in dichloromethane 60ml for 30 minutes by diluting the 12-methoxy -Ni- complex 30g 50ml in dichloromethane was added slowly. After reacting at room temperature for 30 minutes, 200 ml of distilled water was added slowly under ice bath. The precipitate formed was filtered under reduced pressure, washed several times with distilled water, and washed with a small amount of methanol. And dried to obtain 17 g of a dark green object.
- Example 6 The procedure of Example 6 was repeated, except that 24.12 g (0.165 mol, 15 eq) of ZnCl 2 was used.
- a near infrared ray absorbent comprising a novel dithiol-based metal complex having improved solubility in an organic solvent of alcohols as well as ketone-based and halogen-based solvents.
- the near infrared absorber with improved solubility can realize efficient mixing with an organic material such as a polymer resin, the excellent near infrared absorbing property of the dithiol-based metal complex compound is sufficiently exhibited, and the near- Or a thermal infrared shielding filter.
- an optical filter using the near infrared ray absorbent excellent in the selective near infrared ray shielding effect and excellent in high-temperature stability can be obtained by providing the near infrared ray absorbent of the present invention in a manufacturing process step or in a separate master batch form, It can be usefully used for a thermal infrared shielding filter.
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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.TECHNICAL FIELD The present invention relates to a near infrared absorber made of a dithiol-based metal complex, a method for producing the dithiol-based metal complex, an optical filter containing the same and an infrared ray shielding filter. More particularly, By providing a near infrared ray absorbent made of a novel ditol-based nickel complex, it is possible to efficiently mix with an organic material such as a polymer resin mixed in the production of an optical filter, thereby exhibiting excellent near infrared absorption performance of the ditol- Which does not deteriorate the near infrared absorbing ability.
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.Description of the Related Art [0002] Recently, many kinds of image display devices (displays), such as liquid crystal display (LCD), plasma display panel (PDP), electroluminescence display (ELD), cathode ray tube display (CRT) And devices including these have been put into practical use. Of these various image display devices, a color plasma display (PDP) is attracting attention as a large wall-hanging 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. These image display devices, as a rule, display a color image by a combination of three primary colors of red, blue, and green light. However, light of unnecessary wavelength is emitted from the display device, and there is a problem in malfunction of the peripheral electronic device and high quality of the display image. In particular, the plasma display also emits near-infrared rays or electromagnetic waves in the 800 to 1000 nm range. Since the wavelength range of the near-infrared rays overlaps with the wavelength range used in near-infrared communication or remote controllers of other electronic apparatuses, 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.An optical filter containing a specific light absorbing agent is used for the above problem. For example, an optical filter for absorbing near infrared rays is disclosed in Japanese Patent Application Laid-Open Nos. 9-230134 and 11-73115 An optical filter using an aromatic dithiol nickel compound as a light absorber has been reported in JP-A-11-12425, JP-A 2000-206322, and JP-A 2000-212546.
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 optical filters, it is required to selectively absorb wavelength light in the near infrared region and transmit light in the visible light region. However, the conventional light absorbing agent absorbs the visible light region and is not suitable as the light absorbing agent for the optical filter.
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.Of the conventionally known light absorbers, dithiol-based nickel complexes represented by the following formula (13) are typical examples of those having excellent performance as a near-infrared absorbing agent by effectively absorbing near-infrared rays in a wavelength region of 800 to 900 nm.
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. The dithiol-based nickel complex is useful as an antioxidant such as polyolefins, an anti-discoloration agent such as an anti-fouling agent or a color photograph since it has a good inactivating action against singlet oxygen in addition to its use as a near infrared absorber. Furthermore, the dithiol-based nickel complexes have excellent properties applicable to various fields such that they can be usefully utilized as catalysts or liquid crystal materials for photodecomposition and dehydration of water.
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 sufficiently exhibit the properties of the dithiol-based nickel complex, the organic material such as a binder resin, a plastic, an ionic coating or an organic solvent should be dissolved or contained in an optimal amount 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 has a low solubility with respect to an organic material, so that it can not contain a sufficient amount in an organic material, so that the performance can not 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 made efforts to solve the problems of the conventional light absorbents for optical filters. As a result, they have found that a novel dithiol-based nickel complex compound having improved solubility in an organic material and absorbing only near- The present inventors have completed the present invention by producing a novel near infrared absorbing dye in which the performance of the dithiol-based nickel complex is sufficiently exhibited and the near infrared absorbing ability is not deteriorated for a long time, and an optical filter and a thermal infrared ray shielding filter using the same.
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 ray absorbent having a small absorption in the visible ray region, selectively absorbing the wavelength light in the near infrared ray region and improving the solubility in an organic material.
본 발명의 다른 목적은 신규한 디티올계 니켈 착화합물의 제조방법을 제공하는 것이다.Another object of the present invention is to provide a novel method for preparing 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, a thermal infrared ray shielding filter, and a plasma display panel employing the infrared filter, which contain a near infrared absorbent composed of the dithiol-based nickel complex.
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 ray absorbent made of a dithiol-based nickel complex having improved solubility in an organic material.
더욱 상세하게는, 하기 화학식 1로 표시되는 디티올계 금속 착화합물로 이루어진 근적외선 흡수제를 제공하는 것이다.More specifically, the present invention provides a near infrared ray absorbent comprising 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 q-r ', p', q 'and r' are 0 to 3, and [o-o '], [p- ] 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 benzene ring is substituted with 1 to 5 hydroxy groups to improve solubility. At this time, in the dithiol-based metal complex compound in the near infrared absorbing agent of the present invention, the metal element is preferably nickel.
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-based metal complexes of the present invention can be obtained by reacting a compound represented by the general formula (1) in a group consisting of dichloromethane, dichloroethane, methyl ethyl ketone, methyl isobutyl ketone, toluene, ethylene glycol monoethyl ether, ethanol, xylene, tetrahydrofuran and 1,4- And exhibit solubility-improving effects on any one of the selected organic solvents.
또한, 본 발명은 용해도가 개선된 디티올계 금속 착화합물의 제조방법을 제공한다. The present invention also provides a process for preparing 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 a dione compound represented by the formula (11) by oxidizing a compound having a 2-hydroxy group represented by the following formula (10);
화학식 11로 표시되는 디온 화합물과 금속염화물과 반응하여, 화학식 12로 표시되는 디티올계 금속 착화합물을 제조하는 제2단계; 및 A second step of reacting the dione compound represented by formula (11) with a metal chloride to produce a dithiol-based metal complex represented by formula (12); 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.The method according to claim 1 , wherein at least one Lewis acid selected from the group consisting of AlCl 3 , ZnCl 2, and BF 3 is quantitatively added to the organic solution containing the dithiol-based metal complex represented by Chemical Formula 12 to partially control the hydroxylation reaction, To produce 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 q-r ', p', q 'and r' are 0 to 3, and [o-o '], [p- ] 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.In the third step of the production method of the present invention, at least one Lewis acid selected from the group consisting of AlCl 3 , ZnCl 2 and BF 3 is used in an amount of 2 to 15 mol%, more preferably 2 to 10 mol % To carry out a partial hydroxylation reaction to prepare a symmetrical or asymmetric dithiol-based metal complex.
이때, 상기 디티올계 금속 착화합물은 하이드록시기 치환기가 2 내지 5개인 것이 바람직하며, 중심금속은 니켈이 바람직하다.At this time, the dithiol-based metal complex preferably has 2 to 5 hydroxyl group substituents, and the central 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.The present invention also relates to an optical filter manufactured in the form of a film or a panel by applying a composition containing a near infrared absorber and a polymer resin composed of a dithiol-based metal complex represented by Chemical Formula 1 on a glass or transparent base film, 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, among the dithiol-based metal complex compounds, the central metal is preferably nickel, and the polymer resin may be at least one selected from the group consisting of an acrylic resin, a polyester resin, a polycarbonate resin, a urethane resin, a cellulose resin, a polyisocyanate, a polyarylate, May be used.
또한 상기 조성물이 근적외선 흡수제 및 고분자 수지로 이루어지되, 고분자 수지에 대하여, 근적외선 흡수제 1 내지 3 중량%를 함유한다.The composition further comprises a near infrared absorbing agent and a polymer resin, and the polymer resin contains 1 to 3% by weight of a near infrared absorbing agent.
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.Further, the present invention is characterized in that the optical filter or the thermal infrared ray shielding filter is used for an image display device, and in particular, 1 to 3% by weight of a near infrared absorbent composed of a dithiol-based metal complex and an acrylic resin, a polyester resin, a polycarbonate resin, , 98 to 99% by weight of a polymeric resin selected from the group consisting of an acrylic resin, a polyester resin, a cellulose resin, a polyisocyanate, a polyarylate, and an epoxy resin is applied on a glass or transparent base film, A plasma display panel employing an infrared shielding filter is provided.
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 ray absorbent made of a dithiol-based metal complex having a small absorption in the visible ray region, selectively absorbing the wavelength light in the near infrared ray region and improving the solubility in an organic material, It is possible to provide an optical filter, a thermal infrared ray shielding filter and a plasma display panel employing the same that do not deteriorate the near infrared ray absorption ability for a long time by containing a near infrared ray absorbent.
도 1은 본 발명의 디티올계 니켈 착화합물의 자외선 분광기를 이용한 흡수스펙트럼이다. 1 is an absorption spectrum of a dithiol-based nickel complex of the present invention using an ultraviolet spectrometer.
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 provides a near infrared ray absorbent comprising a dithiol-based metal complex represented by Chemical Formula (1), which is a conventional dithiol-based metal complex compound known as a near infrared absorber to solve the problem of low solubility in an organic solvent.
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 q-r ', p', q 'and r' are 0 to 3, and [o-o '], [p- ] 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. The alkyl group of R is preferably a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec- an n-pentyl group, an iso-pentyl group, a sec-pentyl group, a tert-pentyl group and an n-hexyl group, 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 improves the solubility as the hydroxyl group (R = H) increases, preferably 1 to 5, more preferably 2 to 5, To 960 nm wavelength region and is suitable for PDP optical filter applications. If the number of hydroxy groups is more than 5, the effect of improving the solubility is high. However, the long wavelength shift is remarkable, resulting in the deviation from the desired wavelength range and the generation of the by-products reacting with the nickel complex is increased.
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 means that the dithiol-based metal complexes of the present invention are improved in solubility not only in ketone-based solvents and halogen-based solvents but also in alcohols such as ethylene glycol monoethyl ether and ethanol. More specifically, it is preferable to use a solvent 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- And has a 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 region 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 according to the first preferred embodiment of the present invention contains dithiol-based nickel complexes represented by the following general formula (2) or (3) and contains 2 to 5 R = H groups.
화학식 2 
(2)
화학식 3 
(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 dithiol-based nickel complexes selected from symmetrical dithiol-based nickel complexes represented by the following general formulas (4) to (6), and contains 2 to 5 R = H.
화학식 4 
Formula 4
화학식 5 
Formula 5
화학식 6 
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.The near infrared absorber according to the third preferred embodiment of the present invention contains a dithiol-based nickel complex selected from the asymmetric dithiol-based nickel complexes represented by the following general formulas (7) to (9) will be.
화학식 7 
Formula 7
화학식 8 
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 preparing a dithiol-based metal complex contained in the near infrared absorber and 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 a dione compound represented by the formula (11) by oxidizing a compound having a 2-hydroxy group represented by the following formula (10);
화학식 11로 표시되는 디온 화합물과 금속염화물과 반응하여, 화학식 12로 표시되는 디티올계 금속 착화합물을 제조하는 제2단계; 및 A second step of reacting the dione compound represented by formula (11) with a metal chloride to produce a dithiol-based metal complex represented by formula (12); 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.( 1) , at least one Lewis acid selected from the group consisting of AlCl 3 , ZnCl 2, and BF 3 is added to the organic solution containing the dithiol-based metal complex represented by Chemical Formula 12 to partially control the hydroxylation reaction, And a third step of preparing 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.)(Wherein 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].The production method of the present invention is characterized in that at least one Lewis acid selected from the group consisting of AlCl 3 , ZnCl 2 and BF 3 is added to the dithiol-based metal complex in an amount of 2 to 15 mol%, more preferably 2 to 10 mol % ≪ / RTI > to effect a partial hydroxylation reaction. At this time, depending on the equivalent amount of the selected Lewis acid, the change of the absorption wavelength, the solubility change and the yield are affected. When AlCl 3 is selected, it is preferably 2 to 10 mol%, and when ZnCl 2 is used, a change in the desired absorption wavelength, a change in solubility and yield can be obtained by 2 to 15 mol%. However, when the equivalent weight of the Lewis acid exceeds 15 mol%, the solubility is remarkably improved, but the long wavelength shift is remarkable and the yield of by-products reacting with the nickel complex is increased, thereby 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 exhibits excellent solubility in an organic solvent when 1 to 5, more preferably 2 to 5, hydroxyl group substituents are present. When the number of the hydroxy substituent groups is more than 5, the solubility is excellent, but the long-wavelength shift is remarkable, which is outside the desired wavelength range, and it is difficult to separate and purify the desired nickel complex.
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 may be 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- And exhibits excellent solubility in insoluble which is hardly dissolved in the prior art.
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.The third step of the production process of the present invention is a process wherein R = H (hydroxyl group) is quantitatively obtained through hydroxylation reaction using a symmetrical or asymmetric dithiol-based metal compound only substituted with R = CH 3 , To control the substitution reaction. Thus, the solubility in an organic solvent is improved, and at the same time, a symmetric type [compound represented by the general formulas 4 to 6] or an asymmetric type [compound represented by the general formulas 7 to 9] which 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 relates to an optical filter and a thermal infrared ray shielding filter manufactured in the form of a film or a panel by applying a composition containing a near infrared absorber made of a dithiol-based metal complex represented by the above formula (1) and a polymer resin on a glass or transparent base film 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, among the dithiol-based metal complex compounds, the central metal is preferably nickel, and the polymer resin may be at least one selected from the group consisting of an acrylic resin, a polyester resin, a polycarbonate resin, a urethane resin, a cellulose resin, a polyisocyanate, a polyarylate, May be used.
본 발명에서 사용되는 투명한 기재필름은 폴리에스테르 또는 폴리카보네이트를 사용하는 것이 바람직하다.The transparent substrate film used in the present invention is preferably 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 of the near infrared absorber and the polymer resin of the present invention can control the near infrared absorption ratio according to the content of the composition. Preferably, the polymer resin contains 1 to 3% by weight of a near infrared ray absorbent composed of a dithiol-based metal complex compound. If the content of the near infrared absorbing agent is less than 1% by weight, the near infrared ray absorbing ability is insufficient. If the content is more than 3% by weight, the transmittance of the visible ray decreases.
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 process to produce a film or a panel. In the wet process, the coating solution prepared by dissolving or dispersing the near infrared absorber and the polymer resin in an organic solvent A roll coating method, a spin coating method, a casting method, or a melt extrusion method is used, though not limited to the present invention.
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.Wherein the organic solvent is selected from the group consisting of dichloromethane, dichloroethane (DME), methyl ethyl ketone, methyl isobutyl ketone, toluene, ethylene glycol monoethyl ether, ethanol, xylene, tetrahydrofuran and 1,4- And the dithiol-based metal complex of the present invention can be easily dissolved in the organic solvent. As a result, the acrylic resin, the polyester resin, the polycarbonate resin, the urethane resin, the cellulose resin, the polyisocyanate, A polyarylate, and an epoxy-based resin.
특히, 본 발명의 디티올계 금속 착화합물은 케톤계와 할로겐계 용매뿐만 아니라, 에틸렌글리콜모노에틸에테르와 에탄올 등의 알코올류에서도 용해도가 현저히 개선된다[표 2].In particular, the dithiol-metal complex compound of the present invention is remarkably improved in solubility, as well as ketones and halogenated solvents, ethylene glycol monoethyl ether alcohols such as ethanol and the flow 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 produce the near infrared ray shielding filter of the present invention by applying the melt extrusion method, the near infrared ray absorbent of the present invention is dissolved or kneaded in the polymer resin, and then molded into a film or a 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 can provide an optical filter and a thermal infrared ray shielding filter as a method for producing a film by mixing a master batch produced 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.If necessary, additives such as an antioxidant, a heat stabilizer, a viscosity adjuster, a plasticizer, a color improving agent, a lubricant, a nucleating agent, an ultraviolet stabilizer, an antistatic agent, an antioxidant, a binder and a catalyst may be further used in the masterbatch composition And the content of the additive can be adjusted within a range of 1 to 3% by weight of the near infrared absorber.
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 the application in the form of the masterbatch containing the near infrared absorber, the heat shielding film is excellent in the dispersibility of the near infrared absorber, so that unevenness of dyeing does not occur and heat shielding efficiency can be improved. Therefore, it is possible to provide a uniform quality heat shielding film, and it is possible to realize an economical effect by simplifying the process than the conventional dyeing process.
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.Further, the present invention is characterized in that the optical filter or the thermal infrared ray shielding filter is used for an image display device, and in particular, 1 to 3% by weight of a near infrared absorbent composed of a dithiol-based metal complex and an acrylic resin, a polyester resin, a polycarbonate resin, , 98 to 99% by weight of a polymeric resin selected from the group consisting of an acrylic resin, a polyester resin, a cellulose resin, a polyisocyanate, a polyarylate, and an epoxy resin is applied on a glass or transparent base film, A plasma display panel employing an infrared shielding filter is provided.
이하, 본 발명을 실시예에 의하여 상세히 설명한다.Hereinafter, the present invention will be described in detail with reference to examples.
하기 실시예는 본 발명을 예시하는 것일 뿐, 본 발명의 범위가 하기 실시예에 한정되는 것은 아니다. The following examples illustrate 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-trimethoxybenzaldehyde in 50 ml of ethanol, 20 ml of distilled water containing 4.5 g of potassium cyanide was slowly added. After refluxing for 1 hour and cooling, 150 ml of distilled water was added to form a precipitate, which was then filtered under reduced pressure, washed several times with distilled water, and dried to obtain 8.2 g of yellow object.
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: 48 g of 2-hydroxy-1,2-bis (3,4,5-trimethoxyphenyl) ethanone was dissolved in 150 g of pyridine and 100 ml of distilled water containing 50 g of CuSO 4 .5H 2 O Slowly added. After cooling to reflux for 10 hours, 500 ml of distilled water was added to form a precipitate, which was then filtered under reduced pressure, washed several times with distilled water, and then dried to obtain 40 g of a pale yellow object.
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 18 g of P 2 S 5 were placed in 150 ml of 1,4-dioxane and stirred. The solution was refluxed for 5 hours, cooled and filtered. The filtrate was transferred to a 500 ml reactor, and a solution of 11 g of NiCl 2 .H 2 O dissolved in 100 ml of distilled water was slowly added over 1 hour. After completion of the addition, the mixture was refluxed for 30 hours and cooled. 100 ml of ethanol was added to the cooled reactant, and the mixture was filtered under reduced pressure, washed several times with acetone, and then dried to obtain 14 g of a dark green object.
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: After stirring the AlCl 3 of 14.7g (0.11 mol) in dichloromethane 30㎖ for 30 minutes, diluted with 12-methoxy -Ni- complex compound 10g (0.011 mol) prepared in Step 3 in dichloromethane 50㎖ Lt; / RTI > After reacting for 1 hour and 30 minutes at room temperature, 600 ml of distilled water was slowly added while stirring in an ice chamber. The precipitate formed was filtered under reduced pressure, washed several times with distilled water, and then purified. At this time, in the purification method, 12-methoxy-N-complexes starting from the 12-methoxy groups were more easily dissolved in methanol as the hydroxy substituent groups were larger in the methoxy groups, so that impurities were removed by washing with a small amount of methanol. The precipitate was dried, dissolved in ethyl methyl ketone, and filtered under reduced pressure. The filtrate was concentrated to dryness under reduced pressure to obtain 2.3 g of a dark green object.
<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 compounds prepared in Example 1 were analyzed by HPLC and mass spectrometer (LC-Mass spectrometer, VG BIO TECH, model name: VG BIO TECH), and the results are shown in Tables 1 and 2 below.
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 contained a compound in which 1 to 5 hydroxyl groups (R = H) were 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. As a result of measurement at a decomposition temperature of 281.26 ° C using a thermogravimetric analyzer (TGA), mp 258.71, 320.59 and 342.82 ° C peaks were confirmed. As a result of using a differential pressure calorimeter (DSC), three or more substances were mixed Respectively.
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, the search observe the compound as a result, the maximum absorption wavelength (λ max) is 960nm (ε = 2.9 × 10 4 L / cm and g) was measured by a UV spectrometer was dissolved in methyl ethyl ketone [1] Accordingly, it can be used as a near-infrared absorbing agent suitable for use in a plasma display panel (PDP).
2. AlCl2. AlCl
33
당량에 따른 파장변화 Wavelength change according to equivalence
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 AlCl 3 equivalent used in Step 4 of Example 1 was changed as shown in Table 3 below, and the maximum absorption wavelength (? Max ) was measured using a UV spectrometer under the condition of methyl ethyl ketone solvent.
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 of the measurement, the 12-methoxy-substituted Ni complex (Comparative Example 1) prepared in Step 3 of Example 1 showed a maximum absorption wavelength (λ max ) of 930 nm, while the equivalent amount of AlCl 3 , It was confirmed that the number of hydroxy (R = H) substituents increased and that the maximum absorption wavelength (? Max ) shifted quantitatively for a long wavelength.
반면에, AlCl3 과량(10당량 이상)을 사용할 때, 니켈 착화합물이 깨지는 부산물이 과량 생산되어 생산성이 떨어지면, 분리 정제가 어렵다.On the other hand, when using an excessive amount of AlCl 3 (10 equivalents or more), it is difficult to separate and purify if the by-product, which breaks down the nickel complex, is excessively produced and the productivity becomes poor.
3. AlCl3. AlCl
33
당량에 따른 용해도 변화 Solubility change according to equivalents
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 the condition of methyl ethyl ketone solvent. 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 greater the number of hydroxy (R = H) substituents, thereby increasing the solubility significantly. However, when 10 equivalents or more is used, the rate at which nickel metal breaks is higher.
4. AlCl4. AlCl
33
당량에 따른 수율 변화 Yield change according to equivalence
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 according to AlCl 3 equivalents was investigated under the premise of 100 g of the nickel complex compound substituted with 12 methoxy groups as starting materials in the step 4 of Example 1 above. 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 solubilities (g / g) of the dithiol-based nickel complexes of Example 1 were measured for each of 100 g of ethanol, methyl ethyl ketone, ethyl acetate and toluene solvent. 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 shown in Table 5, the dithiol-based nickel complexes prepared in Example 1 were significantly improved in solubility not only in ketone-based and halogen-based solvents but also in alcohols such as ethanol, compared with dithiol-based nickel complexes substituted with methoxy groups.
<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-anisaldehyde was dissolved in 40 ml of ethanol, 20 ml of distilled water containing 22 g of potassium cyanide was slowly added. The mixture was refluxed for 1 hour, cooled, and then 350 ml of distilled water was added to form a precipitate. The precipitate was filtered under reduced pressure, and the precipitate was stirred with 40 ml of ethanol for 20 minutes. After filtration, washed several times with ethanol and dried, ≪ / RTI >
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 placed in 100 ml of 1,4-dioxane and stirred. The solution was refluxed for 28 hours, cooled and filtered. The filtrate was transferred to a 500 ml reactor. A solution of 9 g of NiCl 2 .H 2 O dissolved in 30 ml of distilled water was slowly added over 2 hours. After completion of the addition, the mixture was refluxed for 30 hours and cooled. 200 ml of acetone was added to the cooled reaction product, which was then filtered under reduced pressure, washed several times with acetone, and then dried to obtain 12 g of a dark green object.
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: A stirring 22g of AlCl 3 in dichloromethane 50㎖ for 30 minutes and then diluted 12-methoxy -Ni- complex 21g 60㎖ in dichloromethane was added slowly. After reacting for 30 minutes at room temperature, 200 ml of distilled water was added slowly under ice chamber. The precipitate formed was filtered under reduced pressure, washed several times with distilled water, and washed with a small amount of methanol. And dried to obtain 19 g of a dark green object.
<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 : After 50 g of benzaldehyde was dissolved in 80 ml of ethanol, 70 ml of distilled water containing 8 g of sodium cyanide was slowly added. The mixture was refluxed for 3 hours and then cooled. The precipitate thus formed was filtered under reduced pressure. The precipitate was washed several times with ethanol and then dried to obtain 35 g of a pale yellow object.
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 were mixed with 18 g of P 2 S 5 , Was added to 100 ml of 4-dioxane and stirred. After refluxing for 4 hours, the reaction solution was cooled and filtered. 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 dissolved in distilled water Lt; / RTI > After the addition was complete, the mixture was refluxed for 28 hours and cooled. 50 ml of acetone was added to the cooled reactant, the mixture was filtered under reduced pressure, washed several times with acetone, and then dried to obtain 16 g of a dark green object.
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: After stirring the 20g of AlCl 3 in dichloromethane 60㎖ for 30 minutes by diluting the 12-methoxy -Ni- complex 30g 50㎖ in dichloromethane was added slowly. After reacting at room temperature for 30 minutes, 200 ml of distilled water was added slowly under ice bath. The precipitate formed was filtered under reduced pressure, washed several times with distilled water, and washed with a small amount of methanol. And dried to obtain 17 g of a dark green object.
<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 the 12-methoxy-N-complex prepared in Step 3 of Example 1 was diluted in 50 ml of dichloromethane and 16.1 g (0.11 mol) of ZnCl 2 was added to 30 ml of dichloromethane Lt; / RTI > and the solution was slowly added to the prepared solution. After refluxing for 6 hours, 600 ml of distilled water was slowly added to the mixture while stirring in an ice chamber. The precipitate formed was filtered under reduced pressure, washed several times with distilled water, and then purified. At this time, in the purification method, 12-methoxy-N-complexes starting from the 12-methoxy groups were more easily dissolved in methanol as the hydroxy substituent groups were larger in the methoxy groups, so that impurities were removed by washing with a small amount of methanol. The precipitate was dried, dissolved in ethyl methyl ketone, and filtered under reduced pressure. The resulting solution was concentrated to dryness under reduced pressure to obtain 4.8 g of a dark green object.
<실시예 7> ≪ Example 7 >
ZnCl2를 24.12g(0.165몰, 15eq)을 사용하는 것을 제외하고는, 상기 실시예 6과 동일하게 수행하였다. The procedure of Example 6 was repeated, except that 24.12 g (0.165 mol, 15 eq) of ZnCl 2 was used.
상기에서 살펴본 바와 같이, 본 발명은 As has been seen above,
첫째, 케톤계 및 할로겐계 용매뿐만 아니라, 알코올류의 유기용매에서 용해도가 개선된 신규한 디티올계 금속 착화합물로 이루어진 근적외선 흡수제를 제공하였다. First, there is provided a near infrared ray absorbent comprising a novel dithiol-based metal complex having improved solubility in an organic solvent of alcohols as well as ketone-based and halogen-based solvents.
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.Secondly, since the near infrared absorber with improved solubility can realize efficient mixing with an organic material such as a polymer resin, the excellent near infrared absorbing property of the dithiol-based metal complex compound is sufficiently exhibited, and the near- Or a thermal infrared shielding filter.
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.Thirdly, an optical filter using the near infrared ray absorbent excellent in the selective near infrared ray shielding effect and excellent in high-temperature stability can be obtained by providing the near infrared ray absorbent of the present invention in a manufacturing process step or in a separate master batch form, It can be usefully used for a 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 present invention has been particularly shown and described with reference to exemplary embodiments thereof, it is evident that many alternatives, modifications and variations will be apparent to those skilled in the art, and it is intended that the appended claims be construed as including all such modifications and alterations.
Claims (14)
- 하기 화학식 1로 표시되는 용해도가 개선된 디티올계 금속 착화합물로 이루어진 것을 특징으로 하는 근적외선 흡수제.A near infrared ray absorber characterized by comprising a dithiol-based metal complex having an improved solubility represented by the following 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 q-r ', p', q 'and r' are 0 to 3, and [o-o '], [p- ] 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 ray 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 process according to claim 1, wherein the dithiol-based metal complex is dichloromethane, dichloroethane, methyl ethyl ketone, methyl isobutyl ketone, toluene, ethylene glycol monoethyl ether, ethanol, xylene, tetrahydrofuran, Wherein the organic solvent has a solubility in the range of 0.05 to 7 g / g.
- 제1항에 있어서, 상기 디티올계 금속 착화합물이 930 내지 960 nm 파장영역의 근적외선을 선택적으로 흡수하는 것을 특징으로 하는 상기 근적외선 흡수제.The near infrared ray 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 ray 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 R = H is contained in an amount of 2 to 5.화학식 2(2)
화학식 3(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 dithiol-based metal complex according to claim 1, wherein the dithiol-based metal complex is any one selected from symmetrical dithiol-based nickel complexes represented by the following general formulas (4) to (6) .화학식 4Formula 4
화학식 5Formula 5
화학식 66(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 dithiol-based metal complex according to claim 1, wherein the dithiol-based metal complex is any one selected from asymmetric dithiol-based nickel complexes represented by the following general formulas (7) to (9) Absorbent.화학식 7Formula 7
화학식 88
화학식 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 the following formula (10) to synthesize a dione compound represented by the formula (11);화학식 11로 표시되는 디온 화합물과 금속염화물과 반응하여, 화학식 12로 표시되는 디티올계 금속 착화합물을 제조하는 제2단계; 및 A second step of reacting the dione compound represented by formula (11) with a metal chloride to produce a dithiol-based metal complex represented by formula (12); 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.( 1) , at least one Lewis acid selected from the group consisting of AlCl 3 , ZnCl 2, and BF 3 is added to the organic solution containing the dithiol-based metal complex represented by Chemical Formula 12 to partially control the hydroxylation reaction, And a third step of preparing a dithiol-based metal complex compound having the formula (1).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 q-r ', p', q 'and r' are 0 to 3, and [o-o '], [p- ] 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 of claim 8, wherein characterized in that said first added to AlCl 3, ZnCl 2, and at least one Lewis acid for a dithiol metal complex compound, 2 to 15 mol% is selected from the group consisting of BF 3 in Step 3 A 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.9. The method according to claim 8, wherein the dithiol-based metal complex has 1 to 5 hydroxyl group substituents.
- 유리 또는 투명한 기재필름 상에,On a glass or transparent substrate 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 characterized by being manufactured in the form of a film or a panel by applying a composition containing a near infrared absorber made of the dithiol-based metal complex of any one of claims 1 to 7 and a polymer resin.
- 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.12. The infrared ray shielding filter according to claim 11, wherein the composition comprises a near infrared absorbent and a polymer resin, wherein the polymer resin contains 1 to 3% by weight of a near infrared absorbent.
- 제1항 내지 제7항 중 어느 한 항의 디티올계 금속 착화합물로 이루어진 근적외선 흡수제 1 내지 3 중량% 및 1 to 3% by weight of a near infrared absorbent composed of the dithiol-based metal complex of any one of claims 1 to 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.A composition comprising 98 to 99% by weight of a polymer resin selected from the group consisting of an acrylic resin, a polyester resin, a polycarbonate resin, a urethane resin, a cellulose resin, a polyisocyanate, a polyarylate, Or a transparent infrared ray shielding filter manufactured by applying on a transparent substrate film.
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