CN1771269A - Adhesive film functionalizing color compensation and near infrared ray (nir) blocking and plasma display panel filter using the same - Google Patents

Adhesive film functionalizing color compensation and near infrared ray (nir) blocking and plasma display panel filter using the same Download PDF

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CN1771269A
CN1771269A CNA2005800001605A CN200580000160A CN1771269A CN 1771269 A CN1771269 A CN 1771269A CN A2005800001605 A CNA2005800001605 A CN A2005800001605A CN 200580000160 A CN200580000160 A CN 200580000160A CN 1771269 A CN1771269 A CN 1771269A
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film
replacement
chemical formula
near infrared
infrared ray
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CN100551942C (en
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崔玹硕
朴相炫
李渊权
黄仁皙
金正斗
赵显珠
李东郁
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LG Corp
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    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01JELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J11/00Gas-filled discharge tubes with alternating current induction of the discharge, e.g. alternating current plasma display panels [AC-PDP]; Gas-filled discharge tubes without any main electrode inside the vessel; Gas-filled discharge tubes with at least one main electrode outside the vessel
    • H01J11/20Constructional details
    • H01J11/34Vessels, containers or parts thereof, e.g. substrates
    • H01J11/44Optical arrangements or shielding arrangements, e.g. filters, black matrices, light reflecting means or electromagnetic shielding means
    • GPHYSICS
    • G02OPTICS
    • G02BOPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00Optical elements other than lenses
    • G02B5/20Filters
    • G02B5/208Filters for use with infrared or ultraviolet radiation, e.g. for separating visible light from infrared and/or ultraviolet radiation
    • GPHYSICS
    • G02OPTICS
    • G02BOPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00Optical elements other than lenses
    • G02B5/20Filters
    • G02B5/22Absorbing filters
    • G02B5/223Absorbing filters containing organic substances, e.g. dyes, inks or pigments
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01JELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J9/00Apparatus or processes specially adapted for the manufacture, installation, removal, maintenance of electric discharge tubes, discharge lamps, or parts thereof; Recovery of material from discharge tubes or lamps
    • H01J9/20Manufacture of screens on or from which an image or pattern is formed, picked up, converted or stored; Applying coatings to the vessel
    • H01J9/205Applying optical coatings or shielding coatings to the vessel of flat panel displays, e.g. applying filter layers, electromagnetic interference shielding layers, anti-reflection coatings or anti-glare coatings
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01JELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J2211/00Plasma display panels with alternate current induction of the discharge, e.g. AC-PDPs
    • H01J2211/20Constructional details
    • H01J2211/34Vessels, containers or parts thereof, e.g. substrates
    • H01J2211/44Optical arrangements or shielding arrangements, e.g. filters or lenses
    • H01J2211/444Means for improving contrast or colour purity, e.g. black matrix or light shielding means
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01JELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J2211/00Plasma display panels with alternate current induction of the discharge, e.g. AC-PDPs
    • H01J2211/20Constructional details
    • H01J2211/34Vessels, containers or parts thereof, e.g. substrates
    • H01J2211/44Optical arrangements or shielding arrangements, e.g. filters or lenses
    • H01J2211/448Near infrared shielding means

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  • Engineering & Computer Science (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Toxicology (AREA)
  • Electromagnetism (AREA)
  • Health & Medical Sciences (AREA)
  • Plasma & Fusion (AREA)
  • Manufacturing & Machinery (AREA)
  • Optical Filters (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Devices For Indicating Variable Information By Combining Individual Elements (AREA)
  • Adhesive Tapes (AREA)

Abstract

The present invention relates to an adhesive film functionalizing color compensation and near infrared ray blocking and a plasma display panel filter employing the same. The present invention provides a multifunctional adhesive film for a plasma display panel comprising an acryl-based adhesive and a near infrared ray blocking dye. The present invention also provides a multifunctional adhesive film for a plasma display panel comprising an acryl-based adhesive and a neon-cut dye. The adhesive film may further comprise a near infrared ray blocking dye. The multifunctional adhesive film of the present invention has superior durability at high temperature and humidity with little transmittance change and superior thermal stability. When further comprising a near infrared ray blocking dye, it exerts both color compensation and near infrared ray blocking performances. Because the film has superior adhesivity in itself, an additional adhesive layer is unnecessary, which simplifies the manufacturing process of a plasma display panel filter and a plasma display panel.

Description

Have the adhesive film of color compensation and near infrared ray (NIR) retardance function and use the plasma display panel filter of this adhesive film
With reference to relevant patent
It is right of priority to korean patent application 10-2004-0011798 number of Korea S Department of Intellectual Property submission and the korean patent application 10-2005-0014754 that submitted on February 23rd, 2005 that the application requires on February 23rd, 2004, and at this with it as a reference.
Technical field
The present invention relates to a kind of have adhesive film that resembles such color compensation of neon reduction (neon-cut) and near infrared ray blocking function and the plasma display filter that comprises this adhesive film, relate more specifically to owing to transmittance very little under high temperature and high humidity changes the plasma display filter that has preferable weather resistance, thermostability and fusible adhesive film and use this film.
Background technology
Recently, display panels (PDP) is generally acknowledged as the main two-d display panel that wide screen is provided.
So far, developed the display panels that about 70 inches wide screens can be provided.Be used for reference, Fig. 1 is for showing the synoptic diagram of the general structure of display panels.In Fig. 1, numeral 11 is represented shells, numeral 12 expression drive circuit boards (driving circuit board), digital 13 presentation surface panel assemblies, numeral 14 expression PDP spectral filters, is reached numeral 15 expression lids.
The compensation of PDP spectral filter is composed the purity drop of the red spectrum that causes by the single tangerine coloured light of panel emission, and retardance causes the near infrared ray of telepilot fault and harmful electromagnetic radiation.In order to realize this task, the PDP spectral filter comprises as functional layers such as the color compensation layer of anti-reflecting layer, complementary color purity, near infrared absorption layer, ELECTROMAGNETIC RADIATION SHIELDING layers.Generally speaking, it is stacked to each other that these functional layers are made and used tackiness agent by normal film.
If the number that film has color compensation and near infrared ray blocking function or film simultaneously can be reduced, then can reduce about stacked quality problems and save materials consumption.For example, if give film three functions by form two functional layers on each side of film, then the number of plies of PDP spectral filter can reduce half.Selectively, can come simplified construction by using the tackiness agent that to bring into play this kind function.Typically, dyestuff is used near infrared ray blocking and color compensation.The example of this kind dyestuff is to cut down dyestuff and near infrared ray blocking dye at the light absorbing neon in certain wavelengths zone.Usually, on transparent substrate, be coated with the layer of the mixture that contains binder polymer.In this case, should use tackiness agent that the substrate that has been coated with dye coating on it is inserted in the PDP spectral filter.
The tackiness agent that is generally used for this purpose is rubber-like, poly-(vinyl acetate) class, acryloyl base class, silicone resin class etc.But rubber adhesive has relatively poor resistance to deterioration, poly-(vinyl acetate) tackiness agent has relatively poor thermotolerance and silicon resin adhesive has the shortcoming of binding property aspect.On the other hand; tackiness agent based on acryl is widely used in preparing binder composition owing to good pre-arcing characterisitics; and because the polymer molecule that contains tackiness agent is a mobile and to presser sensor, they present binding property preferably usually when at room temperature it being applied optical pressure.But should flowability often reduce and be included in being used in the tackiness agent and improve the thermotolerance or the wet fastness of the dyestuff of color compensation or near infrared ray blocking performance.So the wearing quality dyestuff that selection can stand high temperature and high humidity is important.
Use the prior art of color compensation and near infrared ray dyestuff as follows.
Japan's publication discloses the optical filter that uses at the azaporphins dyestuff in 570~605nm zone for 2001-248721 number.Can comprise clear binder (based on the tackiness agent of acryl) to improve binding property although this patent is mentioned, not mention used adhesive construction, linking agent in detail, reach coupler.In addition, although initial 15.9% transmittance meets the demands at the 584nm place, do not mention about before the endurance test and after transmittance keep.
Korea S's publication discloses the near infrared ray blocking material by adopting cyanine dyes and prepare in the systemic near infrared ray dyestuff in 550~620nm zone on transparent substrate for 2002-0055410 number.Korea S's publication discloses the contact adhesive composition that contains acryl adhesive resin, near infrared ray dyestuff, UV absorption agent, reaches hindered amine as light stabilizer (hindered aminelight stabilizer) for 2004-0049280 number.Japan's publication disclose for 2001-207142 number contain acryl adhesive resin, cyanine IR absorption agent, and the IR of multi-functional acryl polymkeric substance absorb binder composition, and Japanese publication discloses for 2004-107566 number and has comprised the tackiness agent that acryl resin with specific acid number and polymethine neon are cut down dyestuff.
But Korea S's publication is not mentioned adhesive construction and composition 2002-0055410 number, and the near infrared that Korea S's publication does not have for 2004-0049280 number to propose about near-infrared absorption film blocks effect.And Japanese publication does not have for 2001-207142 number to propose to cut down dyestuff based on the NIR dyestuff of cyanine with based on the neon of cyanine, but occurs the thermotolerance and the photostabilization of difference when using cyanine dyes separately.
And the color compensation film and the near infrared ray blocking film that prepare according to ordinary method are showing difference according to tackiness agent kind, coating condition etc. aspect the weather resistance of high temperature and high humidity.In addition, stacked these films are expensive with inefficient in order to prepare the PDP spectral filter.Therefore, attempted developing multi-functional bonding coat, as comprised the bonding coat of neon cut layer and comprise the bonding coat of near infrared ray blocking layer, but the weather resistance under hot and humid that shows is unsatisfactory.
Summary of the invention
A technical scheme of the present invention provides a kind of multifunctional viscous film with color compensation and near infrared ray blocking function, this film has the splendid weather resistance that the very little transmittance under hot and humid changes, good thermostability, can in considerable time, maintain the transmittance of visible region, and have good near infrared ray blocking performance.
Another technical scheme of the present invention provides a kind of plasma display panel filter and comprises the display panels of this spectral filter, thereby this spectral filter comprises the multifunctional viscous film with color compensation and near infrared ray blocking performance and do not have extra bonding coat can simplify this film.
In order to realize these technical schemes, the invention provides a kind of the comprising of Plasmia indicating panel of being used for based on the tackiness agent of acryl and the multifunctional viscous film of near infrared ray blocking dye.
The present invention also provides a kind of comprise acryl tackiness agent and neon that is used for Plasmia indicating panel to cut down the multifunctional viscous film of dyestuff.Preferably, this adhesive film further comprises near infrared ray blocking dye.
The present invention further provides a kind of plasma display panel filter that at least one side of substrate, comprises at least a above-mentioned multifunctional viscous film.
The present invention further provides a kind of Plasmia indicating panel that comprises this plasma display panel filter.
Description of drawings
Fig. 1 is for showing the synoptic diagram of Plasmia indicating panel structure.
Fig. 2 shows the spectrum change according to the multifunctional viscous film of preparation in the embodiments of the invention 4.
Fig. 3 shows the spectrum change according to the multifunctional viscous film of preparation in the embodiments of the invention 5.
Fig. 4 shows the spectrum change according to the multifunctional viscous film of preparation in the embodiments of the invention 6.
Fig. 5 shows the spectrum change of the adhesive film of preparation among the high temperature durability test back comparative example 1.
Fig. 6 shows behind high temperature/high wet test the spectrum change of the adhesive film of preparation among the comparative example 1.
Fig. 7 shows the spectrum change of the adhesive film of preparation among the comparative example 2.
Fig. 8 demonstration comprises the structure according to the plasma display filter of the embodiment 7 of multifunctional adhesive of the present invention.
Fig. 9 demonstration comprises the structure according to the plasma display filter of the embodiment 8 of multifunctional adhesive of the present invention.
Figure 10 shows the structure of comparative example 3 plasma display filter.
Embodiment
Hereinafter provide detailed description of the present invention.
The invention provides a kind of weather resistance and fusible multifunctional viscous film preferably of having that is used for Plasmia indicating panel, comprise as the splendid binding property of having of adhesive resin and weather resistance and can replace the pressure sensitive adhesive based on acryl, color compensation dyestuff and the near infrared ray dyestuff of conventional tackiness agent (PSA).
Film of the present invention comprises the neon reduction dyestuff that can block 590nm neon light on every side and can block 850nm and 950nm near infrared near infrared ray dyestuff on every side, thereby satisfies the required typical optical characteristics of plasma display filter.
Neon peak around 570~600nm that multifunctional viscous film of the present invention has reduced to be produced by the PDP assembly effectively, and block 800~1100nm the NIR district light to 10% or below.When in hot and humid down test, more specifically 80 ℃ following 500 hours and under 60 ℃, 90%RH 500 hours, the dye strength change 10% or littler in visible and NIR district.Because a film can have color compensation or have color compensation simultaneously and the near infrared ray blocking performance, thus the number of film can be reduced, thereby simplified construction.
Hereinafter provide the description more specifically of adhesive film of the present invention.
The electromagnetic radiation that PDP produces when having the multi-functional film of performance (spectral filter) with retardance work in the front of panel, neon radiation, near infrared ray etc.Tackiness agent (PSA) is used to form film.This tackiness agent should not only have splendid binding property but also (380~780nm) have transmittance preferably in the visible region.
So film of the present invention comprises based on the tackiness agent of acryl and near infrared ray blocking dye.And film of the present invention can comprise based on the tackiness agent of acryl and neon cuts down dyestuff, and further comprises near infrared retardance dyestuff.
Preferably, the tackiness agent as adhesive resin is to have 0 ℃ or following second-order transition temperature (T among the present invention g) the tackiness agent based on acryl.Tackiness agent based on acryl can be by the C that has of 75~99.89wt% 1-12(methyl) acrylate monomer of alkyl, the α of 0.1~20wt% as function monomer, beta-unsaturated carboxylic acid ester monomer, and the polymer monomer copolymerization of 0.01~5wt% with hydroxyl obtain.Those skilled in the art can finish this copolymerization.
More preferably; tackiness agent based on acryl is butyl acrylate (BA)/methacrylic acid hydroxyethyl ester (HEMA) multipolymer or butyl acrylate/vinylformic acid (AA) multipolymer, has better receptivity because these tackiness agents are compared in visible region and near infrared light area with acryl tackiness agent of the prior art.
Near infrared ray blocking dye can be the conventional dyestuff that uses, for example diimmonium (diimmonium) dyestuff.If desired, it can use with metal complex dyes or phthalocyanine pigment.The diimmonium dyestuff is absorption near infrared ray in the wide zone of 900~1200nm.
Near infrared ray blocking dye can for the naphthalene phthalocyanine pigment that is selected from the diimmonium dyestuff that comprises 4 expressions of following chemical formula, the phthalocyanine pigment of following chemical formula 5 expressions, 6 expressions of following chemical formula, and below group at least a of metallized dye of chemical formula 7 and chemical formula 8 expressions.
Figure A20058000016000171
In chemical formula 4, each R 1~R 12Independently for hydrogen atom, halogen atom, replacement or unsubstitutedly have a C 1~C 16Alkyl or replacement or unsubstitutedly have a C 1~C 16Aryl; And X is unit price or divalence organic anion, monovalent anion or divalence inorganic anion.
In chemical formula 5 and 6, each R is independently for hydrogen atom, halogen atom, replacement or unsubstitutedly have a C 1~C 16Alkyl, replacement or unsubstituted phenyl, replacement or unsubstitutedly have a C 1~C 5The alkoxyl group that replaces of alkoxyl group, replacement or unsubstituted allyloxy, fluorine or the five-ring with at least one replacement or unsubstituted nitrogen-atoms; And M is be selected from the group that comprises atoms metal that two hydrogen atoms, divalent metal atom, trivalent or tetravalence replace and oxo-atoms metal at least a, and is preferably Ni, Pt, Pd or Cu.
In chemical formula 7 and 8, each R and R 1~R 4Be hydrogen atom independently, have C 1~C 16Alkyl, aryl, alkoxyl group, phenoxy group, hydroxyl, have C 1~C 16Alkylamino, the virtue amino, trifluoromethyl, have C 1~C 16Alkylthio, arylthio, nitro, cyano group, halogen atom, phenyl or naphthyl.
In chemical formula 4, the unit price organic anion can be organic carboxyl acid salt ion, organic sulfonic acid salt ion, organic boronic salt ion etc.The organic carboxyl acid salt ion can be acetate, lactic acid salt, trifluoroacetate, propionic salt, benzoate, oxalate, succinate or stearate.The organic sulfonic acid salt ion can be metal sulfonate, tosylate, naphthalene monosulfonate, closilate, nitrobenzene-sulfonic acid salt, dodecylbenzene sulfonate, benzene sulfonate, acetylene sulfonate or trifluoro-methanyl sulfonate.Preferably, the organic boronic salt ion is tetraphenyl borate or butyl borphenyl hydrochlorate.
In chemical formula 4, the unit price inorganic anion is preferably the halogenation negatively charged ion, as fluorochemical, muriate, iodide, thiocyanate-, hexafluoro antimonate, perchlorate, periodate, nitrate, a tetrafluoro borate, hexafluorophosphate, molybdate, tungstate, titanate, phosphoric acid salt, and borate.Preferably, the divalence mineral ion is a naphthalene-1,5-stilbene-4,4'-bis-(1-azo-3, 4-dihydroxy-benzene)-2,2'-disulfonate, naphthalene-1,6-stilbene-4,4'-bis-(1-azo-3, 4-dihydroxy-benzene)-2,2'-disulfonate, naphthalene disulfonic acid salt derivative etc.
Neon is cut down dyestuff and is had maximum absorption wavelength and 50nm or the following half-band width of 570~600nm.Preferably, this dyestuff has the structure of intramolecularly or intermolecular metal complex.
For example, neon reduction dyestuff can be to be selected from the porphyrin dye with intramolecularly metal complex that comprises following surface chemistry formula 1 expression, the cyanine dyess with intermolecular metal complex structure that reach following surface chemistry formula 2 and 3 expressions.Preferably, neon shearing dyestuff can be a porphyrin dye.
Figure A20058000016000191
In Chemical formula 1, each R 1~R 8In independently for hydrogen atom, halogen atom, replacement or unsubstitutedly have a C 1~C 16Alkyl or have C 1~C 16The alkoxyl group that replaces of alkoxyl group, replacement or unsubstituted phenyl, replacement or unsubstituted allyloxy, fluorine or the five-ring with at least one replacement or unsubstituted nitrogen-atoms; And M is that hydrogen atom, Sauerstoffatom, halogen atom or coordinate divalence are to tetravalent metal atom.
In Chemical formula 2 and 3, each R is independently for hydrogen atom, replacement or unsubstitutedly have the aliphatic hydrocarbon of 1~30 carbon atom, an aryl that has the alkoxyl group of 1~8 carbon atom or have 6~30 carbon atoms; Each X and Y are halogen atom, nitro, carboxyl, the alkoxyl group with 2~8 carbon atoms, phenyloxycarbonyl, carboxylic acid ester groups independently, have the alkyl of 1~8 carbon atom, the aryl that has the alkoxyl group of 1~8 carbon atom or have 6~30 carbon atoms.
In the M of Chemical formula 1, divalent metal atom can be Cu, Zn, Fe, Co, Ni, Ru, Rd, Pd, Mn, Sn, Mg, Ti etc.; Trivalent metal atom can be replaced by halogen atom, hydroxyl or alkoxyl group, as Al-Cl, Ga-Cl, In-Cl, Fe-Cl, Ru-Cl etc.; Quadrivalent atom can be selected from halogen atom, hydroxyl, be reached two substituting groups replacements of alkoxyl group, as SiCl 2, GaCl 2, TiCl 2, SnCl 2, Si (OH) 2, Ge (OH) 2, Mn (OH) 2, Sn (OH) 2Deng.And M can be and oxygen bonded oxygen metal, as VO, MnO, TiO etc.
Based on the tackiness agent of acryl and the weight ratio of near infrared ray blocking dye is 10: 1~10000: 1.Weight ratio also with the weight of solvent in the binder solution than the molar extinction coefficient of the viscosity of, binder solution, near infrared ray blocking dye, and conceivable transmission ratio change.
Cut down the film of dyestuff for containing neon, the weight ratio that acryl tackiness agent and neon are cut down dyestuff is 10: 1~10000: 1.Weight ratio also with the viscosity of the weight ratio of solvent in the binder solution, binder solution, molar extinction coefficient that neon is cut down dyestuff, and conceivable transmission ratio change.
Multifunctional membrane of the present invention may further include solvent.This solvent can be normally used organic solvent, preferred methylethylketone (MEK), tetrahydrofuran (THF) (THF), ethyl acetate, toluene etc.Do not limit the content of solvent especially.
Adhesive film of the present invention may further include linking agent and coupler.
Linking agent can be as isocyanate crosslinking, epoxy crosslinking agent, aziridine crosslinker, and the multi-functional compounds of metallo-chelate linking agent.More preferably, this linking agent is an isocyanate crosslinking, as tolylene diisocyanate, Xylene Diisocyanate, '-diphenylmethane diisocyanate, hexamethylene diisocyanate etc., but is not limited thereto.Acryl polymkeric substance for per 100 weight parts can use 0.01~2 parts by weight of cross-linking agent.
Preferably, coupler is a silane coupling agent.Silane coupling agent has improved adhesion reliability, especially when placing separately for a long time down hot and humid.Silane coupling agent can be vinyl silanes, epoxy silane, methacrylic acyloxy silane etc.For example, vinyltrimethoxy silane, vinyltriethoxysilane, γ-epoxypropyl Trimethoxy silane etc. can be used alone or in combination.Can use the coupler of 0.01~2 weight part for the acryl polymkeric substance of per 100 weight parts.
The method that does not prepare adhesive film especially.For example, this film can to linking agent that wherein adds predetermined amount and coupler, thereby obtain coating solution by mixing colouring agent and tackiness agent, and coating solution is applied on the film, solidifies then to prepare.Preferably, the coating that obtains has the thickness of at least 10 μ m.Coating can apply (barcoating) by spraying method, cylinder coating, rod, rotary coating waits and finishes.
The present invention also provides the plasma display panel filter that comprises multifunctional viscous film that is used for Plasmia indicating panel.Plasma display panel filter can be by stacked basilar membrane, anti-reflective film (AR film), near infra red film of the present invention, have color compensation or have color compensation simultaneously and the multifunctional viscous film of near infrared ray blocking function, electromagnetic interference film (EMI film), blank screen are handled film etc. and be produced.
Plasma display panel filter can prepare by abundant stacked above-mentioned film on the transparent substrate of being made by glass or polyethylene terephthalate (PET).Spectral filter of the present invention can comprise at least one near infra red film, color compensation film, reach the film that has color compensation and near infrared ray blocking function simultaneously.Each film can be positioned on the substrate or under.Direct when stacked on substrate when at least one multifunctional membrane, do not use tackiness agent.When forming the layer that does not comprise multifunctional membrane, can use the pressure sensitive adhesive (PSA) that is used usually.In other words, electromagnetic interference film and blank screen processing film can be stacked by using conventional tackiness agent.
The present invention further provides a kind of Plasmia indicating panel that comprises plasma display panel filter.Plasmia indicating panel can prepare by method well known in the art, will not be described specifically.
When the spectral filter that comprises adhesive film of the present invention is used in the face equipment, can access have the splendid weather resistance that changes in hot and humid down small transmittance, good thermostability, and in the visible region Plasmia indicating panel of transmittance preferably.
As mentioned above; the adhesive film that is used for Plasmia indicating panel; this adhesive film comprises as the tackiness agent based on acryl of splendid binding property of having of adhesive resin and weather resistance, and color compensation dyestuff or color compensation dyestuff and near infrared ray blocking dye, has the splendid weather resistance that changes in hot and humid down small transmittance, good thermostability, transmittance, an and good near infrared ray blocking performance preferably in the visible region.Especially, this film itself is sticking, thus do not need to use extra tackiness agent during Plasmia indicating panel in preparation, thus simplify preparation process and reduced the thickness of spectral filter.
With preferred embodiment the present invention is described in further detail.But following embodiment just is used to understand the present invention and does not limit the present invention.
[embodiment]
Follow to preparation and test according to multifunctional viscous film of the present invention.
<membrane prepare 〉
1. the preparation of solution: the coating solution that is used to prepare multifunctional viscous film prepared separately or by with cut down as butyl acrylate (BA)/methacrylic acid hydroxyethyl ester (HEMA) multipolymer of adhesive resin or butyl acrylate (BA)/vinylformic acid (AA) multipolymer, neon dyestuff, first near infrared ray blocking dye, and second near infrared ray blocking dye mix and prepare.
2. coating: coating solution is applied to the thickness that reaches 15 μ m on the film.After 3 minutes, use the film lamination coating surface 120 ℃ of dryings.
3. solidify: at room temperature solidified 3 days.
<endurance test 〉
Hot conditions: 80 ℃ of transmittances of preserving 500 hours contrast front and back of film down.
(embodiment 1)
Comprise the membrane prepare of near infrared ray blocking dye
The butyl acrylate (BA) of 100 weight parts (15.5wt%)/methacrylic acid hydroxyethyl ester (HEMA) copolymer solution is dissolved in the ethyl acetate of 84.5ml, diimmonium dyestuff (CIR1081 with chemical formula 4 expression of 0.05 weight part as near infrared ray blocking dye, JapanCarlit Co.), the T-39M as isocyanate crosslinking of 0.05 weight part, and the T-789J as silane coupling agent of 0.07 weight part join in the methylethylketone (MEK) of 45 weight parts, mix then, thereby obtain coating solution.Coating solution is applied to the thickness that reaches 23 μ m on the basilar membrane, thereby obtains multifunctional viscous film.
According to above-mentioned test weather resistance.Provide the result in the following Table 1.
Table 1
Visible region transmittance (%) NIR district transmittance (%)
438nm 450nm 528nm 550nm 586nm 612nm 628nm 850nm 950nm
Beginning 70.4 68.0 71.0 81.4 86.5 87.0 85.3 2.3 3.0
After 500 hours 70.3 67.7 71.7 82.1 87.3 87.4 85.5 2.4 3.1
By table 1 as seen, adhesive film is kept in visible region and the splendid transmittance of near infrared ray (NIR) district demonstration after the high temperature test.
(embodiment 2)
Except the phthalocyanine pigment (IP12, Japan catalyst Co.) that uses chemical formula 5 expressions as outside the near infrared ray blocking dye, prepare adhesive film according to the mode identical with embodiment 1.
(embodiment 3)
Except using butyl acrylate/acrylic acid copolymer soln to replace butyl acrylate (BA)/methacrylic acid hydroxyethyl ester (HEMA) copolymer solution, use the mode identical to prepare adhesive film with embodiment 1 as the tackiness agent based on acryloyl.
(embodiment 4)
The butyl acrylate (BA) of 100 weight parts (15.5wt%)/methacrylic acid hydroxyethyl ester (HEMA) copolymer solution is dissolved in the ethyl acetate of 84.5ml, the porphyrin dye that the Chemical formula 1 of 0.05 weight part is represented, the T-39M as isocyanate crosslinking of 0.05 weight part, and the T-789J as silane coupling agent of 0.07 weight part join in the methylethylketone (MEK) of 45 weight parts, mix then, thereby obtain coating solution.Coating solution is applied to the thickness that reaches 23 μ m on the basilar membrane, thereby obtains multifunctional viscous film.
According to above-mentioned test weather resistance.Provide the result in the following Table 2.The spectrum change of adhesive film is shown in Fig. 2.
Table 2
The transmittance of visible region (%)
400nm 450nm 528nm 550nm 593nm 612nm 628nm
Beginning 68.8 70.3 60.9 52.5 27.9 53.6 74.0
After 500 hours 68.7 70.5 60.5 52.3 28.0 54.1 74.2
By table 1 and Fig. 2 as seen, the adhesive film that comprises the color compensation dyestuff of embodiment 4 shows that in the visible region splendid transmittance keeps.
(embodiment 5)
Butyl acrylate/the acrylic acid copolymer soln of 100 weight parts (14.5wt%) is dissolved in the ethyl acetate of 84.5ml, the porphyrin dye that the Chemical formula 1 of 0.05 weight part is represented, the T-39M as isocyanate crosslinking of 0.23 weight part, and the T-789J as coupler of 0.03 weight part join in the methylethylketone (MEK) of 45 weight parts, mix then, thereby obtain coating solution.Coating solution is applied to basilar membrane, thereby to obtain multifunctional viscous film.
According to above-mentioned test weather resistance.Provide the result in the following Table 3.The spectrum change of adhesive film is shown in Fig. 3.
Table 3
The transmittance of visible region (%)
400nm 450nm 528nm 550nm 593nm 612nm 628nm
Beginning 67.9 69.8 60.7 52.3 27.4 53.0 73.6
After 500 hours 67.0 69.6 60.5 52.4 28.0 53.7 73.6
By table 3 and Fig. 3 as seen, the adhesive film that comprises the color compensation dyestuff of embodiment 5 shows that in the visible region splendid transmittance keeps.
(embodiment 6)
Except the porphyrin dye of further use 0.3 weight part, the diimmonium dyestuff of 0.3 weight part (first near infrared ray blocking dye) (CIR1081, Japan Carlit Co.), reach phthalocyanine pigment (second the near infrared ray blocking dye) (IP12 of 0.1 weight part, Japan catalyst Co.) in addition, prepare adhesive film according to the mode identical with embodiment 4.
Coating solution is applied on the basilar membrane to obtain multifunctional viscous film.
According to above-mentioned test weather resistance.Provide the result in the following Table 4.The spectrum change of adhesive film is shown in Fig. 4.
Table 4
Visible region transmittance (%) NIR district transmittance (%)
400nm 450nm 528nm 550nm 586nm 612nm 628nm 850nm 950nm
Beginning 23.4 583 52.2 48.6 24.3 45.9 63.4 4.2 2.7
After 500 hours 23.6 655.3 52.3 48.5 24.4 45.4 62.9 5.0 4.0
By table 4 and Fig. 4 as seen, the adhesive film that comprises the color compensation dyestuff of embodiment 6 shows in the visible region but also in the NIR district that not only splendid transmittance keeps.
(comparative example 1)
Become following composition by composition and prepare adhesive film coating solution.
Form: the cyanine dyes (0.0214g, the TY102 that cut down dyestuff as neon; Asahi denka), 14BB (100g, have-the OH base based on acryloyl), solidifying agent (0.03g, T-39M), coupler (0.07g, T-789J).
Be coated with on substrate: rod is coated with method, dry thickness 25 μ m.
Afterwards, according to above-mentioned test weather resistance.Provide the result in the following Table 5, and the spectrum change of adhesive film is shown in Fig. 5.
Table 5
The transmittance in NIR district (%)
Wavelength (nm) 450 550 587 628
Before the endurance test 57.6 38.7 11.5 66.5
100 ℃ of weather resistance after following 10 minutes 43.6 39.0 11.9 66.6
In the weather resistance of high temperature (80 ℃) after following 500 hours 43.0 44.3 16.1 67.3
In addition, in table 6, provide the test-results of high temperature and high humidity, and the spectrum change of adhesive film is shown in Fig. 6.
Table 6
The transmittance in NIR district (%)
Wavelength (nm) 450 550 587 628
Before the endurance test 56.6 37.0 10.4 65.4
100 ℃ of weather resistance after following 10 minutes 56.3 37.3 10.7 65.5
Hot and humid (80 ℃, the RH90%) weather resistance after following 500 hours 53.2 46.8 18.1 66.6
By the result as seen, comparative example 1 the adhesive film that comprises the color compensation dyestuff is compared with embodiments of the invention, keeps in the relatively poor transmittance of visible region demonstration.
(comparative example 2)
Become following composition by composition and prepare adhesive film coating solution.
Form: phthalocyanine NIR absorbing dye (0.01g, TY102; Asahi denka), 14BB (100g, have-the OH base based on acryloyl), solidifying agent (0.006g, T-39M), and coupler (0.014g, T-789J).
Be coated with on substrate: rod is coated with method, dry thickness 20 μ m.
Condition of cure: at room temperature 3 days.
Afterwards, according to above-mentioned test weather resistance.Provide the result in the following Table 7, and the spectrum change of adhesive film is shown in Fig. 7.
Table 7
The transmittance in NIR district (%)
Wavelength (nm) 450 550 586 628 854
Before the endurance test 80.9 84.8 84.3 80.7 34.2
In the weather resistance of high temperature (80 ℃) after following 500 hours 81.2 85.1 84.7 82.5 35.4
By the result as seen, comparative example 2 adhesive film is compared with embodiments of the invention, also keeps in the relatively poor transmittance of visible region demonstration.
(embodiment 7)
The preparation of display panels spectral filter
Adhesive film 28, hard glass 26, the pressure sensitive adhesive layer (PSA) 24 of the plasma display panel filter that shows as Fig. 8 (five tunic structures) by preparation among stacked anti-reflective film on glass substrate (AR film) 30, the embodiment 1, reach electromagnetic interference film (EMI film) 22 and prepare.
(embodiment 8)
The preparation of display panels spectral filter
Adhesive film 28, NIR film 29, hard glass 26, the PSA 24 of the plasma display panel filter that shows as Fig. 9 (seven tunic structures) by preparation among stacked anti-reflective film on glass substrate (AR film) 30, the embodiment 4, reach electromagnetic interference film (EMI film) 22 and prepare.
(comparative example 3)
The near infra red film 29 of the color compensation film 25 of plasma display panel filter by stacked anti-reflective film 30, bonding coat 24, comparative example 1, bonding coat 24, comparative example's 2 routine, bonding coat 24, hard glass 26, bonding coat 24, and electromagnetic interference film 22 prepare.Use rubber adhesive (PSA) to come stacked all films.Its structure is shown in Figure 10.Comparative example 3 spectral filter has nine layers of structure.
Can obviously find out from the above, thereby thereby multifunctional viscous film of the present invention is owing to use the tackiness agent based on acryloyl to improve weather resistance and used color compensation dyestuff and near infrared ray blocking dye to make color compensation and near infrared ray blocking performance functionalization as adhesive resin.In addition, this film has splendid near infrared ray transmittance ratio, particularly itself has good binding property and does not need extra tackiness agent owing to this film.So this film can be simplified the structure of plasma display panel filter and can be used for the manufacturing of plasma display panel filter and Plasmia indicating panel.Though the present invention is described in detail according to preferred embodiment, those skilled in the art will appreciate that and make various modifications under the spirit and scope of the present invention as illustrated in can be in not departing from and substitute as claims.

Claims (18)

1, a kind of multifunctional viscous film that is used for Plasmia indicating panel comprises tackiness agent and near infrared ray blocking dye based on acryloyl.
2, multifunctional viscous film as claimed in claim 1, wherein the tackiness agent based on acryloyl is butyl acrylate/methacrylic acid hydroxyethyl ester multipolymer or butyl acrylate/acrylic copolymer.
3, multifunctional viscous film as claimed in claim 1, wherein the content based on the tackiness agent near infrared ray blocking dye of acryloyl for per 100 weight parts is 0.01~10 weight part.
4, multifunctional viscous film as claimed in claim 1, wherein near infrared ray blocking dye be selected from the naphthalene phthalocyanine pigment of the diimmonium dyestuff that comprises 4 expressions of following chemical formula, the phthalocyanine pigment of following chemical formula 5 expressions, 6 expressions of following chemical formula and following chemical formula 7 or chemical formula 8 expressions metal complex dyes group one of at least:
Figure A2005800001600002C1
Wherein
In chemical formula 4, each R 1~R 12Independently for hydrogen atom, halogen atom, replacement or unsubstitutedly have a C 1~C 16Alkyl, replacement or unsubstitutedly have a C 1~C 16Aryl, and X is unit price or divalence organic anion or unit price or divalence inorganic anion;
In chemical formula 5 and 6, each R is independently for hydrogen atom, halogen atom, replacement or unsubstitutedly have a C 1~C 16Alkyl, replacement or unsubstituted phenyl, replacement or unsubstitutedly have a C 1~C 5The alkoxyl group that replaces of alkoxyl group, replacement or unsubstituted allyloxy, fluorine or the five-ring with at least one replacement or unsubstituted nitrogen-atoms, and M be selected from the atoms metal that comprises two hydrogen atoms, divalent metal atom, trivalent or tetravalence and replace, and the group of oxo-atoms metal one of at least, and be preferably Ni, Pt, Pd or Cu; And,
In chemical formula 7 and 8, each R and R 1~R 4Be hydrogen atom independently, have C 1~C 16Alkyl, aryl, alkoxyl group, phenoxy group, hydroxyl, have C 1~C 16Alkylamino, the virtue amino, trifluoromethyl, have C 1~C 16Alkylthio, arylthio, nitro, cyano group, halogen atom, phenyl or naphthyl.
5, multifunctional viscous film as claimed in claim 1, for per 100 weight parts it further contains at least a additive that is selected from the group of the coupler that comprises 0.01~2 parts by weight of cross-linking agent and 0.01~2 weight part based on the pressure sensitive adhesive of acryloyl.
6, plasma display panel filter comprises each multifunctional viscous film of claim 1~5 at least one side of substrate.
7, multifunctional viscous film as claimed in claim 6, it further comprises anti-reflective film (AR film), electromagnetic interference film (EMI film) and blank screen processing film.
8, a kind of Plasmia indicating panel that comprises the spectral filter of claim 6.
9, a kind of multifunctional viscous film comprises based on the tackiness agent and the neon of acryloyl and cuts down dyestuff.
10, multifunctional viscous film as claimed in claim 9, wherein the tackiness agent based on acryloyl is butyl acrylate/methacrylic acid hydroxyethyl ester multipolymer or butyl acrylate/acrylic copolymer.
11, multifunctional viscous film as claimed in claim 9, wherein for the tackiness agent based on acryloyl of per 100 weight parts, the neon that contains 0.01~10 weight part is cut down dyestuff.
12, multifunctional viscous film as claimed in claim 9, wherein neon cut down dyestuff be selected from the porphyrin compound that comprises following surface chemistry formula 1 expression with intramolecularly metal complex structure, and the group of the cyanine compound with intermolecular metal complex structure of following surface chemistry formula 2 and chemical formula 3 expressions one of at least:
Figure A2005800001600005C1
Wherein
In Chemical formula 1,
Each R 1~R 8Independently for hydrogen atom, halogen atom, replacement or unsubstitutedly have a C 1~C 16Alkyl or have C 1~C 16The alkoxyl group that replaces of alkoxyl group, replacement or unsubstituted phenyl, replacement or unsubstituted allyloxy, fluorine or the five-ring with at least one replacement or unsubstituted nitrogen-atoms, and M is that hydrogen atom, Sauerstoffatom, halogen atom or coordinate divalence are to tetravalent metal atom; And
In Chemical formula 2 and 3,
Each R is independently for hydrogen atom, replacement or unsubstitutedly have the aliphatic hydrocrbon of 1~30 carbon atom, an aryl that has the alkoxyl group of 1~8 carbon atom or have 6~30 carbon atoms; And each X and Y are halogen atom, nitro, carboxyl, the alkoxyl group with 2~8 carbon atoms, phenyloxycarbonyl, carboxylic acid ester groups independently, have the alkyl of 1~8 carbon atom, the aryl that has the alkoxyl group of 1~8 carbon atom or have 6~30 carbon atoms.
13, multifunctional viscous film as claimed in claim 9 for the tackiness agent based on acryloyl of per 100 weight parts, further comprises the near infrared ray blocking dye of 0.01~10 weight part.
14, multifunctional viscous film as claimed in claim 9, wherein near infrared ray blocking dye is group at least a of the metal complex dyes of the naphthalene phthalocyanine pigment, following chemical formula 7 or chemical formula 8 expressions that are selected from the diimmonium dyestuff that comprises 4 expressions of following chemical formula, the phthalocyanine pigment of following chemical formula 5 expressions, 6 expressions of following chemical formula:
Figure A2005800001600007C1
Figure A2005800001600008C1
Wherein
In chemical formula 4, each R 1~R 12Independently for hydrogen atom, halogen atom, replacement or unsubstitutedly have a C 1~C 16Alkyl or replacement or unsubstitutedly have a C 1~C 16Aryl, and X is unit price or divalence organic anion or unit price or divalence inorganic anion;
In chemical formula 5 and 6, each R is independently for hydrogen atom, halogen atom, replacement or unsubstitutedly have a C 1~C 16Alkyl, replacement or unsubstituted phenyl, replacement or unsubstitutedly have a C 1~C 5The alkoxyl group that replaces of alkoxyl group, replacement or unsubstituted allyloxy, fluorine or the five-ring with at least one replacement or unsubstituted nitrogen-atoms, and M be selected from the atoms metal that comprises two hydrogen atoms, divalent metal atom, trivalent or tetravalence and replace, and the group of oxo atoms metal one of at least, and be preferably Ni, Pt, Pd or Cu; And,
In chemical formula 7 and 8, each R and R 1~R 4Be hydrogen atom independently, have C 1~C 16Alkyl, aryl, alkoxyl group, phenoxy group, hydroxyl, have C 1~C 16Alkylamino, the virtue amino, trifluoromethyl, have C 1~C 16Alkylthio, arylthio, nitro, cyano group, halogen atom, phenyl or naphthyl.
15, multifunctional viscous film as claimed in claim 9 for the pressure sensitive adhesive based on acryloyl of per 100 weight parts, further contains at least a additive that is selected from the group of the coupler that comprises 0.01~2 parts by weight of cross-linking agent and 0.01~2 weight part.
16, a kind of plasma display panel filter comprises each multifunctional viscous film of claim 9~15 at least in a side of substrate.
17, as the plasma display panel filter of claim 16, it further comprises anti-reflective film (AR film), electromagnetic interference film (EMI film) and blank screen processing film.
18, the Plasmia indicating panel that comprises the spectral filter of claim 16.
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