CN1776465A - Near-infrared shield and display front plate - Google Patents
Near-infrared shield and display front plate Download PDFInfo
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- CN1776465A CN1776465A CNA2005101153166A CN200510115316A CN1776465A CN 1776465 A CN1776465 A CN 1776465A CN A2005101153166 A CNA2005101153166 A CN A2005101153166A CN 200510115316 A CN200510115316 A CN 200510115316A CN 1776465 A CN1776465 A CN 1776465A
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Abstract
The invention relates to a near infrared shielding body with high near infrared shielding property and high photostability, and the absorbency thereof cannot be lowered even if near infrared rays are preserved for a long time. The near infrared shielding body comprises a parent metal (1) and a near infrared absorption layer (2) which is deployed on a major face of the parent metal (1), wherein, the near infrared absorption layer (2) comprises di-sulfite ammonium compound containing sulfonic acid imide derivatives, and compound formed by anion for replacing benzenedithiol metal complex in formula (1) and a gegen ion coalition of cation in formula (2). R1 and R2 in formula (1) are alkyls the carbon atom number of which is 1 to 6, alkane amino-groups carbon atom number of which is 1 to 8, drewamine substituent which is substituted or is not substituted, sulpho-drewamine substituent which is substituted or is not substituted, piperazinyl which is substituted or is not substituted, and phenyl which is substituted or is not substituted; M is transition metal. Q1 and Q2 in formula (2) are a pentabasic or hexahydric nitrogen heterocyclic ring, and a condensed ring containing the pentabasic or hexahydric nitrogen heterocyclic ring; R3 and R4 are the alkyl the carbon atom number of which is 1 to 8, and n is a number that is 2, 3, or 4.
Description
Technical field
The present invention relates to near-infrared shield and used the display front plate of this near-infrared shield.
Background technology
In recent years, as being the display screen of the various e-machines of representative with the large-scale tv, the demand of plasma panel (PDP) increases.PDP encloses the mixed gas that contains xenon and neon between 2 glass sheets, this mixed gas is applied high voltage, will produce ultraviolet ray, and this ultraviolet ray shines the fluorophor that is coated on the glass plate, thereby carries out luminous.
But also can produce the near infrared ray in wavelength 820nm～1100nm zone and electromagnetic wave etc. this moment except ultraviolet ray.Therefore this near infrared wavelength region may becomes the reason of the mistake running that causes them owing to communicate by letter and the employed wavelength region may repetition of the Long-distance Control of other e-machines with near infrared ray.Therefore, the near-infrared shield of absorption near infrared ray is set by the front panel at PDP, absorb this near infrared ray (for example with reference to non-patent literature 1: people such as Hua Gang, " the suitableeest design film of antireflection film characteristic と is made the system technology ", the 1st edition the 2nd printing, technical information association of Co., Ltd., on February 5th, 2002,184 pages).
As this near-infrared shield, known for example have in resin, disperse the near-infrared absorbing compound and constitute membranaceous baffle.The near-infrared absorbing compound is for example diimmonium (ジ ィ モ ニ ゥ system) compound, phthalocyanine compound, cyanines (シ ァ ニ Application) compound etc., known, compare with the situation of independent these compounds of use, be used in combination multiple situation, particularly make up the situation of Diimmonium compound and phthalocyanine compound or cyanine compound, can demonstrate excellent near infrared ray absorbing (for example with reference to patent documentation 1: the spy holds flat 11-316309 communique, patent documentation 2: the spy holds the 2003-21715 communique).
Summary of the invention
But, the phthalocyanine compound of Shi Yonging in the past, in general to the dissolubility of solvent or with the intermiscibility of resin be not good, need import various substituting groups when being used for near-infrared shield, exist manufacturing cost to increase such problem.On the other hand, though the cyanine compound of Shi Yonging can easily obtain in the past, but when being used in combination with Diimmonium compound, if long-time the preservation, between these 2 kinds of near-infrared absorbing compounds, will produce mutual interference effect, have near infrared ray absorbing and visible light permeability such problem that changes.
And then cyanine compound in general photostability is low, the problem of therefore only using the near-infrared shield of cyanine compound also to exist near infrared ray absorbing and visible light permeability to change.
In addition,, require near-infrared shielding and visible light permeability higher, even and at high temperature and high humility and the near-infrared shield that under the rayed condition, also can preserve for a long time for near-infrared shield is used for display front plate.
The invention provides and have high near-infrared shielding, also can not reduce even preserve the near-infrared absorbing ability for a long time, and high near-infrared shield of photostability and the display front plate that uses this near-infrared shield.
Near-infrared shield of the present invention, comprise base material and be configured near infrared ray absorption layer on the interarea of described base material, it is characterized in that, under the condition of 63 ℃ of blackboard temperatures (BPT), relative humidity 50%, from described near infrared ray absorption layer side with illuminance 60W/m
2(in the energy density of 300～400nm scope) irradiation 16 hours is more than or equal to the xenon light time of 380nm smaller or equal to the wavelength of 1200nm, behind the described pre-irradiation of representing with the chromatic diagram of CIE1931XYZ colour system through colourity changes delta x, the Δ y of light respectively smaller or equal to 0.005.
In addition, above-mentioned near infrared ray absorption layer comprises Diimmonium compound that contains the sulfonic acid imide derivative and the compound that is formed by substituted benzene dithiol metal complex anion with structure shown in the following formula (1) and the cationic counter ion counterionsl gegenions combination with structure shown in the following formula (2).
In formula (1), R
1, R
2Expression is selected from least a substituting group in the group of being made up of for base, replacement or unsubstituted piperazinyl and replacement or unsubstituted phenyl alkylamino, replacement or unsubstituted morpholino base, replacement or the unsubstituted thiomorpholine of the alkyl of carbon number 1～6, carbon number 1～8, and M represents transition metal.
In formula (2), Q
1, Q
2Expression is selected from by 5-member heterocyclic ring containing nitrogen, the condensed ring that contains 5-member heterocyclic ring containing nitrogen, hexa-atomic nitrogen heterocyclic ring and contains at least a heterogeneous ring compound in the group that hexa-atomic nitrogenous heterocyclic condensed ring forms, R
3, R
4The alkyl of expression carbon number 1～8, n represents numeral 2,3 or 4.
In addition, display front plate of the present invention is characterized in that, disposes above-mentioned near-infrared shield on substrate.
According to the present invention, can provide to have high near-infrared shielding, can not reduce even preserve the near-infrared absorbing ability for a long time yet, and the high near-infrared shield of photostability.
In addition, according to the present invention, can provide the display front plate that has high near-infrared shielding for a long time.
Description of drawings
Fig. 1 is the sectional view of an example of expression near-infrared shield of the present invention;
Fig. 2 is another routine sectional view of expression near-infrared shield of the present invention;
Fig. 3 is the sectional view of an example of expression display front plate of the present invention;
Fig. 4 is the figure of spectrophotometric transmittance of the near-infrared shield of expression embodiment 1;
Fig. 5 is the figure of the spectrophotometric transmittance of near-infrared shield after fast light test of expression embodiment 1;
Fig. 6 is the figure of reflectivity of anti-reflection layer side of antireflection/near-infrared shielding complex of expression embodiment 4;
Fig. 7 is the figure of spectrophotometric transmittance of antireflection/near-infrared shielding complex of expression embodiment 4;
Fig. 8 is the figure of spectrophotometric transmittance of the near-infrared shield of expression comparative example 1;
Fig. 9 is the figure of spectrophotometric transmittance of the near-infrared shield after the fast light test of expression comparative example 1;
Figure 10 is the figure of spectrophotometric transmittance of the near-infrared shield after the fast light test of expression comparative example 2.
Among the figure, 1 is base material; 2 is near infrared ray absorption layer; 3 is hard conating; 4 is anti-reflection layer; 4a is middle index layer; 4b is a high refractive index layer; 4c is a low-index layer; 11 is display front plate; 12 is substrate; 13 is near-infrared shield; 14 is the electromagnetic shielding body; 15 is electrode.
Embodiment
Near-infrared shield of the present invention has base material and is configured near infrared ray absorption layer on the interarea of this base material.And near-infrared shield of the present invention is characterized in that, under the condition of 63 ℃ of BPT (blackboard temperature), relative humidity 50%, from above-mentioned near infrared ray absorption layer side with illuminance 60W/m
2(in the energy density of 300～400nm scope) irradiation 16 hours is more than or equal to the xenon light time of 380nm smaller or equal to the wavelength of 1200nm, behind the above-mentioned pre-irradiation of representing with the chromatic diagram of CIE1931XYZ colour system through colourity changes delta x, the Δ y of light respectively smaller or equal to 0.005.Thus, can make and have high near-infrared shielding, also can not reduce even preserve the near-infrared absorbing ability for a long time, and the high near-infrared shield of photostability.
One example of above-mentioned near-infrared shield is for following near-infrared shield: have base material and be configured near infrared ray absorption layer on the interarea of this base material, this near infrared ray absorption layer comprises the Diimmonium compound that contains the sulfonic acid imide derivative and by the substituted benzene dithiol metal complex anion with the represented structure of following formula (1) with have the compound that the cationic counter ion counterionsl gegenions combination of the represented structure of following formula (2) forms.
In formula (1), R
1, R
2Expression is selected from least a substituting group in the group of being made up of for base, replacement or unsubstituted piperazinyl and replacement or unsubstituted phenyl alkylamino, replacement or unsubstituted morpholino base, replacement or the unsubstituted thiomorpholine of the alkyl of carbon number 1～6, carbon number 1～8, and M represents transition metal.
In formula (2), Q
1, Q
2Expression is selected from by 5-member heterocyclic ring containing nitrogen, the condensed ring that contains 5-member heterocyclic ring containing nitrogen, hexa-atomic nitrogen heterocyclic ring and contains at least a heterogeneous ring compound in the group that hexa-atomic nitrogenous heterocyclic condensed ring forms, R
3, R
4The alkyl of expression carbon number 1～8, n represents numeral 2,3 or 4.
According to present embodiment, can obtain having high near-infrared shielding, can not reduce even preserve the near-infrared absorbing ability for a long time yet, and the high near-infrared shield of photostability.
Combine with the above-mentioned terminal nitrogen atom that contains the kation position of the imido Diimmonium compound of sulfonic acid substituent at least one, be preferably alkyl with branched structure.Thus, can obtain near-infrared shielding and visible light permeability height, even at high temperature and high humility and the near-infrared shield that under the rayed condition, also can preserve for a long time.
If above-mentioned near infrared ray absorption layer further contains the resin that above-mentioned Diimmonium compound and the above-mentioned compound that is formed by the counter ion counterionsl gegenions combination are disperseed, then these compounds can be disperseed and are fixed on the base material, therefore more preferred.If above-mentioned resin glass transition temperature more than or equal to 80 ℃, then can be fixed above-mentioned Diimmonium compound and the above-mentioned compound that is formed by the counter ion counterionsl gegenions combination more firmly, improve thermotolerance, therefore further preferred.
Having the compound of maximum absorption wavelength more than or equal to 580nm smaller or equal to the wavelength region may of 620nm if above-mentioned near infrared ray absorption layer further contains, then can absorb neon luminous, therefore more preferred of PDP for example.
If above-mentioned near infrared ray absorption layer further contains having the compound of maximum absorption wavelength more than or equal to 540nm smaller or equal to the wavelength region may of 570nm, then can improve for example bright place contrast of display, therefore more preferred.
If above-mentioned near infrared ray absorption layer further contains having the compound of maximum absorption wavelength more than or equal to 480nm smaller or equal to the wavelength region may of 500nm, then can improve for example bright place contrast of the display under three-wavelength fluorescence, therefore more preferred.
If above-mentioned near infrared ray absorption layer mist degree (Haze) value is smaller or equal to 1%, during then as the front panel of for example PDP, can not damage the vividness of image, therefore more preferred.Here, so-called haze value is the turbidity about the inside of plastics or surface, the value of representing with the turbidity value of JIS K7105 defined.
In addition, if the near-infrared shield of present embodiment then can further have defencive function and anti-reflective function at the opposing face configuration hard conating and the anti-reflection layer of the interarea of the above-mentioned base material that disposes above-mentioned near infrared ray absorption layer, therefore more preferred.In the past, near infrared ray absorption layer, anti-reflection layer are fitted with the glass substrate of display front plate respectively separately, but can be as mentioned above by integrated near infrared ray absorption layer on a plate substrate and anti-reflection layer and compound, reduce the parts of fitting with front panel.
In addition, display front plate of the present invention is characterized in that, disposes the near-infrared shield of present embodiment on substrate.Thus, can provide the display front plate that has high near-infrared shielding for a long time.
Below, based on the description of drawings embodiments of the present invention.
Fig. 1 is the sectional view of an example of expression near-infrared shield of the present invention.The near-infrared shield of present embodiment is formed by base material 1 and the near infrared ray absorption layer 2 that is configured on the interarea of base material 1.
For near infrared ray absorption layer 2, as the near-infrared absorbing compound, as long as comprise the Diimmonium compound that contains the sulfonic acid imide derivative and by substituted benzene dithiol metal complex anion with have the compound that the cationic counter ion counterionsl gegenions combination of the represented structure of following formula (2) forms, just do not have particular restriction with the represented structure of following formula (1).
In formula (1), R
1, R
2Expression is selected from least a substituting group in the group of being made up of for base, replacement or unsubstituted piperazinyl and replacement or unsubstituted phenyl alkylamino, replacement or unsubstituted morpholino base, replacement or the unsubstituted thiomorpholine of the alkyl of carbon number 1～6, carbon number 1～8, and M represents transition metal.
In formula (2), Q
1, Q
2Expression is selected from by 5-member heterocyclic ring containing nitrogen, the condensed ring that contains 5-member heterocyclic ring containing nitrogen, hexa-atomic nitrogen heterocyclic ring and contains at least a heterogeneous ring compound in the group that hexa-atomic nitrogenous heterocyclic condensed ring forms, R
3, R
4The alkyl of expression carbon number 1～8, n represents numeral 2,3 or 4.
Kation with the represented structure of above-mentioned formula (2) especially preferably uses following formula (3)～(5) represented kation.
Above-mentioned Diimmonium compound can use for example following formula (6) and (7) represented compound.
In formula (6) and formula (7), R
5～R
12Expression replaces or unsubstituted alkyl, X
-, Y
2-The pairing negative ion of representing 1 valency and divalent respectively, n are represented numeral 1 or 2.
The R that combines with the terminal nitrogen atom at the kation position of formula (6) and formula (7)
5～R
12At least one, be preferably alkyl with branched structure.And, R
5～R
12Can be different separately alkyl, also can be some or all of identical alkyl.As the anionic X of pairing
-, Y
2-As long as contain the sulfonic acid imide derivative, just there is not particular restriction.Contain sulfonic acid imide derivative and above-mentioned R if use
5～R
12At least one be Diimmonium compound with alkyl of branched structure, then can obtain near-infrared shielding and visible light permeability excellence, even and in high temperature and high humility and the near infrared ray absorption layer 2 that under the rayed condition, also can preserve for a long time.Do not have particular restriction as this sulfonic acid imide derivative, for example preferably use perfluoroalkane sulfonic acid acid imide ion etc., particularly, more preferably use the such trifluoromethayl sulfonic acid acid imide ion of two (fluoroform sulphonyl) acid imide acid ion etc.
In addition, near infrared ray absorption layer 2 can further contain the X of formula (6)
-Be for example fluorine ion, chlorion, bromide ion, halogen ions such as iodide ion, thiocyanate ion, the hexafluoro-antimonic acid ion, cross the chlorate ions, the periodic acid ion, nitrate ion, the tetrafluoro boric acid ion, the hexafluorophosphoric acid ion, the molybdic acid ion, the wolframic acid ion, the metatitanic acid ion, the vanadic acid ion, phosphate ion, inorganic ions such as borate ion, acetic acid ion, lactic acid ion, the trifluoracetic acid ion, the propionic acid ion, the benzoic acid ion, oxalic ion, the succinic acid ion, organic carboxyl acid ions such as stearate ion, the Loprazolam ion, the toluenesulfonic acid ion, the naphthalene sulfonic acids ion, the chlorobenzenesulfonic acid ion, the nitrobenzene-sulfonic acid ion, the dodecyl sodium sulfonate ion, the benzene sulfonic acid ion, the ethane sulfonic acid ion, the Diimmonium compound of organic sulfonic acid ions such as trifluoromethayl sulfonic acid ion etc.
In addition, near infrared ray absorption layer 2 can further contain the Y of formula (7)
2-Be for example naphthalene-1; 5-disulfonic acid ion; R acid (beta naphthal-3 for example; the 6-disulfonic acid) ion; G acid (for example 7-croceine acid) ion; H acid (1-amino-8-naphthol-3 for example; the 6-disulfonic acid) ion; benzoyl H acid ion; to chlorobenzene formacyl H acid ion; chloracetyl H acid ion; C acid (3-amino-6-chlorotoluene-4 for example; 4-sulfonic acid) ion; p-toluenesulfonyl R acid ion; naphthalene-1; 6-disulfonic acid ion; 1-naphthols-4; naphthalenedisulfonic acid derivant ions such as 8-disulfonic acid ion; 4; 4 '-diamino-stilbene-2; 2 '-disulfonic acid ion; the naphthalenedicarboxylic acid ion; naphthalene-2; 3 '-dicarboxylic acid ion; the diphenic acid ion; stilbene-4; 4 '-dicarboxylic acid ion; 6-sulfo group-2-oxygen-3-naphthoic acid ion; anthraquinone-1; 8-disulfonic acid ion; 1; 6-diamino-anthraquinone-2; 7-disulfonic acid ion; the amino benzotriazole of 2-(4-sulphonyl)-6--5-azochlorosulfonate acid ion; 6-(3-methyl-5-pyrazoles (ピ ラ ゾ ニ Le))-1,3-disulfonic acid ion; the Diimmonium compound of 1-naphthols-6-(4-amino-3-sulfo group) anilino--organic acid ions such as 3-azochlorosulfonate acid ion.
The above-mentioned Diimmonium compound that contains the sulfonic acid imide derivative is if having the compound of maximum absorption wavelength more than or equal to 950nm smaller or equal to the wavelength region may of 1150nm, and is more preferred.And the above-mentioned compound that is formed by the counter ion counterionsl gegenions combination is if having the compound of maximum absorption wavelength more than or equal to 800nm smaller or equal to the wavelength region may of 900nm, and is more preferred.By making up both, can become the absorption object at the most near infrared ray of the wavelength region may of 820nm～1100nm.
The method that forms near infrared ray absorption layer 2 on an interarea of base material 1 does not have particular restriction, for example can use rubbing methods such as roller coat cloth, mould coating, airblade coating, scraper coating, rotary coating, oppositely coating, intaglio plate coating, print processes such as intaglio printing, serigraphy, offset printing, ink jet printing.
Above-mentioned near infrared ray absorption layer 2 more preferably further contains the resin that the near-infrared absorbing compound is disperseed, and described near-infrared absorbing compound comprises above-mentioned Diimmonium compound and the above-mentioned compound that is formed by the counter ion counterionsl gegenions combination.Thus, nearly infrared absorbing compound disperses and is fixed on the base material.This resin can use acrylic resin, urethane resin, Corvic, epoxy resin, polyvinyl acetate resins, polystyrene resin, celluosic resin, poly-butyral resin, vibrin etc.And, also can use the polymeric blends that mixes these resins more than 2 kinds or 2 kinds.Particularly, if use glass transition temperature more than or equal to 80 ℃ resin, the near-infrared absorbing compound will be firmly fixed by resin, can improve thermotolerance, is preferred therefore.In addition, if, then can improve the heatproof humidity characteristic, therefore more preferred also with the resin that contains the hydrophobicity composition.
In addition, above-mentioned near infrared ray absorption layer 2 can further contain the solvent that dissolves above-mentioned resin.This solvent only otherwise can damage above-mentioned near-infrared absorbing compound and above-mentioned dissolving resin, just do not have particular restriction, for example can use MEK, methyl isobutyl ketone, ethyl acetate, propyl acetate, ethyl cellosolve, butyl cellosolve, toluene, dimethylbenzene, tetrahydrofuran etc.
Above-mentioned near infrared ray absorption layer 2 more preferably further contains the compound that has maximum absorption wavelength in the wavelength region may of 580nm～620nm.Thus, can absorb the luminous of neon.Neon luminous is for example to make one of reason that the color reproducibility of PDP reduces, if use this near-infrared shield to absorb the luminous of neon, then can make more bright-coloured ground of the redness color development of PDP.This compound is so long as the compound that the spectrophotometric transmittance of near infrared ray absorption layer 2 is changed in the whole zone of wavelength 820nm～1100nm, just do not have particular restriction, for example can use the cyanines class, azulenes (ァ ズ レ ニ ウ system) class, this overstates (ス Network ワ リ ウ system) class, diphenylmethanes, triphenylmethane oxazine class, azines, sulfo-pyrans (チ ォ ピ リ ウ system) class, the redox class, the azo class, the azo metal complex salt, a word used for translation porphin coffee quinoline (ァ ザ Port Le Off ィ リ Application) class, the bisdiazo class, the anthraquinone class, organic pigment compounds such as phthalocyanines.In addition, when near infrared ray absorption layer 2 contains resin, the compound that this compound more preferably uses the intermiscibility that can not make this resin and above-mentioned near-infrared absorbing compound to change.
In addition, above-mentioned near infrared ray absorption layer 2 more preferably further contains the compound that has maximum absorption wavelength in the wavelength region may of 540nm～570nm.Thus, can improve for example bright place contrast of display.This compound is so long as the compound that the spectrophotometric transmittance of near infrared ray absorption layer 2 is changed in the whole zone of wavelength 820nm～1100nm, just do not have particular restriction, for example can use cyanines class, camomile lopps, this overstates organic pigment compounds such as class, diphenylmethanes, triphenylmethane, oxazine class, azines, sulfo-pyrans class, redox class, azo class, azo metal complex salt, a word used for translation porphin coffee quinoline class, bisdiazo class, anthraquinone class, phthalocyanines.In addition, when near infrared ray absorption layer 2 contains resin, the compound that this compound more preferably uses the intermiscibility that can not make this resin and above-mentioned near-infrared absorbing compound to change.
And then above-mentioned near infrared ray absorption layer 2 more preferably further contains the compound that has maximum absorption wavelength in the wavelength region may of 480nm～500nm.Thus, can improve for example bright place contrast of the display under three-wavelength fluorescence.This compound is so long as the compound that the spectrophotometric transmittance of near infrared ray absorption layer 2 is changed in the whole zone of wavelength 820nm～1100nm, just do not have particular restriction, for example can use cyanines class, camomile lopps, this overstates organic pigment compounds such as class, diphenylmethanes, triphenylmethane, oxazine class, azines, sulfo-pyrans class, redox class, azo class, azo metal complex salt, a word used for translation porphin coffee quinoline class, bisdiazo class, anthraquinone class, phthalocyanines.In addition, when near infrared ray absorption layer 2 contains resin, the compound that this compound more preferably uses the intermiscibility that can not make this resin and above-mentioned near-infrared absorbing compound to change.
The near-infrared shield of present embodiment more preferably haze value is smaller or equal to 1%.If haze value surpasses 1%, when then for example being used as the front panel of PDP, will produce the impaired such unfavorable condition of vividness of image.
The near-infrared shield of present embodiment preferably at the spectrophotometric transmittance in the zone of wavelength 820nm～1100nm more than or equal to 0.5% smaller or equal to 13%.Therefore and not preferred if surpass 13%, then can become the reason of the color change of the reason of for example mistake running of Long-distance Control and near-infrared shield, at the spectrophotometric transmittance of this wavelength region may.
The thickness of near infrared ray absorption layer 2 is preferably 2 μ m～15 μ m, more preferably 3 μ m～10 μ m.During the thickness less than 2 μ m of near infrared ray absorption layer 2, for the spectrophotometric transmittance that makes near infrared ray (zone of wavelength 820nm～1100nm luminous) smaller or equal to 20%, need to increase the addition of the near-infrared absorbing compound in the resin, thereby can produce undissolved near-infrared absorbing compound, produce haze value and become big such problem.In addition, when thickness surpasses 15 μ m, though the spectrophotometric transmittance in the zone of wavelength 820nm～1100nm can maintain smaller or equal to 20%, but the residual free solvent of meeting in the near infrared ray absorption layer 2, this residual solvent can dissolve the near-infrared absorbing compound again along with the time, thereby becomes problem.
Fig. 2 is another routine sectional view of expression near-infrared shield of the present invention.Among Fig. 2, the component parts identical with near-infrared shield shown in Figure 1 given same symbol, omits its explanation.And same parts has same effect.
The near-infrared shield of present embodiment by base material 1, be configured near infrared ray absorption layer 2 on the interarea of base material 1, be configured in the hard conating 3 on another interarea of this base material 1 and the anti-reflection layer 4 that is configured on this hard conating 3 forms.In addition, above-mentioned anti-reflection layer 4 forms index layer 4a, high refractive index layer 4b and low-index layer 4c from hard conating 3 sides dispose successively by different three layers of refractive index.
The material of hard conating 3 is not so long as hardness height, material with light transmission just have particular restriction.For example can use compositions of thermosetting resin such as ammonia ester class, melamine class, epoxies, acrylic compounds, electromagnetic wave hardening resin composition etc.Particularly more preferably use the high electromagnetic wave hardening resin composition of skin hardness.And above-mentioned hard conating 3 preferably further contains inorganic particles.By containing inorganic particles, hard conating 3 can obtain higher skin hardness, can relax the contraction that causes because of curing such as resins simultaneously.As the material of inorganic particles, for example can use silicon dioxide (silica), tin-doped indium oxide, antimony-doped tin oxide, zirconia etc.
The method that forms hard conating 3 on base material 1 does not have particular restriction, can use for example rubbing methods such as roller coat cloth, mould coating, airblade coating, scraper coating, rotary coating, oppositely coating, intaglio plate coating, print processes such as intaglio printing, serigraphy, offset printing, ink jet printing.The thickness of hard conating 3 is preferably 1 μ m～10 μ m, more preferably 2 μ m～7 μ m.
The average reflectance of anti-reflection layer 4 preferably is more than or equal to 0.05% smaller or equal to 1% scope in the zone of wavelength 450nm～650nm, is smaller or equal to 1.5% scope in the zone of wavelength 650nm～750nm more than or equal to 0.05%.And then, for the catoptrical table look of anti-reflection layer 4, at CIE1976 (L
*a
*b
*) preferred-8≤a in the colour system
*≤ 8 ,-20≤b
*≤-2 scope, more preferably-4≤a
*≤ 3 ,-15≤b
*≤-4 scope, further preferred-1≤a
*≤ 1 ,-10≤b
*≤-6 scope.By setting anti-reflection layer 4 as mentioned above, low at wide wavelength region may reflectivity, can obtain the near-infrared shield that catoptrical colourity is the netrual colour zone.In addition, when near-infrared shield is used for display front plate, can make high-qualityization of display quality of display.
The method that forms anti-reflection layer 4 on hard conating 3 does not have particular restriction, can use for example rubbing methods such as roller coat cloth, mould coating, airblade coating, scraper coating, rotary coating, oppositely coating, intaglio plate coating, print processes such as intaglio printing, serigraphy, offset printing, ink jet printing.
Middle index layer 4a is so long as refractive index n
mFor more than or equal to 1.53 smaller or equal to 1.65 scope, more preferably more than or equal to 1.57 smaller or equal to 1.63 scope, and its material has light transmission, just do not have particular restriction.Can suit to use coating composition after for example that refractive index is high inorganic particles is evenly dispersed in the organic components etc. as its material.As above-mentioned organic components, can use for example crosslinkable organism such as compositions of thermosetting resin or electromagnetic wave hardening resin composition.In addition, as inorganic particles, can use for example particulates such as titanium dioxide, tin oxide, indium oxide, tin-doped indium oxide (ITO), antimony-doped tin oxide (ATO), zirconia, zinc paste, cerium oxide.Particularly, if use ITO particulate or ATO particulate with high conductivity, the charged effect of index layer 4a in then can being prevented, therefore more preferred.
The refractive index n of middle index layer 4a
mWith its thickness d
mProduct n
md
m(optical thickness) is preferably more than and equals the scope of 110nm smaller or equal to 163nm, more preferably more than or equal to the scope of 125nm smaller or equal to 150nm.
High refractive index layer 4b is so long as refractive index n
hFor more than or equal to 1.70 smaller or equal to 1.95 scope, more preferably more than or equal to 1.76 smaller or equal to 1.84 scope, and its material has light transmission, just do not have particular restriction.Can suit to use coating composition after for example that refractive index is the highest inorganic particles titanium oxide microparticle is evenly dispersed in the organic components as its material.As above-mentioned organic components, can use for example crosslinkable organism such as compositions of thermosetting resin or electromagnetic wave hardening resin composition, this high refractive index layer 4b is formed the crosslinked securely film of coating composition.In addition, titanium oxide microparticle more preferably uses a little less than the photocatalysis and the titanium oxide microparticle of the rutile structure that refractive index is high.This be because, there is photocatalysis in anatase structured titanium oxide microparticle, can divide organism such as the resinous principle that is deconstructed into this film and base material by ultraviolet irradiation.The amount of titanium oxide microparticle be preferably the high refractive index layer 4b after the curing general assembly (TW) more than or equal to 50 weight % smaller or equal to 65 weight %.And,, also can in above-mentioned titanium dioxide, add for example electroconductive particles such as antimony oxide, zinc paste, tin oxide so long as can satisfy above-mentioned refractive index.By adding electroconductive particle, can give charged function to high refractive index layer 4b.
The refractive index n of high refractive index layer 4b
hWith its thickness d
hProduct n
hd
h(optical thickness) is preferably more than and equals the scope of 225nm smaller or equal to 325nm, more preferably more than or equal to the scope of 250nm smaller or equal to 300nm.
In addition, the part of the organic components among the above-mentioned high refractive index layer 4b be preferably refractive index for more than or equal to 1.60 smaller or equal to 1.80 scope, more preferably more than or equal to 1.65 organic components smaller or equal to 1.75 scope.This be because, even reduce the amount of the inorganic particles among the high refractive index layer 4b, also can improve refractive index.By reducing the amount of inorganic particles, can prevent the crosslinked decline of organic components among the high refractive index layer 4b, promote the curing of organic components, thereby can improve the mar resistance of this layer.If the refractive index less than 1.60 of above-mentioned organic components, then the minimizing effect of the particulate loading among the high refractive index layer 4b is just insufficient; If this refractive index surpasses 1.80, the tendency that then exists catoptrical yellow hue to strengthen, thus and it is not preferred.As refractive index is more than or equal to 1.60 organic components smaller or equal to the high index of refraction of 1.80 scope, can use organic compound that contains aromatic rings, sulphur, bromine etc. etc., more particularly, can use for example diphenyl sulfide and derivant etc. thereof.
Low-index layer 4c is so long as refractive index n
1For more than or equal to 1.30 smaller or equal to 1.47 scope, more preferably more than or equal to 1.35 smaller or equal to 1.45 scope, and its material has light transmission, just do not have particular restriction.For example can suit to use coating composition after being evenly dispersed in inorganic particles such as fluorine system or silicone-based organic compound, silicon dioxide (silica), magnesium fluoride etc. in the organic components as its material.As above-mentioned organic components, can use for example crosslinkable organism such as compositions of thermosetting resin or electromagnetic wave hardening resin composition.When particularly using ultra-violet solidified resin composition, preferably feed inert gases such as nitrogen, shine to carry out ultraviolet ray under smaller or equal to the condition of 1000ppm at oxygen concentration as the electromagnetic wave hardening resin composition.Thus, can prevent that block hinders polymerization.
The refractive index n of low-index layer 4c
1With its thickness d
1Product n
1d
1(optical thickness) is preferably more than and equals the scope of 110nm smaller or equal to 163nm, more preferably more than or equal to the scope of 125nm smaller or equal to 150nm.
The anti-reflection layer 4 of present embodiment just is not particularly limited to above-mentioned formation so long as can reduce external reflection of light.For example, the number of plies of anti-reflection layer can be defined as individual layer, two layers, the so suitable layer structure of three-decker according to degree and catoptrical quality, the cost of reflection.In order to carry out antireflection, generally be to be the product of refractive index and thickness that optical thickness is decided to be λ/4 (λ represents wavelength) with single layer structure.The situation of two-layer structure, for the reflectivity of the high wavelength of the visibility that only reduces human eye, from base material side lamination high refractive index layer, low-index layer successively, and to make optical thickness separately be λ/4, λ/4; In order to reduce reflectivity in wide wavelength region may, from base material side lamination high refractive index layer, low-index layer successively, and to make optical thickness separately be λ/2, λ/4.The situation of three-decker, in order to reduce reflectivity in wideer wavelength region may, can be from base material side lamination successively index layer, high refractive index layer, low-index layer, and to make optical thickness separately be λ/4, λ/2, λ/4.
In addition, only the near-infrared shield of embodiment 1 also can be used as the parts of display front plate, but more preferably uses the near-infrared shield with multiple functions such as anti-reflective functions as shown in Embodiment 2.
Embodiment 3
Fig. 3 is the sectional view of an example of expression display front plate of the present invention.The display front plate 11 of present embodiment by substrate 12, be configured in the near-infrared shield 13 on the interarea of substrate 12 and electromagnetic shielding body 14, the electrode (ground connection) 15 that is configured on another interarea forms.The material of substrate 12 does not just have particular restriction so long as have the material of light transmission, for example can use tempered glass etc.Can directly use for example near-infrared shield of embodiment 2 as near-infrared shield 13.According to present embodiment, it is superior to obtain near-infrared shielding, even and preserve the display front plate of the function of function with near-infrared shield that the near-infrared absorbing ability also can not reduce and electromagnetic shielding body for a long time.
Embodiment
Below be described more specifically the present invention based on embodiment.But the present invention is not limited to following embodiment.
In 30 weight portion dimethyl formamides (DMF), add 3.8 weight portion N, N, N ', N '-four (aminophenyl)-p-phenylenediamine (PPD), 21 weight portion isobutane bromides, 15 weight portion sal tartari, replace nitrogen on one side, 80 ℃ of reactions 1 hour, reacted 7 hours on one side at 90 ℃, and then 130 ℃ of reactions 1 hour.After cooling off this reactant liquor, filter, in this filtrate, add 30 weight portion isopropyl alcohols, 5 ℃ or following stirring 1 hour.After the crystallization with the methanol wash generation, drying obtains 2.5 weight portion N, N, N ', the crystallization of N '-four (two (right-two (isobutyl) aminophenyl))-p-phenylenediamine (PPD).
Then, in 100 weight portion DMF, add 10 weight portions two (fluoroform sulfone) acid imide acid silver, the above-mentioned synthetic N of 11.8 weight portions, N, N ', N '-four (two (right-two (isobutyl) aminophenyl))-p-phenylenediamine (PPD), 60 ℃ of reactions 3 hours, the silver that isolated by filtration generates, in this filtrate, add 300 weight parts waters again, the post precipitation that generates of filtration washing once more, drying, obtain 15.7 weight portions two (fluoroform sulfone) acid imide acid N, N, N ', N '-four (two (right-two (isobutyl) aminophenyl))-to the benzene diimmonium.Measure the maximum absorption wavelength of so synthetic Diimmonium compound and the result of molar absorptivity, be respectively 1074nm, 10500Lmol
-1Cm
-1
Then, as base material, preparing thickness surperficial, that easy bonding processing has been carried out on two sides, the back side is polyethylene terephthalate (PET) film (Dong Li society system " U-34 ") of 100 μ m; Material as near infrared ray absorption layer, prepare the above-mentioned synthetic Diimmonium compound of 6 weight portions, compound (the Sumitomo system of refining " SD50-E04N " that 1 weight portion is formed by substituted benzene dithiol metal (copper) complex anion with structure shown in the above-mentioned formula (1) and the cationic counter ion counterionsl gegenions combination with structure shown in the above-mentioned formula (2), maximum absorption wavelength is 877nm), and 1 weight portion by substituted benzene dithiol metal (copper) complex anion with have the compound (the Sumitomo system of refining " SD50-E05N ", maximum absorption wavelength are 833nm) that the cationic counter ion counterionsl gegenions combination of structure shown in the above-mentioned formula (2) forms with structure shown in the above-mentioned formula (1), 100 parts by weight of acrylic acid resins (Li Yang society of Mitsubishi system " ダ ィ ヤ Na one Le BR-52 "), 125 weight portion MEKs, 460 parts by weight of toluene.Then, use the coating fluid of miniature intaglio plate spreader after coating on the above-mentioned base material mixes and stirs the material of these near infrared ray absorption layer, make dried thickness become 4 μ m, form near infrared ray absorption layer, thereby make the near-infrared shield of present embodiment.
Measure the spectrophotometric transmittance of above-mentioned near-infrared shield with spectrophotometer (Japanese beam split society's system " U-Best V-570 "), the result as shown in Figure 4, spectrophotometric transmittance in the zone of wavelength 820nm～950nm is smaller or equal to 10%, and the spectrophotometric transmittance in the zone of wavelength 950nm～1100nm is smaller or equal to 5%.In addition, haze value is 0.8%, and (x y) is (0.3215,0.3464) to see through the colourity of light.
In addition, on the near infrared ray absorption layer of above-mentioned near-infrared shield, overlap and have the PET film that cuts off ultraviolet function (Dong Li society system " Le ミ ラ one QT58; the transmitance of 380nm is 0.6%), carry out from having the fast light test of the PET film side irradiates light that cuts off ultraviolet function.Specifically, carry out following exposure experiment: use fast light testing machine (the system ス one パ one キ セ ノ Application ゥ ェ ザ one メ one SX-75 of ス ガ testing machine society), at BPT is that 63 ℃, relative humidity are under 50% the condition, from have cut off ultraviolet function PET film side with illuminance 60W/m
2(in the energy density of 300～400nm scope) irradiation xenon light 16 hours.Have the PET film that cuts off ultraviolet function by use, the xenon light wavelength that shines on the above-mentioned near-infrared shield becomes 380～1200nm.With the above-mentioned spectrophotometric transmittance of similarly measuring the near-infrared shield after this fast light test.Its result compares with the spectrophotometric transmittance before the fast light test at the spectrophotometric transmittance in the zone of wavelength 820nm～1100nm as shown in Figure 5, almost can't see variation, and the colourity that sees through light changes, and Δ x is 0.0011, and Δ y is 0.0023.
At this, colourity changes delta x and Δ y calculate from following mathematical expression.
Δx＝|x
int-x
end|
Δy＝|y
int-y
end|
Here, x in the above-mentioned mathematical expression
IntAnd y
IntRepresent the colourity that sees through light that above-mentioned fast light test is preceding, x
EndAnd y
EndRepresent the colourity that sees through light after the above-mentioned fast light test.
In addition, make near-infrared shield similarly to Example 1 except in the material of the near infrared ray absorption layer of embodiment 1, further adding the anti-neon photopigment of 2.2 weight portions (hillside plot chemistry society's system " TAP-2 ", maximum absorption wavelength is 594nm).Measure spectrophotometric transmittance with method similarly to Example 1, the result is that the spectrophotometric transmittance of wavelength 590nm is 29%, spectrophotometric transmittance in the zone of wavelength 820nm～950nm is smaller or equal to 15%, and the spectrophotometric transmittance in the zone of wavelength 950nm～1100nm is smaller or equal to 10%.And haze value is 0.8%, and (x y) is (0.2984,0.3401) to see through the colourity of light.And then, according to method similarly to Example 1, use above-mentioned near-infrared shield to carry out the result of fast light test, spectrophotometric transmittance in the zone of wavelength 820nm～1100nm is compared with the spectrophotometric transmittance before the fast light test, almost do not change, the colourity that sees through light changes, and Δ x is 0.0012, and Δ y is 0.0025.
Embodiment 3
Except further add 0.15 weight portion maximum absorption wavelength in the material of the near infrared ray absorption layer of embodiment 2 is that this of 484nm overstates that (ス Network ワ リ リ ゥ system) pigment and 0.3 weight portion maximum absorption wavelength are that this of 552nm overstated and made near-infrared shield similarly to Example 1 the pigment.Measure the result of spectrophotometric transmittance according to method similarly to Example 1, the spectrophotometric transmittance of wavelength 490nm is 44.5%, the spectrophotometric transmittance of wavelength 550nm is 35.0%, the spectrophotometric transmittance of wavelength 590nm is 28.5%, spectrophotometric transmittance in the zone of wavelength 820nm～950nm is smaller or equal to 15%, and the spectrophotometric transmittance in the zone of wavelength 950nm～1100nm is smaller or equal to 10%.And haze value is 0.8%, and (x y) is (0.3110,0.3067) to see through the colourity of light.And then the result according to method is similarly to Example 1 carried out fast light test compares with the spectrophotometric transmittance before the fast light test at the regional spectrophotometric transmittance of wavelength 820nm～1100nm, almost do not change, the colourity that sees through light changes, and Δ x is 0.0018, and Δ y is 0.0030.
Embodiment 4
Except the thickness that easy bonding processing has been carried out at surface, the back side is that the cut-out ultraviolet ray PET film (Dong Li society system " Le ミ ラ one QT58 ") of 100 μ m is used for making near-infrared shield similarly to Example 1 the base material.
Then, mixing is also stirred ultra-violet solidified material (JSR society system " デ ソ ラ イ ト Z7501 ") and the 35 weight portion methyl isobutyl ketones of being coated with firmly of esters of acrylic acid that 100 weight portions contain the silica ultramicron, the modulation coating fluid, use that miniature intaglio plate spreader is coated on above-mentioned PET film with this coating fluid with near infrared ray absorption layer side opposite surfaces on, and dry.Subsequently, with 300mJ/cm
2The intensity irradiation ultraviolet radiation, it is solidified, forming thickness on the surface of above-mentioned PET film is the hard conating of 4 μ m.
Then, mixing is also stirred the ultra-violet solidified coating material of esters of acrylic acid (JSR society system " ォ プ ス one TU4005 "), 5 weight portion polyfunctional acrylic esters (Japanese chemical drug society's system " DPHA ") and the 200 weight portion cyclohexanone that 100 weight portions contain ultrafine inorganic particle, be modulated into coating fluid, use miniature intaglio plate spreader that this coating fluid is coated on the above-mentioned hard conating, and dry.Subsequently, with 300mJ/cm
2The intensity irradiation ultraviolet radiation, it is solidified, forming thickness on the surface of above-mentioned hard conating is the middle index layer (refractive index is 1.60) of 72 μ m.
Then, use methacrylate (Japanese chemical drug society system " KAYAMER PM-21 ") and the 65 weight portion cyclohexanone mixed composition of sand mill dispersion, modulation titanium dioxide ultramicron dispersion with 30 parts by weight of titanium oxide ultramicrons (the former テ Network of stone ノ society system " TTO55 (A) "), 1 weight portion dimethylaminoethyl methacrylate (common prosperity society chemistry society's system " ラ イ ト ェ ス テ Le DM "), the phosphorous acidic group of 4 weight portions.Disperse ultra-violet solidified material (Sanyo changes into industrial society system " サ Application ラ ッ De H-601R ") and the 600 weight portion methyl isobutyl ketones of being coated with firmly of 15 parts by weight of acrylic acid ester classes to wherein mixing, be modulated into coating fluid.Use miniature intaglio plate spreader that this coating fluid is coated on the above-mentioned middle index layer, and dry.Subsequently, with 500mJ/cm
2The intensity irradiation ultraviolet radiation, it is solidified, the surface of index layer formation thickness is the high refractive index layer (the shared amount of titanium oxide microparticle is that 60 weight %, refractive index are 1.80 in the solid constituent) of 130 μ m in above-mentioned.
And then, mix and stir the thermosetting low-refraction anti-reflection material (JSR society system " ォ プ ス one TT1006 ") and the 20 weight portion methyl isobutyl ketones of 100 weight portion fluorinated polymkeric substance, be modulated into coating fluid, use miniature intaglio plate spreader that this coating fluid is coated on the above-mentioned high refractive index layer, and dry.Subsequently, carry out thermal treatment in 6 minutes under 120 ℃, forming thickness on the surface of above-mentioned high refractor is the low-index layer (refractive index is 1.41) of 92 μ m.
As mentioned above, make the antireflection/near-infrared shielding complex of present embodiment have hard conating and to comprise the anti-reflection layer of middle index layer, high refractive index layer and low-index layer.
Then, use spectrophotometer (Japanese beam split society's system " U-Best V-570 type ") to measure reflectivity from the anti-reflection layer side of this antireflection/near-infrared shielding complex, the result as shown in Figure 6, average reflectance in the zone of wavelength 450nm～650nm is smaller or equal to 1%, and the average reflectance in the zone of wavelength 650nm～750nm is smaller or equal to 1.5%.In addition, catoptrical table look is at CIE1976 (L
*a
*b
*) a in the colour system
*Be-0.68, b
*Be-8.96.In addition, measure the spectrophotometric transmittance of the antireflection/near-infrared shielding complex of present embodiment according to method similarly to Example 1, the result as shown in Figure 7, spectrophotometric transmittance in the zone of wavelength 850nm～900nm is smaller or equal to 10%, and the spectrophotometric transmittance in the zone of wavelength 900nm～1100nm is smaller or equal to 10%.In addition, haze value is 0.9%, and (x y) is (0.3235,0.3484) to see through the colourity of light.And then, on the anti-reflection layer of above-mentioned antireflection/near-infrared shielding complex, overlap and have the PET film that cuts off ultraviolet function (Dong Li society system " Le ミ ラ one QT58; the transmitance of 380nm is 0.6%); from the anti-reflection layer side with similarly to Example 1 condition irradiation xenon light; carry out the result of fast light test; the spectrophotometric transmittance in the zone of wavelength 820nm～1100nm is compared with the spectrophotometric transmittance before the fast light test; almost do not change, the colourity that sees through light changes, Δ x is 0.0012, and Δ y is 0.0023.
Embodiment 5
Except the thickness that easy bonding processing has been carried out at surface, the back side is that the cut-out ultraviolet ray PET film (Dong Li society system " Le ミ ラ one QT58 ") of 100 μ m is used for the base material, make near-infrared shield similarly to Example 2, above-mentioned PET film with near infrared ray absorption layer side opposite surfaces on lamination hard conating, middle index layer, high refractive index layer, low-index layer successively similarly to Example 4.An interarea of the glass substrate that the near infrared ray absorption layer side and the thickness of this near-infrared shield is 2.3mm is fitted, and then, make the electronic console optical filter (display front plate) of present embodiment with the opposing face applying of the netted film of electromagnetic wave shielding (line width is that 10 μ m, line are spaced apart 250 μ m) with the interarea of the near-infrared shield side of above-mentioned glass substrate.
This filter set is installed to color plasma display, measure bright chamber (bright place) contrast with the assay method (EIAJED-2710A) of the color plasma display module of JEITA's standard, the result is 104.
Embodiment 6
Except the thickness that easy bonding processing has been carried out at surface, the back side is that the cut-out ultraviolet ray PET film (Dong Li society system " Le ミ ラ one QT58 ") of 100 μ m is used for the base material, make near-infrared shield similarly to Example 3, above-mentioned PET film with near infrared ray absorption layer side opposite surfaces on lamination hard conating, middle index layer, high refractive index layer, low-index layer successively similarly to Example 4.An interarea of the glass substrate that the near infrared ray absorption layer side and the thickness of this near-infrared shield is 2.3mm is fitted, and then, make the electronic console optical filter (display front plate) of present embodiment with the opposing face applying of the netted film of electromagnetic wave shielding (line width is that 10 μ m, line are spaced apart 250 μ m) with the interarea of the near-infrared shield side of above-mentioned glass substrate.
Measure bright chamber (bright place) contrast according to method similarly to Example 5 at this light filter, the result is 149.
Comparative example 1
Replace as the anionic Diimmonium compound of pairing (Japanese カ one リ ッ ト society's system " CIR-1081 ") the Diimmonium compound of embodiment 1 except using 6 weight portions to contain the antimony hexafluoride ion, make the near-infrared shield of this comparative example similarly to Example 1.
Measure the spectrophotometric transmittance of above-mentioned near-infrared shield according to method similarly to Example 1, the result as shown in Figure 8, spectrophotometric transmittance in the zone of wavelength 820nm～950nm is smaller or equal to 10%, and the spectrophotometric transmittance in the zone of wavelength 950nm～1100nm is smaller or equal to 5%.And haze value is 0.8%, and (x y) is (0.3217,0.3468) to see through the colourity of light.
In addition, carry out fast light test according to method similarly to Example 1.With the above-mentioned spectrophotometric transmittance of similarly measuring the near-infrared shield after this fast light test.Its result as shown in Figure 9, the spectrophotometric transmittance in the zone of wavelength 820nm～830nm surpasses 13%, the colourity that sees through light changes, Δ x is 0.0053, Δ y is 0.0080, change in color is big.
Comparative example 2
Except using 0.4 weight portion cyanine compound (woods protobiochemistry institute system " NK124 ", maximum absorption wavelength is 928nm) and 0.4 weight portion cyanine compound (hillside plot chemistry society's system " IR-301 ", maximum absorption wavelength is 830nm) replace making the near-infrared shield of this comparative example similarly to Example 1 beyond two kinds of formed compounds of counter ion counterionsl gegenions combination of embodiment 1.
Measure the spectrophotometric transmittance of above-mentioned near-infrared shield according to method similarly to Example 1, consequently, spectrophotometric transmittance in the zone of wavelength 820nm～950nm is smaller or equal to 15%, and the spectrophotometric transmittance in the zone of wavelength 950nm～1100nm is smaller or equal to 10%.And haze value is 0.8%, and (x y) is (0.3200,0.3442) to see through the colourity of light.In addition, carry out fast light test according to method similarly to Example 1.With the above-mentioned spectrophotometric transmittance of similarly measuring the near-infrared shield after this fast light test.Its result as shown in figure 10, the spectrophotometric transmittance in the zone of wavelength 820nm～830nm surpasses 13%, the colourity that sees through light changes, Δ x is 0.007, Δ y is 0.009.
The possibility of utilizing on the industry
As mentioned above, carry out fast light test even the present invention can provide, also have high near infrared ray and hide Covering property, the near-infrared shield that near infrared absorbability can not reduce. In addition, by using this The near-infrared shield of invention can provide the display that is suitable for electronic console, particularly PDP Use front panel.
Claims (11)
1. near-infrared shield is characterized in that, comprise base material and be configured near infrared ray absorption layer on the interarea of described base material, under the condition of 63 ℃ of blackboard temperatures, relative humidity 50%, from described near infrared ray absorption layer side with illuminance 60W/m
2(in the energy density of 300～400nm scope) irradiation 16 hours is more than or equal to the xenon light time of 380nm smaller or equal to the wavelength of 1200nm, behind the described pre-irradiation of representing with the chromatic diagram of CIE1931XYZ colour system through colourity changes delta x, the Δ y of light respectively smaller or equal to 0.005.
2. near-infrared shield according to claim 1, it is characterized in that described near infrared ray absorption layer comprises Diimmonium compound that contains the sulfonic acid imide derivative and the compound that is formed by substituted benzene dithiol metal complex anion with structure shown in the following formula (1) and the cationic counter ion counterionsl gegenions combination with structure shown in the following formula (2);
In formula (1), R
1, R
2Expression is selected from least a substituting group in the group of being made up of for base, replacement or unsubstituted piperazinyl and replacement or unsubstituted phenyl alkylamino, replacement or unsubstituted morpholino base, replacement or the unsubstituted thiomorpholine of the alkyl of carbon number 1～6, carbon number 1～8, and M represents transition metal;
In formula (2), Q
1, Q
2Expression is selected from by 5-member heterocyclic ring containing nitrogen, the condensed ring that contains 5-member heterocyclic ring containing nitrogen, hexa-atomic nitrogen heterocyclic ring and contains at least a heterogeneous ring compound in the group that hexa-atomic nitrogenous heterocyclic condensed ring forms, R
3, R
4The alkyl of expression carbon number 1～8, n represents numeral 2,3 or 4.
3. near-infrared shield according to claim 2 is characterized in that, combine with the terminal nitrogen atom at the kation position of described Diimmonium compound substituent at least one be alkyl with branched structure.
4. according to claim 2 or 3 described near-infrared shields, it is characterized in that described near infrared ray absorption layer further contains the resin that described Diimmonium compound and the described compound that is formed by the counter ion counterionsl gegenions combination are disperseed.
5. near-infrared shield according to claim 4 is characterized in that the glass transition temperature of described resin is more than or equal to 80 ℃.
6. according to claim 2 or 3 described near-infrared shields, it is characterized in that described near infrared ray absorption layer further contains at the compound that has maximum absorption wavelength more than or equal to 580nm smaller or equal to the wavelength region may of 620nm.
7. according to claim 2 or 3 described near-infrared shields, it is characterized in that described near infrared ray absorption layer further contains at the compound that has maximum absorption wavelength more than or equal to 540nm smaller or equal to the wavelength region may of 570nm.
8. according to claim 2 or 3 described near-infrared shields, it is characterized in that described near infrared ray absorption layer further contains at the compound that has maximum absorption wavelength more than or equal to 480nm smaller or equal to the wavelength region may of 500nm.
9. according to claim 2 or 3 described near-infrared shields, it is characterized in that the haze value of described near infrared ray absorption layer is smaller or equal to 1%.
10. according to claim 2 or 3 described near-infrared shields, it is characterized in that, described near-infrared shield further contains hard conating and anti-reflection layer, and described hard conating and described anti-reflection layer are to be configured on the opposing face of interarea of the described base material that disposes described near infrared ray absorption layer.
11. display front plate is characterized in that, disposes any described near-infrared shield of claim 1～10 on substrate.
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|---|---|---|---|
| JP2004334904 | 2004-11-18 | ||
| JP2004334904 | 2004-11-18 | ||
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101201542B (en) * | 2006-09-26 | 2011-10-12 | 罗门哈斯电子材料有限公司 | Coating compositions for photolithography |
| CN106814417A (en) * | 2017-03-14 | 2017-06-09 | 浙江博达光电有限公司 | The optical low-pass filter and its manufacture method of day and night type |
| WO2022016524A1 (en) * | 2020-07-24 | 2022-01-27 | Huawei Technologies Co., Ltd. | Infrared cut filter, infrared cut lens and camera module |
-
2005
- 2005-11-14 CN CNB2005101153166A patent/CN100538410C/en not_active Expired - Fee Related
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101201542B (en) * | 2006-09-26 | 2011-10-12 | 罗门哈斯电子材料有限公司 | Coating compositions for photolithography |
| CN106814417A (en) * | 2017-03-14 | 2017-06-09 | 浙江博达光电有限公司 | The optical low-pass filter and its manufacture method of day and night type |
| CN106814417B (en) * | 2017-03-14 | 2023-05-09 | 浙江博达光电有限公司 | Day and night dual-purpose optical low-pass filter and manufacturing method thereof |
| WO2022016524A1 (en) * | 2020-07-24 | 2022-01-27 | Huawei Technologies Co., Ltd. | Infrared cut filter, infrared cut lens and camera module |
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| CN100538410C (en) | 2009-09-09 |
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