CN100495082C - Wavelength-selective absorption filter - Google Patents
Wavelength-selective absorption filter Download PDFInfo
- Publication number
- CN100495082C CN100495082C CNB2005800426821A CN200580042682A CN100495082C CN 100495082 C CN100495082 C CN 100495082C CN B2005800426821 A CNB2005800426821 A CN B2005800426821A CN 200580042682 A CN200580042682 A CN 200580042682A CN 100495082 C CN100495082 C CN 100495082C
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- Prior art keywords
- wavelength
- selective absorption
- pigment
- resin
- class
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- 239000004327 boric acid Substances 0.000 description 1
- 229940006460 bromide ion Drugs 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 1
- 125000004369 butenyl group Chemical group C(=CCC)* 0.000 description 1
- 125000006226 butoxyethyl group Chemical group 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- OEYIOHPDSNJKLS-UHFFFAOYSA-N choline Chemical compound C[N+](C)(C)CCO OEYIOHPDSNJKLS-UHFFFAOYSA-N 0.000 description 1
- 229960001231 choline Drugs 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 150000004696 coordination complex Chemical class 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 229910001431 copper ion Inorganic materials 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- TYIXMATWDRGMPF-UHFFFAOYSA-N dibismuth;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Bi+3].[Bi+3] TYIXMATWDRGMPF-UHFFFAOYSA-N 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- XXJWXESWEXIICW-UHFFFAOYSA-N diethylene glycol monoethyl ether Chemical compound CCOCCOCCO XXJWXESWEXIICW-UHFFFAOYSA-N 0.000 description 1
- 229940075557 diethylene glycol monoethyl ether Drugs 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- UBHZUDXTHNMNLD-UHFFFAOYSA-N dimethylsilane Chemical compound C[SiH2]C UBHZUDXTHNMNLD-UHFFFAOYSA-N 0.000 description 1
- JZZIHCLFHIXETF-UHFFFAOYSA-N dimethylsilicon Chemical compound C[Si]C JZZIHCLFHIXETF-UHFFFAOYSA-N 0.000 description 1
- 150000002009 diols Chemical class 0.000 description 1
- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 125000005448 ethoxyethyl group Chemical group [H]C([H])([H])C([H])([H])OC([H])([H])C([H])([H])* 0.000 description 1
- 238000000855 fermentation Methods 0.000 description 1
- 230000004151 fermentation Effects 0.000 description 1
- 125000001207 fluorophenyl group Chemical group 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 125000001072 heteroaryl group Chemical group 0.000 description 1
- MBAKFIZHTUAVJN-UHFFFAOYSA-I hexafluoroantimony(1-);hydron Chemical compound F.F[Sb](F)(F)(F)F MBAKFIZHTUAVJN-UHFFFAOYSA-I 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 229910003437 indium oxide Inorganic materials 0.000 description 1
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 description 1
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-M iodide Chemical compound [I-] XMBWDFGMSWQBCA-UHFFFAOYSA-M 0.000 description 1
- 229940006461 iodide ion Drugs 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 150000007974 melamines Chemical class 0.000 description 1
- 150000001455 metallic ions Chemical class 0.000 description 1
- GRVDJDISBSALJP-UHFFFAOYSA-N methyloxidanyl Chemical group [O]C GRVDJDISBSALJP-UHFFFAOYSA-N 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- KYTZHLUVELPASH-UHFFFAOYSA-N naphthalene-1,2-dicarboxylic acid Chemical class C1=CC=CC2=C(C(O)=O)C(C(=O)O)=CC=C21 KYTZHLUVELPASH-UHFFFAOYSA-N 0.000 description 1
- 150000002791 naphthoquinones Chemical class 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 125000004998 naphthylethyl group Chemical group C1(=CC=CC2=CC=CC=C12)CC* 0.000 description 1
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical class OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 239000012766 organic filler Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- UGFMBZYKVQSQFX-UHFFFAOYSA-N para-methoxy-n-methylamphetamine Chemical compound CNC(C)CC1=CC=C(OC)C=C1 UGFMBZYKVQSQFX-UHFFFAOYSA-N 0.000 description 1
- 125000002255 pentenyl group Chemical group C(=CCCC)* 0.000 description 1
- VLTRZXGMWDSKGL-UHFFFAOYSA-M perchlorate Chemical compound [O-]Cl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-M 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 125000004344 phenylpropyl group Chemical group 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 150000003016 phosphoric acids Chemical class 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000010695 polyglycol Substances 0.000 description 1
- 229920000151 polyglycol Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 229920001289 polyvinyl ether Polymers 0.000 description 1
- 239000001103 potassium chloride Substances 0.000 description 1
- 235000011164 potassium chloride Nutrition 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- QCTJRYGLPAFRMS-UHFFFAOYSA-N prop-2-enoic acid;1,3,5-triazine-2,4,6-triamine Chemical compound OC(=O)C=C.NC1=NC(N)=NC(N)=N1 QCTJRYGLPAFRMS-UHFFFAOYSA-N 0.000 description 1
- 125000004368 propenyl group Chemical group C(=CC)* 0.000 description 1
- 238000012797 qualification Methods 0.000 description 1
- 150000004053 quinones Chemical class 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 230000003252 repetitive effect Effects 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 230000037387 scars Effects 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- FZHAPNGMFPVSLP-UHFFFAOYSA-N silanamine Chemical compound [SiH3]N FZHAPNGMFPVSLP-UHFFFAOYSA-N 0.000 description 1
- 229920005573 silicon-containing polymer Polymers 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- IIACRCGMVDHOTQ-UHFFFAOYSA-N sulfamic acid Chemical compound NS(O)(=O)=O IIACRCGMVDHOTQ-UHFFFAOYSA-N 0.000 description 1
- 125000000020 sulfo group Chemical group O=S(=O)([*])O[H] 0.000 description 1
- 150000003504 terephthalic acids Chemical class 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 1
- 125000003396 thiol group Chemical class [H]S* 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- OVTCUIZCVUGJHS-VQHVLOKHSA-N trans-dipyrrin Chemical class C=1C=CNC=1/C=C1\C=CC=N1 OVTCUIZCVUGJHS-VQHVLOKHSA-N 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 1
- AAAQKTZKLRYKHR-UHFFFAOYSA-N triphenylmethane Chemical compound C1=CC=CC=C1C(C=1C=CC=CC=1)C1=CC=CC=C1 AAAQKTZKLRYKHR-UHFFFAOYSA-N 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 150000003672 ureas Chemical class 0.000 description 1
- 150000003673 urethanes Chemical class 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- 238000009941 weaving Methods 0.000 description 1
- 125000001834 xanthenyl group Chemical class C1=CC=CC=2OC3=CC=CC=C3C(C12)* 0.000 description 1
- RNWHGQJWIACOKP-UHFFFAOYSA-N zinc;oxygen(2-) Chemical compound [O-2].[Zn+2] RNWHGQJWIACOKP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B47/00—Porphines; Azaporphines
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B53/00—Quinone imides
- C09B53/02—Indamines; Indophenols
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
- G02B1/04—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of organic materials, e.g. plastics
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/20—Filters
- G02B5/22—Absorbing filters
- G02B5/223—Absorbing filters containing organic substances, e.g. dyes, inks or pigments
Abstract
This invention provides a wavelength-selective absorption optical filter that exhibits high level and broad absorption in a near infrared region, further absorbs neon light, and exhibits high light transmittance in other visible light region. The wavelength-selective absorption optical filter is less likely to cause a change in optical properties with the elapse of time and is highly durable. The wavelength-selective absorption optical filter comprises a transparent base material and a wavelength-selective absorption layer having a single or multilayer structure stacked on the base material. The wavelength-selective absorption layer comprises a resin, an near infrared absorptive coloring matter (A) and a coloring matter (B), and the wavelength-selective absorption optical filter has maximum absorption at a wavelength of 800 to 1200 nm and a wavelength of 550 to 620 nm. The wavelength-selective absorption optical filter is characterized in that one type of the near infrared absorptive coloring matter (A) is an aromatic diimmonium coloring matter (a) of which the counter ion is bis(trifluoromethansulfonyl)imidic acid, and one type of the coloring matter (B) is a porphyrin coloring matter or azaporphyrin coloring matter (b).
Description
Technical field
The present invention relates to the optical filter of a kind of absorption near infrared ray and neon light, specifically, relate to following Wavelength-selective absorption filter, it has broad absorption near infrared region, also absorb neon light, and the light penetration height of other visible region, even in addition in hot and humid keeping down, optical characteristics through the time change also lessly, the permanance aspect is good.
Background technology
Optical filter with near infrared receptivity has the character of blocking near infrared ray and visible light being passed, and is used in the various uses.
In recent years, as slim big view display, plasma scope receives publicity, yet the problem that is caused the e-machine generation misoperation of using the near infrared ray remote control from plasma scope by the near infrared ray that penetrates is arranged, thereby be provided with the near-infrared absorbing light filter in the front of plasma scope.
As the near-infrared absorbing light filter, proposed: (1) contains the light filter of metallic ions such as copper or iron in phosphoric acid class glass; (2) with different folded layer by layer of refractive index, by making through the interference of light, and the interference light filter that certain wavelengths is seen through; (3) in multipolymer, contain the acrylic resin light filter of copper ion; (4) will in resin, disperse or dissolve the folded layer by layer light filter of infrared ray absorbing pigment.
In the middle of them, the light filter of (4) is owing to processability, productivity are good, and the degree of freedom of optical design is also bigger, therefore proposes to make the whole bag of tricks (for example with reference to patent documentation 1～9) of this light filter.
Patent documentation 1: the spy opens communique 2002-No. 82219
Patent documentation 2: the spy opens communique 2002-No. 214427
Patent documentation 3: the spy opens communique 2002-No. 303720
Patent documentation 4: the spy opens communique 2002-No. 333517
Patent documentation 5: the spy opens communique 2003-No. 82302
Patent documentation 6: the spy opens communique 2003-No. 96040
Patent documentation 7: the spy opens flat 11-No. 305033 communiques
Patent documentation 8: the spy opens flat 11-No. 326629 communiques
Patent documentation 9: the spy opens flat 11-No. 326631 communiques
Patent documentation 10: the spy opens communique 2000-No. 227515
Patent documentation 11: the spy opens communique 2002-No. 264278
Patent documentation 12: the international pamphlet that discloses No. 97/38855
Patent documentation 13: the spy opens communique 2003-No. 114323
Patent documentation 14: the spy opens communique 2002-No. 138203
In the middle of these methods, though the scheme with ability that the near infrared ray that will penetrate from plasma scope blocks is fully also arranged, under hot and humid long-time down situation about using, the ageing stability of optical characteristics is abundant inadequately.
Method as the ageing stability that is suppressed at the optical characteristics under the hot and humid long-time down situation about using, following method was proposed, that is, the glass temperature that constitutes the resin of near infrared ray absorption layer is made as method (for example with reference to patent documentation 7～10) more than the operational support temperature of the machine that uses the near-infrared absorbing light filter; Reduce the method (for example with reference to patent documentation 10,11) of the residual solvent amount of near infrared ray absorption layer.
In addition, known aromatic series two imido (diimmonium) the compounds pigment that uses as near infrared absorbing coloring matter is in general to (for example with reference to patent documentation 12 the 17th page) a little less than the heat tolerance.
So, rotten technology as the pigment that in the near infrared ray absorption layer that contains two imido compounds, suppresses to cause by heat, following method etc. was proposed, promptly, two imido compounds are refining, make to contain in the near infrared ray absorption layer in DSC measures to have the method (for example with reference to patent documentation 13) of the two specific imido compounds of endothermic peak in the temperature more than 220 ℃; Make and contain the method that fusing point is two imido compounds more than 190 ℃ (for example with reference to patent documentation 14) in the near-infrared shielding layer.
In addition, plasma scope be owing to also can send near neon orange-colored light (wavelength 600nm), if so just keep the ageing stability of near infrared ray absorption layer, then damage the problem of the clarity of the bright-coloured color rendition of this display or image in addition.
Summary of the invention
The objective of the invention is to, a kind of Wavelength-selective absorption filter is provided, is to have big and wide absorption near infrared region, also absorb neon light, and to other the high selection absorbing light optical light filter of light penetration of visible region, its optical characteristics through the time with low uncertainty, permanance is good.
In order to solve described problem, the inventor etc. further investigate, and the result has finished the present invention finally.That is, the present invention is as follows.
First invention is a kind of Wavelength-selective absorption filter, be on transparent base, the stacked wavelength selective absorption layers that contains the single or multiple lift of resin, near infrared absorbing coloring matter (A) and pigment (B) forms, and the Wavelength-selective absorption filter that has very big absorption at wavelength 800～1200nm and wavelength 550～620nm place, it is characterized in that
The a kind of of described near infrared absorbing coloring matter (A) is with the aromatic series two imido class pigments (a) of two (trifluoromethane sulfonyl group) imidic acids as counterion,
The a kind of of described pigment (B) is porphyrin class pigment or aza porphyrin class pigment (b).
Second invention is the Wavelength-selective absorption filter described in following first invention, it is characterized in that the wavelength selective absorption layers of multilayer is that the neon that forms the near infrared ray absorption layer contain resin and near infrared absorbing coloring matter (A) successively on transparent base, contain resin and pigment (B) blocks that (neon-cut) layer forms.
The 3rd invention is the Wavelength-selective absorption filter described in following first invention, it is characterized in that, with respect to described aromatic series two imido class pigments (a) 100 mass parts, contain described porphyrin class pigment or described aza porphyrin class pigment (b) 5～100 mass parts (mass ratio) in the wavelength selective absorption layers.
The 4th invention is the Wavelength-selective absorption filter described in following first invention, it is characterized in that the resin that constitutes wavelength selective absorption layers is an acrylic resin.
The 5th invention is the Wavelength-selective absorption filter described in following first invention, it is characterized in that, the wavelength selective absorption layers of individual layer is on described transparent base, coating contains the coating fluid A of organic solvent, resin, the fragrant same clan two imido class pigments (a), porphyrin class pigment or aza porphyrin class pigment (b), is dried to form.
The 6th invention is the Wavelength-selective absorption filter described in following first invention, it is characterized in that, the wavelength selective absorption layers of multilayer comprises: near infrared ray absorption layer, it is on described transparent base, coating contains the coating fluid B of organic solvent, resin and aromatic series two imido class pigments (a), is dried to form; Neon blocks layer, and it is that coating contains the coating fluid C of organic solvent and resin, porphyrin class pigment or aza porphyrin class pigment (b), is dried to form above this near infrared ray absorption layer tight.
The 7th invention is the Wavelength-selective absorption filter described in following the 5th or the 6th invention, it is characterized in that, it is 2～12 surfactant that coating fluid A or B also contain HLB.
The 8th invention is the Wavelength-selective absorption filter described in following the 7th invention, it is characterized in that surfactant is silicon class surfactant or fluorine class surfactant.
Under the situation of the front of Wavelength-selective absorption filter of the present invention being located at plasma scope, not only can be identical with Wavelength-selective absorption filter in the past, the unwanted near infrared ray that absorption is penetrated from display, prevent the misoperation of precision machinery, and because with unwanted neon light absorption, therefore the sharpness height of image, and by temperature or humidity cause with low uncertainty, thereby can reduce plasma scope high image quality through the time change.
Embodiment
So-called Wavelength-selective absorption filter of the present invention is on transparent base; the stacked resin that contains; the wavelength selective absorption layers of the single or multiple lift of near infrared absorbing coloring matter (A) and pigment (B) forms; and the Wavelength-selective absorption filter that has very big absorption at wavelength 800～1200nm and wavelength 550～620nm; it is characterized in that; the a kind of of described near infrared absorbing coloring matter (A) is that a kind of of described pigment (B) is porphyrin class pigment or aza porphyrin class pigment (b) with the aromatic series two imido class pigments (a) of two (trifluoromethane sulfonyl group) imidic acids as counterion.
Below, with the present invention is described in detail.
(transparent base)
Among the present invention, though transparent base is not particularly limited, preferred total light penetration is more than 80%, and turbidity is below 5%.Under the situation that the transparency of base material is wanting in, not only can reduce the brightness of display, and the sharpness of image (sharp) becomes not good.
As this kind transparent base, for example can enumerate plastic sheeting or thin slice, the glass of polyesters, acrylic compounds, cellulose family, polyethylene kind, PP type, polyolefins, polyvinyl chloride, polycarbonate-based, phenol, polyurethanes etc. and their the two or more arbitrarily material of having fitted.The good polyester film of balance of preferred thermotolerance, flexibility, more preferably pet film.
What is called is suitable for the polyester film as transparent base used among the present invention, be meant the film of following manufacturing, promptly, as the dicarboxylic acid composition, use terephthalic acids, isophthalic acid, aromatic dicarboxylic acid or its esters such as naphthalene dicarboxylic acids, as diol component, make spent glycol, diglycol, 1,4-butylene glycol, neopentyl glycols etc. carry out esterification or ester exchange reaction, make it to carry out polycondensation reaction then, after the polyester sheet drying that will so obtain, fusion in extruder, the not stretching thin slice that will get with laminar extruding from T shape mould are carried out heat fixation then and are handled at least along an axial tension, relaxation processes.
Described film is considered from viewpoints such as intensity, preferred especially biaxially oriented film.As drawing process, can enumerate tubulose pulling method, simultaneously biaxial stretch-formed method, biaxial stretch-formed method etc. one by one, yet from considerations such as planarity, dimensional stability, uneven thickness, preferably biaxial stretch-formed one by one method.Biaxial stretch-formed one by one rule, carries out roll-in with the multiplying power below 5.0 times more than 2.0 times along long side direction and stretches under the temperature of (below Tg+30 ℃) more than the glass temperature (Tg) of polyester in this way along long side direction.Next, in stenter (tenter), after the preheating, under the temperature below 150 ℃ more than 120 ℃, stretch with the multiplying power broad ways below 5.0 times more than 1.2 times.Then, to this biaxially oriented film, under the temperature of (fusing point-10 ℃ below) more than 220 ℃, carry out heat fixation and handle.Then, by on Width, making it to relax 3%～8%, just can make the polyester film that is suitable as transparent base used among the present invention.In addition, for the dimensional stability of the long side direction that further improves film, also can and handle with vertical relaxation.
In film,, preferably make it to contain particle and form projection at film surface in order to give the property handled (coiling after for example stacked).As the particle that film is contained, can enumerate thermotolerance macromolecule particles such as inorganic particulates such as silica, smalite, talcum, lime carbonate, zeolite, aluminium oxide, acrylic acid, PMMA, nylon, polystyrene, polyester, benzoguanamine formalin condensation product.Consider that from the viewpoint of the transparency preferably the content of the particle in the film is few, below for example preferred above 1000ppm of 1ppm.In addition, consider, preferably select and the approaching particle of employed resin refractive index from the viewpoint of the transparency.In addition, in order to give various functions to film as required, also can contain photostabilizer (ultraviolet screener), pigment, anti-live agent etc.
Used transparent base both can be a single thin film among the present invention, the laminated film more than 2 layers of can be stacked also top layer and central core.For the situation of laminated film, has the advantage that can design the function of top layer and central core independently.For example, contain particle and form concavo-convexly on the surface, make the thick central core of thickness not contain particle in fact by the top layer that only makes thin thickness, just can be when keeping the property handled, as the whole transparency that further improves of laminated film.The manufacture method of described laminated film is not particularly limited, if but consider productivity, then especially preferably utilize following so-called coetrusion to make, promptly, the raw material of top layer and central core is extruded from extruder separately, the mould that leads, behind the thin slice that obtained not stretching, with it at least along an axial orientation.
Though the thickness of transparent base is according to starting material and difference, yet under the situation of using mylar, more than the preferred 35 μ m, more preferably more than the 50 μ m.On the other hand, below the preferred 260 μ m of thickness, more preferably below the 200 μ m.Under the little situation of thickness, not only the property handled becomes bad easily, and under situation about heating when reducing residual solvent amount in the wavelength selective absorption layers dry, produces hot gauffer easily in film, makes planarity become bad.On the other hand, under the big situation of thickness, not only aspect cost, problem is arranged, and when preserving with the drum coiling, it is bad to be easy to generate the planarity that is caused by the coiling defective.
(middle layer)
Wavelength-selective absorption filter of the present invention has the formation of the wavelength selective absorption layers of stacked single or multiple lift on transparent base, yet the purpose for the transparency of connecting airtight property that improves transparent base and wavelength selective absorption layers or raising transparent base also can be provided with the middle layer.And, in film, do not contain under the situation of particle, when making film,, can when keeping the property handled, obtain the transparency of height by the middle layer of containing particle is set simultaneously.
As the resin that constitutes described middle layer, can enumerate polyester resin, urethane resin, polyester urethane resin, acrylic resin, melamine resin etc., yet it well is crucial making the connecting airtight property with base material and wavelength selective absorption layers when selecting, for example, if constituting the resin of base material and wavelength selective absorption layers is the ester class, then preferably selected have polyesters, a polyester urethane class of similar structure.
In described middle layer, for connecting airtight property of raising, improve the purpose of water tolerance, also can contain crosslinking chemical and form crosslinked configuration.As crosslinking chemical, can enumerate urea class, epoxies, melamine class, isocyanates.Particularly, at resin at high temperature.Cause under the high humility that the effect of utilizing crosslinking chemical to obtain is fairly obvious under the situation of albefaction or intensity reduction.And, also can not use crosslinking chemical, but use graft copolymerization resin with self-crosslinking as resin.
In the middle layer, for form concavo-convex on the surface and improve the purpose of sliding, also can contain various particles.As the particle that is contained in the middle layer, for example can enumerate inorganic particulates such as silica, smalite, talcum, lime carbonate, zeolite, aluminium oxide; Organic fillers such as acrylic acid, PMMA, nylon, styrene, polyester, benzoguanamine formalin condensation product.And, consider from the viewpoint of the transparency, preferably select and the approaching particle of employed resin refractive index.
In addition, for the middle layer being given various functions, also can contain surfactant, anti-live agent, pigment, ultraviolet light absorber etc.
Though the middle layer under the situation with required function, also can be an individual layer, yet as required, can stackedly be more than 2 layers also.
For the thickness in middle layer, so long as have required function, just be not particularly limited, yet below the above 5 μ m of preferred 0.01 μ m.Under the little situation of thickness, be difficult to embody function as the middle layer, on the contrary, under the big situation of thickness, it is bad that the transparency becomes easily.
The middle layer preferably utilizes rubbing method setting.As rubbing method, can use the intaglio printing coating method, lick the mode of being coated with, impregnation method, spraying method, curtain-type coating method, air knife coating method, scraper plate coating method, contrary roller coat cover known coating processes such as mode, can adopt the streamline that coating layer is set in the manufacturing process of film to apply (in-line coat) mode, coated off-line (off-line coat) mode of coating layer etc. is set after thin film fabrication.In the middle of these modes, the streamline coating method is not only good aspect cost, and owing to by making coating layer contain particle, just need not contain particle in transparent base, therefore can improve the transparency to heavens, so preferred.
(wavelength selective absorption layers)
Wavelength-selective absorption filter of the present invention on transparent base directly or folder every the stacked wavelength selective absorption layers in ground, middle layer, its layer by the single or multiple lift that comprises the pigment with near-infrared absorbing ability constitutes.
So-called near infrared absorbing coloring matter is the pigment that the near infrared range below the above 1200nm of wavelength 800nm has very big absorption, can enumerate compounds such as two imido classes, phthalocyanines, dithiol metal complex class, naphthalene phthalocyanines, azo class, polymethine class, anthraquinone class, naphthoquinones class, pyrans class, thiapyran class, squarilium class, croconium class, four dehydrogenation choline (tetradehydrocholine) classes, triphenylmethane, cyanine class, azo class, ammonia (aminium) class.These compounds can use separately, and also can mix more than 2 kinds and use, yet among the present invention, need contain two imide salt compounds with following formula (I) expression, the absorption of its near infrared range is big, and the uptake zone field width, and the transmitance of visible region is also high in addition.
[changing 1]
As the R in the described general formula (I)
1～R
8Concrete example, can enumerate alkyl such as (1) methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl, isobutyl, the tert-butyl group, n-pentyl, n-hexyl, n-octyl, 2-hydroxyethyl, 2-cyano ethyl, 3-hydroxypropyl, 3-cyano group propyl group, methoxy ethyl, ethoxyethyl group, butoxyethyl group; (2) aryl such as phenyl, fluorophenyl, chlorphenyl, tolyl, diethylamino phenyl, naphthyl; (3) alkenyls such as vinyl, propenyl, butenyl group, pentenyl; (4) aralkyl such as benzyl, p-luorobenzyl, p-chlorphenyl, phenyl propyl, naphthyl ethyl.
In addition, as R
9～R
12, can enumerate hydrogen, fluorine, chlorine, bromine, diethylamino, dimethylamino, cyano group, nitro, methyl, ethyl, propyl group, trifluoromethyl, methoxyl, ethoxy, propoxyl group etc.
In the formula (I), X
-Can enumerate fluorine ion, chlorion, bromide ion, iodide ion, perchlorate ion, hexafluoro-antimonic acid salt ion, hexafluorophosphoric acid salt ion, tetrafluoro boric acid ion, two (trifluoromethane sulfonyl group) imidic acid ion etc.And, among the present invention, use (aftermentioneds) such as aza porphyrin class pigments, therefore described X owing to block pigment as neon
-Need contain near infrared absorbing coloring matter as two (trifluoromethane sulfonyl group) imidic acid ions.This compound can be used as commercially available product and obtains, and for example can enumerate Japanese Carlit system CIR-1085, CIR-RL, Japanese chemical drug system IRG-068.
Wavelength-selective absorption filter of the present invention is except described two imide salt compounds with formula (I) expression, for the purpose that enlarges and adjust the absorption region of near infrared range, the near infrared absorbing coloring matter that also can add other.The preferred material that can not promote the deterioration of two imido salt pigments specifically, can be enumerated the phthalocyanines, anthocyanidin, the two thiophenol metal complex class that have absorption peak below the above 1200nm of 800nm.
Among the present invention, for the absorption of controlling required near infrared range, the transmitance in the visible region, the amount of near infrared absorbing coloring matter preferably is adjusted into, and reaches 0.01g/m on the arbitrary face of the thickness direction of wavelength selective absorption layers
2Above 1.0g/m
2Below.Under the less situation of the amount of near infrared absorbing coloring matter, the receptivity deficiency in the near infrared range, on the contrary, under more situation, the transparency in the visible region is not enough, thereby the problem of the brightness reduction of display is arranged.
Among the present invention, in wavelength selective absorption layers, need to contain neon and block pigment.Plasma scope send with near the 600nm as the so-called neon orange-colored light at center, in redness, be mixed with orange, thereby the shortcoming that can't obtain bright-coloured redness is arranged.Block pigment by containing neon, just can solve described problem.
So-called neon blocks pigment and is meant the pigment that has absorption maximum in the wavelength region may below the above 620nm of 550nm among the present invention, specifically, can enumerate cyanine class, squarilium class, azomethine class, xanthene class, oxonols class, azo class, phthalocyanines, quinones, Azulenium class, pyrans class, croconium class, dithiol metal complex class, Pyrromethene class, aza porphyrin class etc.These pigments can use separately, also can mix more than 2 kinds and use, yet among the present invention, need to use porphyrin class pigment or aza porphyrin class pigment.
So-called porphyrin class pigment or aza porphyrin class pigment are the pigments with following formula (II), (III) expression.R in formula (II) and the formula (III)
11～R
14And R
15～R
22Concrete example can to enumerate hydrogen atom, halogen atom, nitro, cyano group, hydroxyl, amino, carboxyl, sulfonic group, carbon number be 1～20 alkyl, alkylhalide group, alkoxy, alkoxy alkoxy, aryloxy group, alkyl monosubstituted amino, dialkyl amido, aralkyl, aryl, heteroaryl, alkyl sulfenyl or artyl sulfo, also can be independently of one another form ring except aromatic ring by concatenating group.M can enumerate metallic atom, 3 valencys, one substituted metal atom, 4 valencys, two substituted metal atoms or the oxygen metallic atom of 2 hydrogen atoms, divalent.
[changing 2]
[changing 3]
This compound can be used as commercially available product and obtains, and for example can enumerate hillside plot chemical industry system TAP-2, TAP-5, TAP-9, TAP-10, TAP-12, Mitsui Chemicals system PD-319, PD-311.
The content that neon blocks pigment preferably is adjusted into, and the wavelength region may of the Wavelength-selective absorption filter of gained below the above 620nm of 550nm has precipitous absorption, and the transmitance under the maximum absorption wavelength reaches below 30%.Specifically, be preferably on the transparent base, with 0.001g/m
2Above 0.1g/m
2Following scope exists neon to block pigment.
Among the present invention, wavelength selective absorption layers is made of single or multiple lift and forms.As wavelength selective absorption layers, preferably be made as and in identical overlay, mix existence with the individual layer formation of two (trifluoromethane sulfonyl group) imidic acid as aromatic series two imido class pigments (a), porphyrin class pigment or two kinds of pigments of aza porphyrin class pigment (b) of counterion.
Among the present invention; in the wavelength selective absorption layers of individual layer; must adopt with the aromatic series two imido class pigments of two (trifluoromethane sulfonyl group) imidic acid as near infrared absorbing coloring matter as counterion; blocking pigment as neon must adopt the reason of porphyrin class pigment or aza porphyrin class pigment to be; be present in the identical overlay by these two kinds of pigments are mixed, can obtain to improve the effect of the permanance of this wavelength selective absorption layers.And; though it is still indeterminate to improve the mechanism of permanance; but can infer and be; certain interaction takes place with aza porphyrin class pigment (or porphyrin class pigment) in two (trifluoromethane sulfonyl group) imidic acids as the counterion of two imido class pigments, can suppress the deterioration of the pigment that caused by humidity and temperature.
In addition, among the present invention, as wavelength selective absorption layers, can use and block the multilayer that layer forms by the neon that on transparent base, forms the near infrared ray absorption layer that contains resin and near infrared absorbing coloring matter (A) successively, contains resin and pigment (B) and constitute a wavelength selective absorption layers that forms.As wavelength selective absorption layers; by be made as with contain separately respectively with two (trifluoromethane sulfonyl group) imidic acid as folding layer by layer of the aromatic series two imido class pigments (a) of counterion and porphyrin class pigment or aza porphyrin class pigment (b) multilayer constitute, also can obtain the effect of improving of permanance with the wavelength selective absorption layers of individual layer in the same manner.Its reason is still indeterminate, interact between pigment (a) and pigment (b) yet block near infrared ray absorption layer and neon on the interface of layer, and on described interface, cause moving of pigment, can obtain and the identical effect of situation that in identical layer, has pigment (a) and pigment (b).
Aza porphyrin class pigment (or porphyrin class pigment) preferably contains more than 5 mass parts with respect to two imido class pigments, 100 mass parts, more preferably more than 10 mass parts.Preferred 100 mass parts of the upper limit are more preferably below 50 mass parts.Be not under the situation of preferred range at the ratio with respect to aromatic series two imido class pigments such as aza porphyrin class pigment, do not produce described interaction, thereby the situation of the raising that is difficult to obtain permanance is arranged.
Among the present invention, near infrared absorbing coloring matter or neon block pigment by to be dispersed or dissolved in the state in the resin, utilize rubbing method to be laminated on the transparent base.As resin, so long as near infrared absorbing coloring matter or neon can be blocked the resin that pigment dissolves equably or disperses, just be not particularly limited, yet can use polyesters, acrylic compounds, polyamide-based, polyurethanes, polyolefins, polycarbonate-based resin rightly.Wherein, preferred good acrylic resin aspect the transparency when hybrid pigment, thermotolerance, the solvent resistance; particularly under the situation of using the two imido class pigments that have two (trifluoromethane sulfonyl group) imidic acids as counterion; from considering, preferably adopt acrylic resin with the connecting airtight property of base material or with the viewpoint of the compatibility of pigment.
In addition, the glass temperature of described resin is preferably used more than the operational support temperature of machine of Wavelength-selective absorption filter.When the glass temperature of described resin when the serviceability temperature of the machine that uses Wavelength-selective absorption filter is following, then be scattered in reaction easily between the pigment in the resin, and resin absorbs the moisture in the extraneous gas etc., it is big that the deterioration of pigment or resin becomes.In addition, among the present invention, the glass temperature of resin is as long as more than the serviceability temperature of the machine that uses Wavelength-selective absorption filter, just be not particularly limited, yet preferred especially more than 85 ℃ below 160 ℃.
The glass temperature of described resin less than 85 ℃ situation under, can cause the interaction of pigment and resin, the interaction between pigment etc., chromatogenous sex change.In addition, under glass temperature surpasses 160 ℃ situation, with this resin dissolves in solvent, when coating on the transparent base, if carry out sufficient drying, then must be made as high temperature, thereby produce the deterioration of the bad and pigment of planarity that the hot fold by base material causes.In addition, at low temperatures under the dry situation, owing in drying, need for a long time, so the productivity variation, it is bad that productivity becomes.In addition, also might be dry fully, under solvent residues in situation in filming in large quantities, identical when the serviceability temperature of the machine that uses Wavelength-selective absorption filter is following with described glass temperature, can cause the sex change of two imido salt pigments of poor durability.
Using layer to constitute under the situation of the wavelength selective absorption layers that forms by multilayer, because it is different with two imido salt pigments that neon blocks resin used in the layer, porphyrin class pigment or aza porphyrin class pigment (b) are from good in the permanance aspect, so the influence of the glass temperature of resin or drying condition is little.But, blocking resin used in the layer as neon, used under the situation of the strong resin of the polarity of amine and so on, blocked at neon on the interface of layer and the near infrared ray absorption layer that contains two imido salt pigments, had the situation of the permanance deterioration that makes two imido salt pigments.
As blocking resin used in the layer, can use polyesters, acrylic compounds, polyamide-based, polyurethanes, polyolefins, polycarbonate-based resin rightly at the neon that does not contain two imido salt pigments.In the middle of these resins, the transparency during preferred hybrid pigment, the acrylic resin that the thermotolerance aspect is good.In addition, in fitting, also bonding agent can be used as resin with antireflection film, glass, anti electromagnetic wave film.
As bonding agent, can enumerate known acrylic-based adhesives, silicon class bonding agent, carbamates bonding agent, polyvinyl butyral bonding agent (PVB), ethene-vinyl acetate class bonding agent (EVA) etc., polyvinylether, saturated amorphous polyester, melamine resin etc.In the middle of these bonding agents, consider preferred acrylic adhesives from the viewpoint of the transparency.
Acrylic adhesives is for example by constituting with the resin as main body such as acrylate or methacrylate.In addition, for bonding agent, also can be as required, for example one or more of the crosslinking chemical of metal complex class, isocyanates, epoxies are mixed together use as rigidizer and described resin of binding property.
The amount of the near infrared absorbing coloring matter in the wavelength selective absorption layers is with respect to more than the preferred 1 quality % of resin below the 10 quality %.Under the less situation of the amount of the near infrared absorbing coloring matter in resin, in order to realize required near-infrared absorbing ability, just need to increase the coating amount of wavelength selective absorption layers, just need high temperature and/or long-time for carrying out sufficient drying with it together, cause that easily the planarity of the deterioration of pigment or base material is bad.On the contrary, under the more situation of the amount of the near infrared absorbing coloring matter in resin, the interaction grow between pigment, even reduced residual solvent, also cause easily pigment through the time sex change.
Among the present invention, to constitute the wavelength selective absorption layers that forms be that the coating fluid A that will contain organic solvent, resin, the fragrant same clan two imido class pigments (a), porphyrin class pigment or aza porphyrin class pigment (b) coats on the transparent base by the layer of individual layer, is dried to form.In addition, constitute the wavelength selective absorption layers that forms and comprise by the layer of multilayer: near infrared ray absorption layer, it is that the coating fluid B that will contain organic solvent, resin and aromatic series two imido class pigments (a) coats on the transparent base, is dried to form; Neon blocks layer, and it is that coating contains the coating fluid C of organic solvent and resin, porphyrin class pigment or aza porphyrin class pigment (b), is dried to form above this near infrared ray absorption layer tight.
At this moment, preferably contain surfactant among described coating fluid A or the B.In addition, though in coating fluid C, also can contain surfactant,, also can not contain surfactant using under the situation of bonding agent as resin.
By containing surfactant in the coating fluid used in the formation of wavelength selective absorption layers, just can improve the coating outward appearance of wavelength selective absorption layers, particularly can improve by coming off of causing of small bubble, by foreign matter etc. adhere to the depression that causes, the spring in the drying process is spattered.Heat treated when in addition, the surfactant in the wavelength selective absorption layers (coating layer) can be because of coating layer dry is oozed out to the surface.Consequently, can give sliding to the surface of coating layer.In addition, do not form concave-convex surface even do not contain the particle of the deterioration reason that becomes the transparency in wavelength selective absorption layers or opposing face, it is good that the property handled becomes, the easier drum that is wound as.
Among the present invention, the HLB of surfactant is to be crucial below 12 more than 2.The lower limit of HLB preferred 3, preferred especially 4.On the other hand, the higher limit of HLB preferred 11, preferred especially 10.Under the low situation of HLB, because of the deficiency of surfactivity ability, levelability will be not enough.On the contrary, under the high situation of HLB, not only sliding deficiency, and wavelength selective absorption layers absorbs moisture easily, makes the ageing stability of two imido class pigments become bad.
And, the Hydorophil Lyophile Balance of the W.C.Griffin name of the Atlas Powder company that so-called HLB is the U.S., be the balance of hydrophilic group contained in the molecule with surfactant and lipophilic group as the characteristic value indexing value, this value is low more, then lipophilicity is high more, on the contrary, the high more then water wettability of this value is high more.
The content of surfactant is important with respect to the resin that constitutes wavelength selective absorption layers below 2 quality % more than the 0.01 quality %.Under the less situation of the content of surfactant, the raising of coating outward appearance or the effect deficiency of giving sliding, on the contrary, under more situation, wavelength selective absorption layers absorbs moisture easily, promotes the deterioration of pigment.
Surfactant can use material known such as cationic, anionic species, nonionic class rightly, from considering with the problems such as deterioration of near infrared absorbing coloring matter, preferably do not have the nonionic class of polar group, the silicon class that more preferably the surfactivity ability is good or fluorine class surfactant.
As silicon class surfactant, can enumerate dimethyl-silicon, amino silane, acrylic silane, the vinyl benzyl base silane, the vinyl benzyl amino silane, diglycidyl silane, hydrosulphonyl silane, dimethylsilane, dimethyl silicone polymer, poly-oxyalkylsiloxane, the hydrogenated diene modified polyorganosiloxane, the vinyl modified siloxane, the hydroxyl modification siloxane, amino modified siloxane, carboxy-modified siloxane, the halogenation modified siloxane, the epoxy radicals modified siloxane, the methacryloxy modified siloxane, sulfhydryl modified siloxane, the fluorine modified siloxane, alkyl-modified siloxane, phenyl modified siloxane, alkylene oxide modified siloxane etc.
As fluorine class surfactant, can enumerate tetrafluoroethylene, perfluoroalkyl ammonium salt, perfluoro alkyl sulfonic acid acid amides, perfluoro alkyl sulfonic acid sodium, perfluoroalkyl sylvite, perfluoroalkyl carboxylate, fluorinated alkyl sulfonate, perfluoroalkyl ethylene oxide adduct, perfluoroalkyl leptodactyline, the amino sulfonate of perfluoroalkyl, perfluoralkyl phosphate, perfluoroalkyl alkylate, perfluoroalkyl alkyl betaine, perfluoroalkyl halogenation thing etc.
Among the present invention, wavelength selective absorption layers is that the coating fluid that will contain resin, near infrared absorbing coloring matter, surfactant is coated with drying and stacked on transparent base, and this coating fluid is considered from the viewpoint of screening characteristics, need utilize organic solvent diluting.
As this organic solvent, can alcohols such as (1) methyl alcohol, ethanol, n-propanol, isopropyl alcohol, normal butyl alcohol, tridecanol, cyclohexanol, 2-methyl cyclohexanol be shown example; (2) ethylene glycol, diglycol, triethylene glycol, polyglycol, propylene glycol ,-glycols such as the dipropylene glycol that contracts, glycerine; (3) glycol ethers such as glycol monoethyl ether, the inferior ether of glycol monomethyl, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, butyl carbitol, ethylene glycol monomethyl ether acetate, glycol monomethyl ethylhexoate, glycol monomethyl butylacetic acid ester, diglycol monotertiary methyl acetic acid ester, diglycol monotertiary ethylhexoate, diglycol monotertiary butylacetic acid ester; (4) ester classes such as ethyl acetate, the inferior isopropyl ester of acetate, n-butyl acetate; (5) ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, cyclopentanone, isophorone, diacetone alcohol can perhaps be use mixing two or more they independent uses.
Preferably with respect to employed whole organic solvents in the coating fluid, contain the following good ketone aspect the dissolubility of pigment of the above 80 quality % of 30 quality %, other organic solvent is preferably considered levelability, drying property and is selected.In addition, the boiling point of organic solvent is preferred more than 60 ℃ below 180 ℃.Under low-boiling situation, the solid formation branch concentration of coating fluid changes in the coating, and applied thickness is difficult to stabilization.On the contrary, under the high situation of boiling point, the organic solvent amount that remains in filming increases, and it is bad that ageing stability becomes.
As with near infrared absorbing coloring matter and resin dissolves or be scattered in method in the organic solvent, can enumerate the method for stirring, dispersion and pulverizing under heating.By heating, can improve pigment and dissolving resin, can prevent the harmful effect that causes by dissolved matter not etc. to the coating outward appearance.In addition,, resin and pigment are scattered in the coating fluid with the graininess below the 0.3 μ m, just can form the good layer of the transparency by disperseing and pulverizing.As dispersion machine and comminutor, can use known machine, specifically, can enumerate bowl mill, sand mill, horizontal pulverizer (ア ト ラ イ -), edge runner, stirrer (agitator), colloid mill, ultrasonic homogenizer, homomixer, ball mill, wet type airslide disintegrating mill, coating oscillator, butterfly stirring machine, planetary stirring machine, Henschel stirring machine etc.
Therefore in coating fluid, exist under the situation of dust or the not dissolved matter more than the 1 μ m,, before being coated with, need remove with filtrator etc. because the outward appearance after the coating becomes bad.As filtrator, can use various filtrators rightly, however the preferred dust of the size of removing 1 μ m more than 99% or the filtrator of dissolved matter not of using.Be coated with the dust that contains more than the 1 μ m or not dissolved matter coating fluid and under the situation about being dried, around it, can produce depression etc., form the defective of the following size of the above 1000 μ m of 100 μ m sometimes.
Solid the branchs concentration that forms such as contained resin and pigment preferably is made as more than the 10 quality % below the 30 quality % in the coating fluid.Divide under the low situation of concentration solid formation, not only need time of spending many in the drying after coating, the productivity variation, and also the quantity of solvent that remains in filming increases, and it is bad that ageing stability becomes.On the contrary, divide under the high situation of concentration solid formation, the viscosity of coating fluid uprises, and the levelability deficiency makes the coating outward appearance become bad.Consider that from the aspect of coating outward appearance preferably the viscosity with coating fluid is adjusted into below the above 300cps of 10cps, preferably will form branch concentration, organic solvent etc. admittedly and be adjusted into this scope that reaches.
Among the present invention, as the method for wavelength selective absorption layers being coated on the transparent base, can use the intaglio printing coating method rightly, lick the mode of being coated with, impregnation method, spraying method, curtain-type coating method, air knife coating method, scraper plate coating method, contrary roller coat cover used method usually such as mode, excellent coating method, lip-coat coating method.In the middle of them, the intaglio printing coating method that preferably can be coated with equably, preferred especially reverse gravure mode.In addition, below the preferred 80mm of the diameter of intaglio plate.Under the bigger situation of diameter, the frequency that produces the fluctuating striped in flow direction can increase.
The dried coating weight of wavelength selective absorption layers is not particularly limited, however the preferred 1g/m of lower limit
2, more preferably 3g/m
2, the preferred 50g/m of the upper limit
2, more preferably 30g/m
2Under the less situation of dried coating weight, it is not enough that near infrared receptivity becomes easily.When increasing the amount of the near infrared absorbing coloring matter in the resin, the pigment quantitative change that then is present on the interface of surface and fixed bed is many, is subjected to the influence of the resin of extraneous gas or fixed bed easily for this reason.Consequently, cause the deterioration of pigment etc. easily, it is bad that ageing stability becomes.On the contrary, under the more situation of dried coating weight, though near infrared receptivity is very abundant, the transparency in the visible region reduces, and the brightness of display reduces.When reducing the amount of the near infrared absorbing coloring matter in the resin, though then can regulate optical characteristics, it is insufficient that drying becomes easily for this reason.Consequently, the ageing stability of pigment becomes bad because of the residual solvent in filming.On the other hand, carrying out fully under the dry situation, the planarity of base material becomes bad.
As coating fluid is coated with on transparent base, dry method, can enumerate known heated-air drying, infrared heater etc., however the preferred fast heated-air drying of rate of drying.
The stage of the constant rate of drying at the initial stage after coating is preferably in more than 20 ℃ below 80 ℃, use 2m/ second～hot blast of 30m/ second comes dry.Carry out under the situation of initial stage drying (hot blast temperature height, the air quantity of hot blast is big) the small defective that be easy to generate that the small coating shedding that derives from bubble, small spring spatter, crack etc. filmed on high strength ground.On the contrary, under the situation of the initial stage drying of making weak (hot blast temperature is low, and the air quantity of hot blast is little),, expensive drying time, aspect cost, problem is arranged though outward appearance becomes well.In coating fluid, do not add under the situation of surfactant, be easy to generate described small defective, need weaken the initial stage drying widely.
In the operation of falling rate of drying, need be made as the temperature higher than the initial stage drying, reduce the solvent in filming, preferred temperature is more than 120 ℃ below 180 ℃.Particularly preferred lower limit is 140 ℃, and higher limit is 170 ℃.Under the lower situation of temperature, be difficult to reduce the solvent in filming, become residual solvent, make pigment through the time stability become not enough.On the contrary, be made as under the situation of high temperature, not only the planarity of base material becomes bad because of hot fold, and near infrared absorbing coloring matter is because of the heat deterioration.In addition, as by the time, preferred more than 5 seconds below 180 seconds.Under short situation of time, residual solvent becomes many in filming, and it is bad that ageing stability becomes, and on the contrary, under long situation of time, not only productivity becomes bad, and produces hot fold in base material, and it is bad that planarity becomes.Consider that from the viewpoint of productivity and planarity the upper limit by the time especially preferably was made as 30 seconds.
In the terminal stage of drying, preferably hot blast temperature is made as below the glass temperature of resin, become below the glass temperature of resin with the actual temperature of state stably base material.Still keeping high temperature ground to take out under the situation of drying oven, can become bad, situations such as the damage of generation are not only being arranged, and have the situation of curling that produces in applicator surface slip in the roller surface contacts.
(Wavelength-selective absorption filter)
Among the present invention, so-called Wavelength-selective absorption filter is the optical filter that has very big absorption at wavelength 800～1200nm and wavelength 550～620nm place.Transmitance in the near infrared region of this Wavelength-selective absorption filter below the above 1200nm of wavelength 800nm is low more good more.Specifically, the transmitance of near infrared region is preferred below 20%, and is preferred especially below 10%.Under the high situation of transmitance,, can't prevent to use the misoperation of the e-machine of near infrared ray remote control to the near infrared incomplete absorption that from plasma scope, penetrates.
In addition, the mean transmissivity of visibility region preferably is higher than the mean transmissivity of near infrared region, and preferably below the above 620nm of wavelength 550nm, more preferably in wavelength 570nm～600nm, has precipitous absorption.Specifically, the transmitance under the maximum absorption wavelength in the described wavelength coverage is preferred below 40%, preferred especially below 30%.Under the high situation of transmitance in this zone, will be difficult to obtain the neon light absorption that from plasma scope, to penetrate, make the red good effect of color development.In addition, under the very wide situation of the absorption in this zone,, therefore have the tendency of the brightness reduction of plasma scope because the transmitance of the integral body of visible region reduces.The transmitance of removing the following visible region of the above 620nm of wavelength 550nm is high more good more, preferred more than 50%, preferred especially more than 60%.Under the low situation of transmitance, can hinder the color development of display, form the low image of brightness.
The adjustment of transmitance can utilize the amount of near infrared absorbing coloring matter of coating weight, the per unit area of wavelength selective absorption layers to change.
As the tone of Wavelength-selective absorption filter, when showing with the Lab chromatic diagram, a value is preferred-10.0～+ 10.0, b value preferably-10.0～+ 10.0.If this scope, even then under the situation of the front of being located at plasma scope, also can become Natural color, thereby preferred.
As the method for adjusting tone, can utilize the amount of near infrared absorbing coloring matter of coating weight, per unit area of wavelength selective absorption layers and the mixing of other pigment or the optimization of drying condition to realize.And, exist at the front of Wavelength-selective absorption filter described later or the back side under the situation of the bonding coat that has been colored or other optical filter, comprise also that preferably its ground is adjusted into Natural color with the tone of Wavelength-selective absorption filter.
As the coating outward appearance of wavelength selective absorption layers, must be able to not have maximum gauge is more than the 300 μ m, more preferably the defective of the size of 100 μ m.When being located at the front of plasma scope, it is such that the above defective of 300 μ m will become bright spot, and defective is obviously changed.In addition, the thin striped of overlay, unequally also obviously changed, thereby become problem in the display front.
Even Wavelength-selective absorption filter is preferably placed under high temperature, high humility for a long time, the transmitance of near infrared transmitance, visible light can not change yet.Under the ageing stability condition of poor under high temperature, the high humility, not only the tone of the image of display changes, but also has the situation that the effect of the misoperation of the e-machine that has prevented to use the near infrared ray remote control of the present invention disappears.
Mix existence as the aromatic series two imido class pigments (a) of counterion with porphyrin class pigment or aza porphyrin class pigment (b) by making with two (trifluoromethane sulfonyl group) imidic acid; it is good that ageing stability will become; yet in addition; kind, the thickness of coating layer, drying condition by control used organic solvent in the coating fluid reduces the residual solvent amount in the wavelength selective absorption layers; perhaps, also can make it more good by adjusting the content of the pigment in the resin.
In addition; as previously mentioned; the wavelength selective absorption layers that use is formed by constituting of following multilayer; promptly; on transparent base, form successively to contain resin and to block layer as the near infrared ray absorption layer of the aromatic series two imido class pigments (a) of counterion, the neon that contains resin and porphyrin class pigment or aza porphyrin class pigment (b) and form with two (trifluoromethane sulfonyl group) imidic acid; then considering from the viewpoint of ageing stability, is preferred embodiment.
In addition, the amount of the residual solvent of wavelength selective absorption layers is few more good more, yet preferably is made as below the 3 quality %.If reach below the 3 quality %, then in ageing stability, there is not difference in fact.But, when in order further to reduce the residual solvent amount, when for example drying being made as to harsh condition, the planarity that then can the produce light filter disadvantage such as bad that becomes, in the method for drying under reduced pressure and so on, productivity can reduce.
Among the present invention,, also can on face identical or opposite face, directly or by bonding agent conductive layer be set with the infrared ray absorbing layer for stopping the harmful electromagnetic purpose that from display, penetrates.This conductive layer no matter be to use wire netting still be conductive film which kind of can, under the situation of having used wire netting, need have aperture opening ratio at the wire netting conductive layer more than 50%.If the aperture opening ratio of wire netting is low,, have the problem that light penetration reduces though then electromagnetic wave shielding performance becomes well.Thus, in order to obtain good light penetration, aperture opening ratio need reach more than 50%.As wire netting used among the present invention, also can use the high metal forming of electric conductivity is implemented etch processes and made netted material; Used the net of the textile-like of metal fibre; The fiber that has adhered to metal in gimmicks such as the surface of macromolecular fibre use plated films.Used metal in this electromagnetic wave absorbing layer is so long as the electric conductivity height, have good stability, no matter be which kind of metal can, be not particularly limited, yet consider preferably copper, nickel, tungsten etc. from viewpoints such as processability, costs.
In addition, under the situation of having used conductive film, transparency conducting layer no matter be which kind of conducting film can, yet the preferable alloy oxide.Like this, just can obtain more high visible line transmitance.In addition, among the present invention, under the situation of the conductivity of wanting to improve transparency conducting layer, the repetitive construct more than three layers of preferable alloy oxide/metal/metal oxide.By with metallic multilayerization, just can when keeping higher luminous ray transmitance, obtain electric conductivity.As long as used metal oxide has electric conductivity and luminous ray permeability among the present invention, no matter be which kind of metal oxide can then.As an example, tin oxide, indium oxide, indium tin oxide, zinc paste, titanium dioxide, bismuth oxide etc. are arranged.Being an example more than, is not special qualification.In addition, consider used preferred gold, silver of metal level and contain their compound among the present invention from the viewpoint of electric conductivity.
In addition, under situation, be under three layers the situation for example repeating the number of plies with the conductive layer multiple stratification, the thickness of silver layer preferred 50
～200
, more preferably 50
～100
Under the thicker situation of Film Thickness Ratio, light penetration reduces, and under thinner situation, resistance value will rise.In addition, as the thickness of metal oxide layer, preferred 100
～1000
, more preferably 100
～500
Under the situation thicker than this thickness, will be painted and make tone reversal, under thinner situation, resistance value will rise.In addition, under the situation of carrying out the multiple stratification more than three layers, for example as metal oxide/silver/metal oxide/silver/metal oxide, be made as under five layers the situation, the thickness of the metal oxide at center can be compared to most except that the thickness of the metal oxide layer it bigger.By setting like this, the light penetration of multilayer film integral body will improve.
Among the present invention, also can on the face identical of Wavelength-selective absorption filter or opposite face, directly or by bonding agent anti-reflection layer, anti-glare layer be set with wavelength selective absorption layers.In addition, constitute in the wavelength selective absorption layers that forms, also can block and use resin of binding property in the layer, neon is blocked layer give the function of bonding coat, and be fitted on glass plate, the resin flake, can also directly be fitted on the display at neon at layer by multilayer.In addition, also can form adhesive phase on the surface of the wavelength selective absorption layers of individual layer.
In the Wavelength-selective absorption filter of the present invention,, also the layer with ultraviolet absorption ability can be set for improving sunproof purpose.In order to give ultraviolet absorption ability, as long as in the random layer of wavelength selective absorption layers, transparent base, adhesive phase, anti-reflection layer, anti-glare layer, add ultraviolet light absorber.Ultraviolet light absorber can use material known such as organic class ultraviolet screener, mineral-type ultraviolet screener.
Embodiment
Below, provide embodiments of the invention and comparative example.In addition, the assay method of used characteristic value and Evaluation on effect method are as follows among the present invention.
The viscosity of＜coating fluid 〉
Coating fluid is adjusted to 20 ℃, uses the Brookfield viscometer (BL) of Tokyo measuring instrument system, 60rpm measures with rotor speed.
＜total light penetration, turbidity 〉
(Japanese electric look industry system NDH2000), has been measured total light penetration and turbidity to use turbidimeter.
＜light penetration 〉
Use spectrophotometer (Hitachi's system, U-3500 type), in the scope of wavelength 1100nm～200nm,, indoor air is measured as the reference of transmitance to wavelength selective absorption layers side irradiates light.
＜tone 〉
Use colour difference meter (Japanese electric look industry system, ZE-2000),, adopt illuminant-C, measured a value, the b value of Lab chromatic diagram with 2 degree field angle as standard light to wavelength selective absorption layers side irradiates light.
＜ageing stability 〉
After in the atmosphere of 80 ℃ of temperature, humidity 95%, having placed 48 hours, described transmitance, tone have been measured.As the variable quantity of tone, utilize following formula 1 to obtain Δ E.And the value of Δ E is more little, and the variation of expression tone is few more.
Δ E=√ ((a value before handling-processing back a value)
2+ (b value before handling-processing back b value)
2)
…(1)
In addition, transmitance through the time variation delta T before and after handling utilize following formula 2 to try to achieve.Δ T value is more little, and the expression variable quantity is few more.
Variable quantity (%)=(| the transmitance before the transmitance-processing after the processing | the transmitance the before/processing) * 100
…(2)
＜the outward appearance of filming 〉
(1) tiny flaw
Light filter after the formation wavelength selective absorption layers is positioned on the white film, and following evaluation has been carried out in visualization under the fluorescent light of 3 wavelength.And tiny flaw is the every 100m of instrumentation
2The number of the defective of the size that 300 μ m of area are above is graded according to following judgment standard.
◎: tiny flaw is less than 1
Zero: tiny flaw is more than 1 and less than 5
△: tiny flaw is more than 5 and less than 10
*: tiny flaw is more than 10
(2) coating is bad
For bad having or not of coating such as coating spot, stripeds, be that Wavelength-selective absorption filter is positioned on the white film, visualization wavelength selective absorption layers face under the fluorescent light of 3 wavelength is graded according to following judgment standard.
◎:, can't see that also coating is bad even in mobile Wavelength-selective absorption filter, observe
Zero: when when at mobile Wavelength-selective absorption filter the time, observing, find that a little coating is bad
△: when when at mobile Wavelength-selective absorption filter the time, observing, find that coating is bad
*: even make under the static state of Wavelength-selective absorption filter, also can find to apply bad
＜connecting airtight property 〉
Utilization according to JIS K 5400 8.5.1 regulation determination of test method connecting airtight property.Specifically, use clearance gap to apply 100 cancellate cutting scars from a side of stacked wavelength selective absorption layers as the tool guide of 2mm, with viscose paper jointing tape (Nichiban corporate system " No. 405 ", 24mm is wide) be attached on the cancellate cutting scar face, and after making it fully to adhere to, utilize visual state when vertically drawing stripping to observe with acrylic panel (sumitomo chemical company system " sumipex ") friction.
Zero: do not have the grid of peeling off
△: though there is the grid of peeling off, the grid of peeling off is less than 10
*: the grid more than 10 is peeled off
Embodiment 1
(making of base material)
With intrinsic viscosity is the pet resin input twin shaft screw extruder of 0.62dl/g, melt extrudes with 290 ℃ from T shape mould, on cooling rotating metallic roller, when applying static it is connected airtight curing, has obtained the thin slice that do not stretch.
Then, this thin slice that do not stretch is heated to 90 ℃ with the roll-in drawing machine, has carried out behind the longitudinal stretching with 3.5 times,, make that dried coating weight reaches 0.5g/m on the longitudinal stretching film at the following coating fluid A of the two sided coatings of described longitudinal stretching film
2, make it under wind speed 10m/ second, 120 ℃ hot blast to have formed middle coating layer by 20 seconds.Then, in stenter, be heated to be 140 ℃, after having carried out 3.7 times of cross directional stretchs, it is heat-treated in lax 5%, obtained having the biaxial stretch-formed pet film of middle coating layer on the two sides in 235 ℃ of lower edge width (laterally) direction.The film thickness of gained is 100 μ m, and total light penetration is 90.2%, and turbidity is 0.5%.
(the middle coating layer composition of coating fluid A)
Ion exchange water 50.0 quality %
Isopropyl alcohol 28.9 quality %
Acrylic acid-melamine resin 10.0 quality %
(Japanese Carbide industry (strain) system, A-08 divide concentration Gu form: 46 quality %)
Polyester resin 10.0 quality %
(Japan's weaving system, バ イ ロ Na-Le MD-1250 divides concentration Gu form: 30 quality %)
Poly-methyl methacrylate base class cross-linking agent particle 1.0 quality %
(Japanese catalyzer system, エ Port ス -MA1001)
Silicon class surfactant 0.1 quality %
(Dowconing system, ペ イ Application Star De 32)
(modulation of the coating fluid B that wavelength selective absorption layers is used)
With following mass ratio, with toluene, methyl ethyl ketone, mixed with resin,, after resin dissolves, add pigment and surfactant in the stirring down of heating, stir more than 30 minutes.Then, with the nominal filtering accuracy be the filtrator of 1 μ m will be not dissolved matter remove, modulated coating fluid B.
Toluene 39.995 quality %
Methyl ethyl ketone 40.000 quality %
Acrylic resin 18.776 quality %
(Rayon of Mitsubishi system, BR-80, Tg=105 ℃)
Fragrance two imido class pigments, the 0.695 quality % of the same clan
(Japanese Carlit system CIR1085, counterion: two (trifluoromethane sulfonyl group) imidic acid)
Phthalocyanines pigment 0.357 quality %
(Japanese catalyzer system, IR-10A)
Aza porphyrin class pigment 0.118 quality %
(hillside plot changes into system, TAP-2)
Silicon class surfactant 0.059 quality %
(the Dowconing system, ペ イ Application Star De 57, HLB=6.7)
(making of Wavelength-selective absorption filter)
(divide concentration Gu form: 20 quality % with described coating fluid B, viscosity: 40cps) use diameter as the oblique line intaglio plate of 60cm oppositely be coated in described in the middle of a side of coating layer, make the transmitance of dried 950nm reach 4.3% and (be expressed as 8.0g/m with dried coating weight
2), under 40 ℃, the hot blast of 5m/ second, make it by 20 seconds, under 150 ℃, the hot blast of 20m/ second, make it by 20 seconds, under 90 ℃, the hot blast of 20m/ second, make it to be dried then by 10 seconds, obtained Wavelength-selective absorption filter.And the aromatic series two imido class pigments (a) in the wavelength selective absorption layers are (a)/(b)=100/17 with the mass ratio of aza porphyrin class pigment (b).
The Wavelength-selective absorption filter of gained is strong in the absorption of near infrared region, and the transmitance height in the visible region has precipitous absorption in addition near 590nm.In addition, ageing stability or coating outward appearance are also good.
The kind of pigment used in the wavelength selective absorption layers is shown in the table 1, the rerum natura of the Wavelength-selective absorption filter of gained is shown in table 2 and the table 3.
Embodiment 2
Except having used following coating fluid C, obtained Wavelength-selective absorption filter in the same manner with embodiment 1.And the aromatic series two imido class pigments (a) in the wavelength selective absorption layers are (a)/(b)=100/17 with the mass ratio of aza porphyrin class pigment (b).
(modulation of the coating fluid C that wavelength selective absorption layers is used)
With following mass ratio, with toluene, cyclopentanone, mixed with resin,, after resin dissolves, add pigment and surfactant in the stirring down of heating, stir more than 30 minutes.Then, with the nominal filtering accuracy be the filtrator of 1 μ m will be not dissolved matter remove, modulated coating fluid C.
Toluene 40.088 quality %
Cyclohexanone 40.088 quality %
Copolymer polyester resin 18.776 quality % with fluorene skeleton
(Canebo system, O-PET, Tg=150 ℃)
Fragrance two imido class pigments, the 0.695 quality % of the same clan
(Japanese Carlit system CIR1085, counterion: two (trifluoromethane sulfonyl group) imidic acid)
Phthalocyanines pigment 0.176 quality %
(Japanese catalyzer system, IR-12)
Aza porphyrin class pigment 0.118 quality %
(hillside plot changes into system, TAP-2)
Silicon class surfactant 0.059 quality %
(the Dowconing system, ペ イ Application Star De 57, HLB=6.7)
The Wavelength-selective absorption filter of gained is identical with embodiment 1, and the absorption of near infrared region is strong, and the transmitance height in the visible region has precipitous absorption in addition near 590nm.In addition, ageing stability or coating outward appearance are also good.But, slightly bad with the connecting airtight property of base material.
The kind of pigment used in the wavelength selective absorption layers is shown in the table 1, the rerum natura of the Wavelength-selective absorption filter of gained is shown in table 2 and the table 3.
Comparative example 1
Except having used following coating fluid D, obtained Wavelength-selective absorption filter in the same manner with embodiment 1.
(modulation of the coating fluid D that wavelength selective absorption layers is used)
With following mass ratio, with toluene, methyl ethyl ketone, mixed with resin,, after resin dissolves, add pigment and surfactant in the stirring down of heating, stir more than 30 minutes.Then, with the nominal filtering accuracy be the filtrator of 1 μ m will be not dissolved matter remove, made coating fluid D.
Toluene 39.998 quality %
Methyl ethyl ketone 39.998 quality %
Acrylic resin 18.825 quality %
(Rayon of Mitsubishi system, BR-80)
Fragrance two imido class pigments, the 0.697 quality % of the same clan
(Japanese Carlit system, CIR1085, counterion: two (trifluoromethane sulfonyl group) imidic acid)
Phthalocyanines pigment 0.358 quality %
(Japanese catalyzer system, IR-10A)
Squarilium class pigment 0.065 quality %
(consonance fermentation system, SD184)
Silicon class surfactant 0.059 quality %
(the Dowconing system, ペ イ Application Star De 57, HLB=6.7)
The Wavelength-selective absorption filter of gained is identical with embodiment 1, and the absorption of near infrared region is strong, and the transmitance height in the visible region has precipitous absorption in addition near 590nm.But ageing stability is bad.
The kind of pigment used in the wavelength selective absorption layers is shown in the table 1, the rerum natura of the Wavelength-selective absorption filter of gained is shown in table 2 and the table 3.
Comparative example 2
Except having used following coating fluid E, obtained Wavelength-selective absorption filter in the same manner with embodiment 1.And the aromatic series two imido class pigments (a) in the wavelength selective absorption layers are (a)/(b)=100/19 with the mass ratio of aza porphyrin class pigment (b).
(modulation of the coating fluid E that wavelength selective absorption layers is used)
With following mass ratio, with toluene, methyl ethyl ketone, mixed with resin,, after resin dissolves, add pigment and surfactant in the stirring down of heating, stir more than 30 minutes.Then, with the nominal filtering accuracy be the filtrator of 1 μ m will be not dissolved matter remove, made coating fluid E.
Toluene 40.002 quality %
Methyl ethyl ketone 40.002 quality %
Acrylic resin 18.839 quality %
(Rayon of Mitsubishi system, BR-80)
Fragrance two imido class pigments, the 0.622 quality % of the same clan
(Japanese catalyzer system IRG022, counterion: hexafluoro-antimonic acid)
Phthalocyanines pigment 0.358 quality %
(Japanese catalyzer system, IR-10A)
Aza porphyrin class pigment 0.118 quality %
(hillside plot changes into system, TAP-2)
Silicon class surfactant 0.059 quality %
(the Dowconing system, ペ イ Application Star De 57, HLB=6.7)
The Wavelength-selective absorption filter of gained is identical with embodiment 1, and the absorption of near infrared region is strong, and the transmitance height in the visible region has precipitous absorption in addition near 590nm.But ageing stability is bad.
The kind of pigment used in the wavelength selective absorption layers is shown in the table 1, the rerum natura of the Wavelength-selective absorption filter of gained is shown in table 2 and the table 3.
Embodiment 3
(modulation of the coating fluid F that the near infrared ray absorption layer in the wavelength selective absorption layers is used)
With following mass ratio, with toluene, methyl ethyl ketone, mixed with resin,, after resin dissolves, add pigment and surfactant in the stirring down of heating, stir more than 30 minutes.Then, with the nominal filtering accuracy be the filtrator of 1 μ m will be not dissolved matter remove, modulated coating fluid F.
Toluene 40.056 quality %
Methyl ethyl ketone 40.057 quality %
Acrylic resin 18.776 quality %
(Rayon of Mitsubishi system, BR-80, Tg=105 ℃)
Fragrance two imido class pigments, the 0.695 quality % of the same clan
(Japanese Carlit system, CIR1085, counterion: two (trifluoromethane sulfonyl group) imidic acid)
Phthalocyanines pigment 0.357 quality %
(Japanese catalyzer system, IR-10A)
Silicon class surfactant 0.059 quality %
(the Dowconing system, ペ イ Application Star De 57, HLB=6.7)
(neon in the wavelength selective absorption layers blocks the modulation of the coating fluid G of layer usefulness)
After following mass ratio mixing, stir more than 30 minutes.Then, with the nominal filtering accuracy be the filtrator of 1 μ m will be not dissolved matter remove, modulated coating fluid G.
Methyl ethyl ketone 49.808 quality %
Acrylic adhesives 49.847 quality %
(always grind the chemistry system, SK ダ イ Application 1435 divides 30 weight % Gu form)
Aza porphyrin class pigment 0.045 quality %
(hillside plot changes into system, TAP-2)
Rigidizer 0.150 quality %
(always grinding the chemistry system, L-45)
Rigidizer 0.150 quality %
(always grinding the chemistry system, TD-75)
(making of Wavelength-selective absorption filter)
On the middle coating layer formation face that obtains in the same manner with embodiment 1, use diameter oppositely to apply described coating fluid F as the oblique line intaglio plate of 60cm, make the transmitance of dried 950nm reach 4.3% and (be expressed as 8.0g/m with dried coating weight
2), under 40 ℃, the hot blast of 5m/ second, make it by 20 seconds, under 150 ℃, the hot blast of 20m/ second, make it by 20 seconds, under 90 ℃, the hot blast of 20m/ second, make it to be dried then by 10 seconds, formed near infrared ray absorption layer.Then, use lip-coater that described coating fluid G is coated on the near infrared ray absorption layer, make dried coating amount reach 16g/m
2, under 40 ℃, the hot blast of 5m/ second, make it by 20 seconds, under 150 ℃, the hot blast of 20m/ second, make it by 20 seconds, under 90 ℃, the hot blast of 20m/ second, make it to be dried then by 10 seconds, form neon and blocked layer.That is, obtained having by near infrared ray absorption layer and neon and blocked the two-layer Wavelength-selective absorption filter that constitutes the wavelength selective absorption layers that forms of layer.And the aromatic series two imido class pigments (a) in the wavelength selective absorption layers are (a)/(b)=100/17 with the mass ratio of aza porphyrin class pigment (b).
The Wavelength-selective absorption filter of gained is strong in the absorption of near infrared region, and the transmitance height in the visible region has precipitous absorption in addition near 590nm.In addition, ageing stability or coating outward appearance are also good.
The kind of pigment used in the wavelength selective absorption layers is shown in the table 1, the rerum natura of the Wavelength-selective absorption filter of gained is shown in table 2 and the table 3.
[table 1]
[table 2]
[table 3]
Wavelength-selective absorption filter of the present invention is because the transmitance near infrared region and neon light zone is low, the transmitance height of visible region, and optical characteristics through the time with low uncertainty, permanance is good, therefore by being located at the front of plasma scope, can stably show image well, and, can prevent to use the misoperation of the precision machinery of near infrared ray remote control, have very great help for industrial circle.
Claims (8)
1. Wavelength-selective absorption filter, be on transparent base, the stacked wavelength selective absorption layers that contains the single or multiple lift of resin, near infrared absorbing coloring matter (A) and pigment (B) forms, and the Wavelength-selective absorption filter that has very big absorption at wavelength 800～1200nm and wavelength 550～620nm place, it is characterized in that
The a kind of of described near infrared absorbing coloring matter (A) is with the aromatic series two imido class pigments (a) of two (trifluoromethane sulfonyl group) imidic acids as counterion,
The a kind of of described pigment (B) is porphyrin class pigment or aza porphyrin class pigment (b).
2. Wavelength-selective absorption filter according to claim 1, it is characterized in that the wavelength selective absorption layers of multilayer is that the neon that forms the near infrared ray absorption layer contain resin and near infrared absorbing coloring matter (A) successively on transparent base, contain resin and pigment (B) blocks layer and forms.
3. Wavelength-selective absorption filter according to claim 1, it is characterized in that, wavelength selective absorption layers contains described porphyrin class pigment or described aza porphyrin class pigment (b) 5～100 mass parts (mass ratio) with respect to described aromatic series two imido class pigments (a) 100 mass parts.
4. Wavelength-selective absorption filter according to claim 1 is characterized in that, the resin that constitutes wavelength selective absorption layers is an acrylic resin.
5. Wavelength-selective absorption filter according to claim 1, it is characterized in that, the wavelength selective absorption layers of individual layer is on described transparent base, coating contains the coating fluid A of organic solvent, resin, the fragrant same clan two imido class pigments (a), porphyrin class pigment or aza porphyrin class pigment (b), is dried to form.
6. Wavelength-selective absorption filter according to claim 1, it is characterized in that, the wavelength selective absorption layers of multilayer comprises: near infrared ray absorption layer, it is on described transparent base, coating contains the coating fluid B of organic solvent, resin and aromatic series two imido class pigments (a), is dried to form; Neon blocks layer, and it is that coating contains the coating fluid C of organic solvent and resin, porphyrin class pigment or aza porphyrin class pigment (b), is dried to form above this near infrared ray absorption layer tight.
7. according to claim 5 or 6 described Wavelength-selective absorption filters, it is characterized in that it is 2～12 surfactant that coating fluid A or B also contain HLB.
8. Wavelength-selective absorption filter according to claim 7 is characterized in that, surfactant is silicon class surfactant or fluorine class surfactant.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP381283/2004 | 2004-12-28 | ||
| JP2004381283 | 2004-12-28 |
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| CNB2005800426821A Expired - Fee Related CN100495082C (en) | 2004-12-28 | 2005-12-26 | Wavelength-selective absorption filter |
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|---|---|
| KR (1) | KR100761646B1 (en) |
| CN (1) | CN100495082C (en) |
| TW (1) | TWI296650B (en) |
| WO (1) | WO2006070717A1 (en) |
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| KR100780390B1 (en) * | 2007-07-06 | 2007-11-28 | (주)제이피에스 마이크로텍 | The synthesis method of near infrared dye and solution on capsulated with polymer resin |
| KR101102356B1 (en) * | 2009-07-15 | 2012-01-03 | 한국과학기술원 | Method and Apparatus for Controlling Sleep Mode in Wireless Communication Networks |
| KR101969612B1 (en) | 2011-10-14 | 2019-04-16 | 제이에스알 가부시끼가이샤 | Optical filter, solid state image-capturing device using same, and camera module using same |
| CN105122095B (en) * | 2013-04-10 | 2017-07-21 | 旭硝子株式会社 | Infrared ray masking wave filter, solid-state imager, camera device and display device |
| JP6966850B2 (en) * | 2016-03-18 | 2021-11-17 | 日東電工株式会社 | An optical member, and a backlight unit and a liquid crystal display device using the optical member. |
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| JP2000081511A (en) * | 1998-06-30 | 2000-03-21 | Nippon Kayaku Co Ltd | Ir cut filter |
| JP2001264532A (en) * | 2000-03-15 | 2001-09-26 | Toyobo Co Ltd | Infrared ray absorbing filter |
| CN1234107C (en) * | 2000-02-01 | 2005-12-28 | 三井化学株式会社 | Filter for displaying, display unit and production method therefor |
| EP1403666A4 (en) * | 2001-07-04 | 2008-04-16 | Nippon Kayaku Kk | Diimonium salt compound, near-infrared absorbing filter and optical information recording medium using the same |
| JP2004264805A (en) * | 2002-06-10 | 2004-09-24 | Mitsubishi Chemicals Corp | Filter for electronic display and electronic display device using the filter |
| JP2005258170A (en) * | 2004-03-12 | 2005-09-22 | Asahi Glass Co Ltd | Optical film and its manufacturing method |
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2005
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| KR20060120586A (en) | 2006-11-27 |
| TWI296650B (en) | 2008-05-11 |
| TW200630470A (en) | 2006-09-01 |
| KR100761646B1 (en) | 2007-09-27 |
| WO2006070717A1 (en) | 2006-07-06 |
| CN101076746A (en) | 2007-11-21 |
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