CN101107258A - Borate and near-infrared ray absorption material - Google Patents

Borate and near-infrared ray absorption material Download PDF

Info

Publication number
CN101107258A
CN101107258A CNA2006800030602A CN200680003060A CN101107258A CN 101107258 A CN101107258 A CN 101107258A CN A2006800030602 A CNA2006800030602 A CN A2006800030602A CN 200680003060 A CN200680003060 A CN 200680003060A CN 101107258 A CN101107258 A CN 101107258A
Authority
CN
China
Prior art keywords
infrared
borate
absorbing
group
dyestuff
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CNA2006800030602A
Other languages
Chinese (zh)
Inventor
伊藤彰男
石田知史
饭田俊哉
石井尊子
小林信弘
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Nippon Shokubai Co Ltd
Original Assignee
Nippon Shokubai Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Nippon Shokubai Co Ltd filed Critical Nippon Shokubai Co Ltd
Publication of CN101107258A publication Critical patent/CN101107258A/en
Pending legal-status Critical Current

Links

Images

Landscapes

  • Optical Filters (AREA)

Abstract

The invention provides a borate for a near-infrared ray absorption material, having an anion represented by the formula (1): [BR1 mR 2 4-m]-(wherein R1 represents an aryl with the electro-attracting group; R2 represents an organic group, halogen group or hydroxyl group; m is an integer of 1 to 4). The borate can improve the durability of the near-infrared ray absorption dye, especially fire-resisting property and damp proofness.

Description

Borate and near-infrared-absorbing material
Technical field
The present invention relates to be used for near-infrared-absorbing material borate, contain this boratory near-infrared-absorbing material, and the spectral filter that is used for plasma display and optical-semiconductor element that uses this near-infrared-absorbing material.Especially, the present invention relates to have raising the near-infrared absorbing dyestuff weather resistance borate, contain the transparency and the good boratory near-infrared-absorbing material of weather resistance in the visible region, and the spectral filter that is used for plasma display and optical-semiconductor element that uses this near-infrared-absorbing material.
Background technology
In recent years, have been noted that and be applicable to thin and the PDP big area screen (plasma display panel).PDP produces the near infrared ray of wavelength 800nm to 1000nm when plasma discharge, and has this near infrared ray to cause the problem of the telepilot malfunction of household electrical appliance.In addition, because the optical-semiconductor element that uses has hypersensitivity near infrared region, so need remove near infrared ray in CCD photographic camera etc.In this case, need have high near-infrared absorbing ability and in the visible region near-infrared-absorbing material of high transparent.
As near-infrared-absorbing material, the material of the dyestuff that extensive known adding can absorption near infrared ray.As this near-infrared absorbing dyestuff, use dyestuff based on cyanine, poly-methine dyestuff, the sour cyanines radical dye in side, porphyryl dyestuff, dithiol metal complex compound radical dye traditionally, based on the dyestuff of phthalocyanine, based on the dyestuff of diimmonium etc.In the middle of these, based on the dyestuff of diimmonium since its under the wavelength that is not shorter than 900nm high near-infrared absorbing ability and in the visible region the high transparency and therefore be widely used (for example referring to US-B-6,255,031 and US-B-6,522,463).As the near-infrared-absorbing material that is used for optical-semiconductor element, also use a class (for example referring to US-A-5,567,778) that contains based on the compound of cupric phosphate.
In addition, because PDP produces discharge in mainly by the rare gas gas atmosphere that particularly neon is formed that is encapsulated in the panel, and, make that fluorescent substance R, the G and the B that are contained in the interior cell of panel are luminous by means of the vacuum ultraviolet ray that produces when the discharge.In this emission process, also emitted the unwanted hertzian wave of PDP work simultaneously, therefore also need shielding electromagnetic wave.In addition, for inhibitory reflex light, also need anti-reflective film and antiglare film (the anti-film that dodges).Therefore, usually by near-infrared absorption film, emi shielding film and anti-reflective film being laminated to as preparing the spectral filter that is used for plasma display on the glass of supporting substrate or the impact absorption sheet.Front surface side that can be by being placed in PDP or by use tackiness agent or pressure-sensitive adhesive directly bonding use this class to be used for the spectral filter of plasma display.
Summary of the invention
Yet representative sometimes may poor durability based on the near-infrared absorbing dyestuff of the dyestuff of diimmonium, and the deterioration of near-infrared absorbing ability or paintedly may cause serious problem in indicating meter or optical-semiconductor element are used.This deterioration is considered to be caused by the deterioration of dyestuff that for example heat, moisture and light cause the dyestuff deterioration by multiple factor.Therefore, challenged the various improvement of the weather resistance of near-infrared absorbing dyestuff traditionally, yet effect is still insufficient.In addition, owing to be difficult to improve in the near-infrared-absorbing material content, therefore be difficult to obtain the good thin-film material of near-infrared absorbing ability based on the compound of cupric phosphate.
Therefore, an object of the present invention is to provide and to be advantageously used in the near-infrared-absorbing material (dyestuff) with the weather resistance, particularly thermotolerance that improve the near-infrared absorbing dyestuff and the borate of wet fastness.
Another object of the present invention provides the transparency and the good near-infrared-absorbing material of weather resistance in the visible region.
Another purpose of the present invention provides the spectral filter that is used for plasma display, the spectral filter that is used for optical-semiconductor element, and the plasma display and the optical-semiconductor element that use near-infrared-absorbing material.
The inventor has furtherd investigate raising near-infrared absorbing dyestuff, mode especially for the weather resistance of the near-infrared-absorbing material in the spectral filter, discovery has the weather resistance that the borate that is connected the aryl on the boron atom that contains electron-withdrawing group can improve the near-infrared absorbing dyestuff, particularly thermotolerance and wet fastness, and it is good to add the transparency and the weather resistance (particularly thermotolerance and wet fastness) of this boratory near-infrared-absorbing material in the visible region.In addition, the inventor finds by using this near-infrared-absorbing material, can obtain transparent good spectral filter that is used for plasma display and the spectral filter that is used for optical-semiconductor element in weather resistance and the visible region.Based on these discoveries, finished the present invention.
That is, can realize this purpose by a kind of like this borate that is used for near-infrared-absorbing material, this borate has the negatively charged ion by following formula (1) expression:
[BR 1 mR 2 4-m] - (1)
R wherein 1Expression has the aryl of electron-withdrawing group; R 2Expression organic group, halogen group or hydroxyl; M is 1 to 4 integer.
In addition, can realize another purpose by the near-infrared-absorbing material that comprises borate of the present invention and near-infrared absorbing dyestuff.
The spectral filter that is used for plasma display of near-infrared-absorbing material that can the application of the invention and be used for the spectral filter of optical-semiconductor element and use the plasma display of these spectral filters and optical-semiconductor element to realize another purpose.
Because borate of the present invention has improved the weather resistance of near-infrared absorbing dyestuff, particularly thermotolerance and wet fastness, and can not weaken the transparency in the visible region in addition, therefore it can be advantageously used in various near-infrared-absorbing materials (dyestuff), comprises in the dyestuff based on diimmonium that endurance issues is arranged traditionally.
In addition, be used for plasma display or optical-semiconductor element by the spectral filter that use is contained boratory near-infrared-absorbing material of the present invention, owing to kept the transparency in near-infrared absorbing ability and the visible region for a long time, therefore can improve the outward appearance of indicating meter or optical-semiconductor element.
By explaining following preferred embodiment and accompanying drawing, above and other purpose of the present invention, embodiment and other advantages will become obvious.
Description of drawings
Fig. 1 is the Visible-to-Near InfaRed absorption spectrum of the diimmonium TEPB salt that obtains in embodiment 3-1.
Fig. 2 is the IR spectrum of the diimmonium TEPB salt that obtains in embodiment 3-1.
Fig. 3 is the Visible-to-Near InfaRed absorption spectrum that is used for the diimmonium SbF6 salt of comparative example 2-1.
Fig. 4 is the IR spectrum that is used for the diimmonium SbF6 salt of comparative example 2-1.
Fig. 5 is the Visible-to-Near InfaRed absorption spectrum that is used for the diimmonium BPh4 salt of comparative example 3-1.
Fig. 6 is the IR spectrum that is used for the diimmonium BPh4 salt of comparative example 3-1.
Fig. 7 is the Visible-to-Near InfaRed absorption spectrum of the near-infrared-absorbing material A6 for preparing in embodiment 6-3.
Fig. 8 is the Visible-to-Near InfaRed absorption spectrum of the near-infrared-absorbing material B5 for preparing in comparative example 5-2.
Fig. 9 is the Visible-to-Near InfaRed absorption spectrum of the near-infrared-absorbing material B6 for preparing in comparative example 6-2.
Figure 10 is the Visible-to-Near InfaRed absorption spectrum of the indoles TEPB salt for preparing in embodiment 12-1.
Figure 11 is the IR spectrum of the indoles TEPB salt for preparing in embodiment 12-1.
Figure 12 is the Visible-to-Near InfaRed absorption spectrum that is used for the TEPBNa of embodiment 12-1.
Figure 13 is the IR spectrum that is used for the TEPBNa of embodiment 12-1.
Figure 14 is the Visible-to-Near InfaRed absorption spectrum that is used for the indoles PF6 of embodiment 12-1.
Figure 15 is the IR spectrum that is used for the indoles PF6 of embodiment 12-1.
Embodiment
To explain the present invention in detail below.
A first aspect of the present invention relates to the borate that is used for near-infrared-absorbing material, and it has the negatively charged ion by following formula (1) expression:
[BR 1 mR 2 4-m] - (1)
R wherein 1Expression has the aryl of electron-withdrawing group; R 2Expression organic group, halogen group or hydroxyl; M is 1 to 4 integer.
(1) negatively charged ion of formula (1)
The negatively charged ion that is used for the present invention is the borate anion by formula (1) expression, and is bonded on the boron atom by the aryl that will have electron-withdrawing group, can improve the weather resistance of near-infrared absorbing dyestuff.
R in the formula (1) 1Expression has the aryl of electron-withdrawing group, and is not particularly limited.Preferred be connected with the aryl with 6 to 12 carbon atoms of electron-withdrawing group on it, and for example comprise phenyl, naphthyl and the xenyl that is connected with electron-withdrawing group on it.In the middle of above-mentioned aryl, the phenyl that is connected with electron-withdrawing group on it (is R 1Be the phenyl that is connected with electron-withdrawing group on it) be preferred economically.
Although the R in the formula (1) 1In electron-withdrawing group be not particularly limited but its especially preferably at least a being selected from by-C pF 2P+1(p is a natural number) ,-NO 2,-CN ,-F ,-Cl and-substituting group in the group that Br forms, and it is more preferably at least a being selected from by-CF 3,-C 2F 5Substituting group in the group of forming with-F, and especially preferably-F.When containing a plurality of electron-withdrawing group in the aryl, each electron-withdrawing group can be identical or different.In the present invention, especially, use-F can improve thermotolerance and wet fastness.Therefore, the R in the formula (1) 1Pentafluorophenyl group (C preferably 6F 5) ,-C 6HF 4,-C 6H 2F 3,-C 6H 3F 2,-C 6H 4F ,-C 6F 4CF 3,-C 6F 3(CF 3) 2,-C 6F 2(CF 3) 3,-C 6F (CF 3) 4,-C 6(CF 3) 5Deng, preferred especially pentafluorophenyl group.
In the present invention, have the borate anion of introducing the aryl of electron-withdrawing group on it, can improve the thermotolerance and the wet fastness of near-infrared absorbing dyestuff by adding.
In formula (1) by R 2The substituting group of expression is not particularly limited, as long as it is organic group, halogen atom or hydroxyl, and this organic group can have electron-withdrawing group and gets final product.Organic group comprises, for example can have substituently to have the aryl (for example phenyl, naphthyl and xenyl) of 1 to 12 carbon atom and have alkyl of 1 to 12 carbon atom etc., but be not particularly limited to this.Particularly, can enumerate straight chain, side chain or alicyclic alkyl for example methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, sec-butyl, the tertiary butyl, n-pentyl, 1-methyl butyl, 1-ethyl propyl, 1,2-dimethyl propyl, 1,1-dimethyl propyl, neo-pentyl, n-hexyl and cyclohexyl.Especially, when organic group is alkyl, its preferably have electron-withdrawing group and more preferably wherein all or part of hydrogen atom replaced by fluorine atom.Particularly, can enumerate trifluoromethyl, 2,2,2-trifluoroethyl, 3,3,3-trifluoro propyl, 4,4,4-trifluoro butyl, perfluor ethyl, perfluoro propyl, perfluoro butyl etc.Halogen atom for example specifically comprises-F ,-Cl ,-Br and-I, more preferably-F.
In the present invention, the m in the formula (1) is not particularly limited, as long as it is 1 to 4, yet it is preferably 4, promptly has by [B (R 1) 4] -Structure a kind of of expression.When m is not less than 2 in the present invention, can comprise a plurality of R in the borate anion 1, and a plurality of in this case R 1Each can be identical or different.
As borate anion, for example can enumerate [B (C by formula (1) expression 6F 5) 4] -(four (pentafluorophenyl group) borate), [B (C 6F 4CF 3) 4] -, [B (C 6F 5) 3(C 6H 5)] -, [B (C 6F 5) 2(C 6H 5) 2] -, [B (C 6F 5) (C 6H 5) 3] -, [B (C 6F 5) 3F] -, [B (C 6F 5) 2F 2] -, [B (C 6F 5) F 3] -, [B (C 6F 5) 3(CF 3)] -, [B (C 6F 5) 2(CF 3) 2] -, [B (C 6F 5) (CF 3) 3] -, [B (C 6F 5) 3(C 6F 4CF 3)] -, [B (C 6F 5) 2(C 6F 4CF 3) 2] -, [B (C 6F 5) (C 6F 4CF 3) 3] -, [B (C 6F 4CF 3) 3F] -, [B (C 6F 4CF 3) 2F 2] -, [B (C 6F 4CF 3) F 3] -, [B (C 6F 4CF 3) 3(CF 3)] -, [B (C 6F 4CF 3) 2(CF 3) 2] -, [B (C 6F 4CF 3) (CF 3) 3] -, [B (C 6F 5) 3(C 6H 13)] -, [B (C 6F 5) 2(C 6H 13) 2] -, [B (C 6F 5) (C 6H 13) 3] -, [B (C 6H 4CF 3) 4] -, [B (C 6H 3F 2) 4] -Deng.In the present invention, in the example of borate anion, more preferably [B (C 6F 5) 4] -In the present invention, borate anion can be separately or is used with two or more mixed form.
(2) comprise the anionic salt of formula (1)
The anionic salt that comprises formula (1) can be at the borate anion of formula (1) and have the salt that forms between the positively charged ion of near-infrared absorbing ability, perhaps at the borate anion of formula (1) and do not have the salt that forms between the positively charged ion of near-infrared absorbing ability.In last situation, borate can serve as near-infrared-absorbing material (dyestuff), and the weather resistance that can show raising particularly thermotolerance and wet fastness.In one situation of back, owing to itself can not show the near-infrared absorbing ability, therefore by mix weather resistance, particularly thermotolerance and the wet fastness of the mixing near-infrared-absorbing material (dyestuff) that can significantly improve gained with the near-infrared absorbing dyestuff.
To explain back one situation below, borate promptly of the present invention is at the borate anion of formula (1) and does not have the embodiment of the salt that forms between the positively charged ion of near-infrared absorbing ability.
As the anionic salt that contains with good grounds formula of the present invention (1), can use the salt of following borate anion: basic metal is the salt of lithium, sodium, potassium, rubidium and caesium for example; Alkaline-earth metal is the salt of beryllium, magnesium, calcium, strontium and barium for example; Transition metal is the salt of silver, copper for example; Ammonium salt is ammonium, positive fourth ammonium, dimethylammonium, TMA (TriMethylAmine), three second ammoniums, three different third ammoniums, three positive fourth ammoniums, tetramethylammonium, Tetrylammonium, four positive fourth ammonium and N for example, N-dimethyl hexamethylene ammonium; Aniline salt is methylphenylamine, N for example, accelerine, N, N-dimethyl-4-monomethylaniline, N, N-Diethyl Aniline, N, N-phenylbenzene aniline and N, N, N-trimethylaniline; Pyridinium salt is pyridine for example, the N-picoline, the N-butyl-pyridinium, N-methyl-4-picoline, the N-benzyl-pyridine, 3-methyl-N-butyl-pyridinium, the 2-picoline, the 3-picoline, the 4-picoline, 2, the 3-lutidine, 2, the 4-lutidine, 2, the 6-lutidine, 3, the 4-lutidine, 3, the 5-lutidine, 2,4, the 6-trimethylpyridine, 2-fluorine pyridine, 3-fluorine pyridine, 4-fluorine pyridine, 2, the 6-difluoro pyridine, 2,3,4,5,6-five fluorine pyridines, the 2-chloropyridine, the 3-chloropyridine, the 4-chloropyridine, 2, the 3-dichloropyridine, 2, the 5-dichloropyridine, 2, the 6-dichloropyridine, 3, the 5-dichloropyridine, 3,5-two chloro-2,4, the 6-trifluoromethyl pyridine, the 2-bromopyridine, the 3-bromopyridine, the 4-bromopyridine, 2, the 5-dibromo pyridine, 2, the 6-dibromo pyridine, 3, the 5-dibromo pyridine, the 2-cyanopyridine, the 3-cyanopyridine, the 4-cyanopyridine, 2 hydroxy pyrimidine, the 3-pyridone, the 4-pyridone, 2, the 3-dihydroxy-pyridine, 2, the 4-dihydroxy-pyridine, 2-methyl-5-ethylpyridine, 2-chloro-3-cyanopyridine, the 4-carboxamide pyridine, 4-formaldehyde pyridine, the 2-phenylpyridine, the 3-phenylpyridine, the 4-phenylpyridine, 2,6-phenylbenzene pyridine, the 4-nitropyridine, 4-methoxypyridine, 4-vinylpridine, the 4-mercaptopyridine, the 4-tert .-butylpyridine, 2, the 6-di-tert-butyl pyridine, the 2-benzyl-pyridine, the 3-acetylpyridine, the 4-ethylpyridine, the 2-pyridinecarboxylic acid, the 4-pyridinecarboxylic acid, the 2-benzoyl pyridine; Imidazole salts is imidazoles, 1-Methylimidazole, 1-ethyl-3-Methylimidazole, 1-propyl group-3-Methylimidazole, 1-butyl-3-Methylimidazole, 1-hexyl-3-Methylimidazole, 1-methyl-3-octyl group imidazoles, 1-methyl-N-benzyl imidazole, 1-methyl-3-(3-phenyl propyl) imidazoles, 1-butyl-2 for example, 3-methylimidazole, 1-ethyl-2, the 3-methylimidazole; Pyrrolidinium is 1-ethyl-1-crassitude and 1-butyl-1-crassitude for example; Quinolinium is quinoline, isoquinoline 99.9 for example; Carbon salt is triphenylcarbenium and three-4-p-methoxy-phenyl carbon for example; Microcosmic salt is 3,5-dimethylphenyl phosphorus, triphenyl phosphorus, tetraethyl-phosphorus and tetraphenylphosphonium for example; Sulfonium salt is trimethylsulfonium and triphenylsulfonium for example; Salt compounded of iodine is phenylbenzene iodine and two-4-p-methoxy-phenyl iodine etc. for example.In this case, when borate anion is used as the form of alkaline earth salt, adopt the wherein form of two borate anions of each earth alkali metal according to salt of the present invention.
In the middle of these salt, the positively charged ion that does not preferably have the near-infrared absorbing ability comprises an alkali metal salt, ammonium salt and nitrogenous organic cation salt.Particularly, preferred use comprise have sodium, any cationic salt of ammonium, pyridine, aniline, imidazoles, tetramethyleneimine and quinoline structure.Particularly preferably, can use for example boratory N of four (pentafluorophenyl groups), N-Dimethylcyclohexyl ammonium salt, N, N-dimethyl-4-methylcyclohexyl ammonium salt, N, N-diethylbenzene amine salt, 1-methyl-imidazole salts and quinolinium.Because borate does not have the near-infrared absorbing ability, therefore preferably it is used with the near-infrared absorbing dyestuff.In this case, borate can be separately or is used with two or more mixed form.
In this respect, in the present invention, positively charged ion can perhaps use as the counter ion of two or more cationic mixed forms as borate anion separately as the counter ion use of borate anion.
Can suitably select to be formulated in the amount of the anionic salt of the formula (1) in the near-infrared-absorbing material of the present invention although depend on application, its be preferably based on 1mol with the near-infrared absorbing dyestuff that is used in combination 0.5 to 8mol, more preferably 1 to 5mol.In this case, the amount of preparation that is lower than the anionic salt of 0.5mol will provide insufficient add-on and the boron atom aryl bonding with electron-withdrawing group, this can not provide competent weather resistance to improve, and the amount that surpasses 8mol will can not provide and add suitable effect and can not be economic.
A kind of situation before explaining then, borate promptly wherein of the present invention are at the borate anion of formula (1) and the positively charged ion with near-infrared absorbing ability, particularly have the embodiment of the salt that forms between the organic cation of near-infrared absorbing ability.In this case, because borate itself also can serve as the near-infrared absorbing dyestuff, therefore borate of the present invention itself can serve as near-infrared-absorbing material, and pass through in the existence of borate anion, this near-infrared-absorbing material has good weather resistance, particularly thermotolerance and wet fastness.
Can form for the counter ion of the borate anion of formula (1) and positively charged ion with near-infrared absorbing ability and be not particularly limited, as long as it is the positively charged ion that has good near-infrared absorbing ability under 700 to 1200nm wavelength.For example, can comprise diimmonium positively charged ion and cyanine dyes base positively charged ion.In the middle of these, diimmonium positively charged ion near-infrared absorbing ability under 900 to 1200nm wavelength is good, and cyanine dyes base positively charged ion near-infrared absorbing ability under 700 to 1000nm wavelength is good.
When forming when being the diimmonium positively charged ion for the counter ion of the borate anion of formula (1) and positively charged ion with near-infrared absorbing ability, the diimmonium positively charged ion is not particularly limited, as long as it has good filtration near infrared ray effect under 900 to 1200nm wavelength, and the positively charged ion of preferred following formula (2).This class has the high transparency by the diimmonium positively charged ion of following formula (2) expression in the visible region, and by being used for the plasma display optical device, it can improve the outward appearance of indicating meter, perhaps by being used for the spectral filter that optical-semiconductor element is used, it can strengthen the susceptibility of CCD photographic camera.
Figure A20068000306000141
In representing the cationic formula of diimmonium (2), by R 3To R 10The substituting group of expression comprises hydrogen atom, halogen atom and has the alkyl of 1 to 10 carbon atom, perhaps has 1 to 10 carbon atom and have substituent alkyl.
As halogen atom, can comprise for example fluorine atom, chlorine atom, bromine atoms and iodine atom.
As alkyl with 1 to 10 carbon atom, for example can comprise straight chain, side chain or alicyclic alkyl for example methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, sec-butyl, the tertiary butyl, n-pentyl, 1-methyl butyl, 1-ethyl propyl, 1,2-dimethyl propyl, 1,1-dimethyl propyl, neo-pentyl, n-hexyl and cyclohexyl.
But as with can have substituent substituting group with alkyl bonding of 1 to 10 carbon atom, can comprise cyano group; Hydroxyl; Halogen atom is fluorine atom, chlorine atom and bromine atoms for example; Alkoxyl group with 1 to 6 carbon atom is methoxyl group, oxyethyl group, positive propoxy and n-butoxy for example; Alkoxyl group alkoxyl group with 2 to 8 carbon atoms is methoxymethoxy, oxyethyl group methoxy base, methoxy ethoxy, ethoxy ethoxy, methoxy propoxy, methoxyl group butoxy and oxyethyl group butoxy for example; Alkoxyl group alkoxyl group alkoxyl group with 3 to 15 carbon atoms, for example methoxymethoxy methoxyl group, methoxymethoxy oxyethyl group, methoxy ethoxy oxyethyl group and ethoxy ethoxy ethoxy; Allyloxy; Aryloxy with 6 to 12 carbon atoms is phenoxy group, tolyloxy, xylyloxy and naphthyloxy for example; Alkoxy carbonyl with 2 to 7 carbon atoms is methoxycarbonyl, ethoxy carbonyl, positive propoxy carbonyl, isopropoxy carbonyl and n-butoxy carbonyl for example; Alkyl carbonyl oxy with 2 to 7 carbon atoms is methyl carbonyl oxygen base, ethyl oxy carbonyl, n-propyl carbonyl oxygen base and normal-butyl carbonyl oxygen base for example; Alkoxyl group carbonyl oxygen base with 2 to 7 carbon atoms is methoxyl group carbonyl oxygen base, oxyethyl group carbonyl oxygen base, positive propoxy carbonyl oxygen base, n-butoxy carbonyl oxygen base etc. for example.Particularly, R 3To R 10Comprise trifluoromethyl, 2,2,2-trifluoroethyl, 3,3,3-trifluoro propyl, 4,4,4-trifluoro butyl, pentafluoroethyl group, perfluoro propyl, perfluoro butyl etc.
In the present invention, R 3To R 10Can be an identical or different class, yet preferably they all be identical.In addition, about the bonding position of diamines, in view of synthetic contraposition with respect to the nitrogen-atoms that is bonded to the phenylenediamine skeleton is easily, although be not particularly limited to this.
The method of the salt between the diimmonium positively charged ion of the borate anion of production formula (1) and formula (2) is not particularly limited, and can be by known method or the production of improving one's methods by currently known methods.For example, can coexist as by the borate anion that makes formula (1) by oxygenant for example silver salt or by electrolytic oxidation with 1, produce the salt between borate anion and the diimmonium positively charged ion in the system of 4-phenylenediamine derivative oxidation.For example, its can by with JP-B-43-25335 in the similar method production of method described.
Particularly, can obtain wherein all substituting group (R in the following manner 3To R 10) identical 1,4-phenylenediamine derivative: the product reduction that will obtain by the Ullmann reaction of right-phenylenediamine and 1-chloro-4-oil of mirbane to be obtaining the amine compound by following formula (4) expression,
Figure A20068000306000161
Preferably under 50 to 140 ℃ water soluble polar solvent for example among DMF (N, dinethylformamide), DMI (1,3-dimethyl-2-imidazolone) and the NMP (N-Methyl pyrrolidone) with this amine compound with corresponding to desirable R 3To R 10Halogenide (for example work as R 3To R 10All be i-C 4H 9The time be BrCH 2CH (CH 3) 2) reaction.In above method, can introduce multiple substituting group by multiple halogenide is used in combination.
Subsequently, to synthetic 1 thus, 4-phenylenediamine derivative is with the water-soluble soluble polar solvent of borate (for example four (pentafluorophenyl group) Sodium Tetraborate) of formula (1) for example among DMF, DMI and the NMP, again by add oxygenant for example silver salt and with mixture 5 to 70 ℃ of reactions down, can obtain the salt between the diimmonium positively charged ion of the borate anion of formula (1) and formula (2).In addition, silver salt is different with using, and can adopt electrolytic oxidation.In this case, the borate of formula (1) is to be no less than the every mol 1 of 2mol/, and the amount of 4-phenylenediamine derivative is used.
As selection, can also be by in organic solvent, the diimmonium dyestuff that has by the borate anion of formula (1) expression being produced in known Diimmonium salt and the borate anion reaction of being represented by formula (1).As the salt of the borate anion that can be used for this method, can comprise an alkali metal salt, alkaline earth salt and transition metal salt etc. by the borate anion of formula (1) expression with formula (1).Preferred as alkali salt, and more preferably lithium salts, sodium salt, sylvite, for example boratory lithium salts of four (pentafluorophenyl groups), sodium salt, sylvite.
In addition, as the diimmonium dyestuff, can use the diimmonium positively charged ion and hexafluoro-antimonic acid salt ion, perchlorate ion, phosphofluoric acid salt ion and a tetrafluoro borate ionic salt that comprise formula (2).
For the amount of the borate anion that is used for the reaction between organic solvent mesoboric acid salt compound and known diimmonium dyestuff, borate compound is not less than 2mol with every 1mol Diimmonium salt, and preferred 2 to 5mol and more preferably 2 to 4mol/ amount is used.The amount that is lower than 2mol will provide low substitute proportion, and the amount that is higher than 5mol is with uneconomical.
As the organic solvent that is used to react, for example can use aromatic solvent for example toluene and dimethylbenzene; Based on the solvent of ketone for example acetone, methylethylketone and mibk; Based on the solvent of ester for example ethyl acetate and butylacetate; Based on the solvent of nitrile acetonitrile for example; Based on the solvent of alcohol for example methyl alcohol, ethanol and Virahol; Based on the solvent of ether for example tetrahydrofuran (THF) and dibutyl ether; Based on the solvent of glycol ethers for example ethylene glycol butyl ether and propylene glycol positive propyl ether; Based on the solvent of acid amides for example methane amide and N, dinethylformamide; With based on the solvent of halogen for example methylene dichloride and chloroform.These solvents can be separately or are used with the mixed form of two or more solvents.Can preferably use the solvent that has high resolution for borate compound and Diimmonium salt.
The amount of the solvent that will use is preferably 1 to 100 times of gross weight of borate compound and Diimmonium salt, and more preferably 2 to 50 times.Being lower than 1 times amount will provide the solvability of poor borate compound and Diimmonium salt, and surpass 100 times amount with uneconomical.Consider the decomposition that suppresses Diimmonium salt, temperature of reaction preferably is not higher than 60 ℃, and more preferably 10 to 50 ℃.Reaction is spontaneous finishing usually.
When desirable compound separated by reaction soln is left standstill, it can reclaim by filtration.Even when by reaction soln being left standstill when also not making desirable compound deposition, can be by deionized water being added reaction soln form desirable compound thus and by filtering with its recovery and with desirable compound separation.The amount of the deionized water that uses is preferably 5 to 1000 times of reaction soln weight, more preferably 10 to 500 times.To reduce productive rate less than 5 times amounts, and the amount above 1000 times is with uneconomical, because produced too a large amount of waste water.The product with deionized water that reclaims can be cleaned to remove the unwanted ion from raw material.
In this embodiment, particularly the borate in the situation of the salt between borate anion and diimmonium positively charged ion have near-infrared absorbing ability high under 900 to 1200nm wavelength and in the visible region the high transparency, and therefore can be advantageously used for the near-infrared absorbing dyestuff.By adding this borate, can obtain near-infrared-absorbing material.In addition, it also can be used as optical recording material.
Be that this borate has the near-infrared absorbing ability in the borate anion of formula (1) and the situation during based on the salt between the positively charged ion of cyanine dyes when borate of the present invention equally.Positively charged ion based on cyanine dyes is not particularly limited in this case, as long as it has high near-infrared absorbing ability under 700 to 1000nm wavelength.Preferably, can use positively charged ion based on indoles.Particularly, can comprise positively charged ion, although they never are limited to this by following formula (a) to (i) expression.Borate in these embodiments have near-infrared absorbing ability high under 700 to 1000nm wavelength and in the visible region the high transparency, and therefore can be advantageously used for the near-infrared absorbing dyestuff.By adding this borate, can obtain near-infrared-absorbing material.In addition, it also can be used as optical recording material.
Figure A20068000306000191
Figure A20068000306000201
(3) near-infrared absorbing dyestuff
Borate of the present invention can improve the weather resistance of near-infrared-absorbing material (dyestuff), particularly thermotolerance and wet fastness.Therefore, a second aspect of the present invention relates to the near-infrared-absorbing material that comprises borate of the present invention and near-infrared absorbing dyestuff.As mentioned above, because borate of the present invention can improve weather resistance, particularly thermotolerance and the wet fastness of near-infrared-absorbing material (dyestuff), therefore near-infrared-absorbing material of the present invention can be realized good weather resistance, particularly thermotolerance and wet fastness.In addition, near-infrared-absorbing material of the present invention is good equally in the transparency of visible region.
In the present invention, described in clauses and subclauses (2), when borate of the present invention was salt between the borate anion of formula (1) and the positively charged ion with near-infrared absorbing ability, borate itself can be the near-infrared absorbing dyestuff.Therefore, in this case, the near-infrared-absorbing material of a second aspect of the present invention can be a borate of the present invention itself.In this case, near-infrared-absorbing material can be formed or can be made up of two or more boratory mixtures by a kind of borate.Even in this case,, another kind of near-infrared absorbing dye combinations as described below can be used in order to help desirable near-infrared absorbing ability or to absorb in order under another near infrared ray wavelength, to realize.In addition, can and have salt between the positively charged ion of near-infrared absorbing ability and the borate anion of formula (1) and the salt that do not have between the positively charged ion of near-infrared absorbing ability are used in combination with the borate anion of formula (1).By this use, can further improve weather resistance, particularly thermotolerance and the wet fastness of dyestuff.In addition, when borate of the present invention was salt between the borate anion of formula (1) and the positively charged ion that does not have the near-infrared absorbing ability, this being used in combination of near-infrared absorbing dyestuff as described below was necessary.By boratory existence, can improve the weather resistance of near-infrared absorbing dyestuff, particularly thermotolerance and wet fastness.
The near-infrared absorbing dyestuff that can be used in the near-infrared-absorbing material of the present invention is not particularly limited, and except the borate anion of aforesaid formula (1) and have the salt between the positively charged ion of near-infrared absorbing ability, for example can use known near-infrared absorbing dyestuff.Particularly, can comprise based on cyanine, based on poly-methine, based on side's sour cyanines (squarylium), based on porphyrin, based on the dithiol metal complex compound, based on phthalocyanine, based on the near-infrared absorbing dyestuff of diimmonium etc.In the middle of these, good based on cyanine with based on transparent good in the visible region of the near-infrared absorbing dyestuff of diimmonium based on the near-infrared absorbing dye durability of the near-infrared absorbing dyestuff of phthalocyanine, therefore preferred these dyestuffs that use.
In the present invention, the dyestuff based on diimmonium is to comprise the diimmonium positively charged ion of formula (2) and the salt of counter anion.Counter ion are not particularly limited; and can use chloride ion; bromide ion; iodide ion; perchlorate; nitrate ion; the benzene sulfonate ion; right-the toluenesulphonic acids salt ion; the methylsulfuric acid salt ion; the ethylsulfuric acid salt ion; the propyl group sulfate ion; the Tetrafluoroboric acid salt ion; tetraphenylborate ion; four (pentafluorophenyl group) borate ion; two (trifluoromethane sulfone) imide ion; two (pentafluoride ethane sulfone) imide ion; pentafluoride ethane sulfone trifluoromethane sulfone imide ion; trifluoromethane sulfone heptafluoro-propane sulfone imide ion; nine fluorine butane sulfone trifluoromethane sulfone imide ions; 1,3-disulfonyl base R 1216 imide ion; the phosphofluoric acid salt ion; the benzene sulfinic acid salt ion; acetate ions; the trifluoroacetic acid salt ion; the propionic salt ion; the benzoate ion; oxalate ion; the succinate ion; the malonate ion; the oleate ion; the stearate ion; citrate ion; bisphosphate hydrogen salt ion; the biphosphate salt ion; pentachloro-stannate ion; the chlorosulfonate ion; the fluoro sulfonate ion; the trifluoro-methanyl sulfonate ion; the hexafluoroarsenate salt ion; the hexafluoro-antimonic acid salt ion; molybdate ion; tungstate ion; the titanate ion; the zirconate ion; sulfate ion; vanadate ion; borate ion etc.In this case, because as by shown in the formula (2), therefore the diimmonium positively charged ion is a divalent cation, and for example when using monovalent anion for example during chloride ion, the dyestuff based on diimmonium according to the present invention has two negatively charged ion of each diimmonium positively charged ion connection.In the middle of these salt, salt between diimmonium positively charged ion and hexafluoro-antimonic acid salt ion, perchlorate ion, phosphofluoric acid salt ion, Tetrafluoroboric acid salt ion, two (trifluoromethane sulfone) imide ions and four (pentafluorophenyl group) borate ion, the salt between preferred especially diimmonium positively charged ion and four (pentafluorophenyl group) borate ion is preferred for the present invention.Here, the salt between diimmonium positively charged ion and four (pentafluorophenyl group) borate ion is a boratory example that has the near-infrared absorbing ability in a first aspect of the present invention.
Be used for the dyestuff based on cyanine of the present invention and be not particularly limited,, and can preferably use based on the positively charged ion of indoles and the salt between the counter anion as long as it is the transparency and the good class of near-infrared absorbing ability in the visible region.As positively charged ion, can preferably use positively charged ion, yet be not limited to this by formula (a) to (i) expression based on indoles.As counter anion, can use the similar counter anion of in dyestuff, listing based on diimmonium, be not particularly limited.Here, be a boratory example that in a first aspect of the present invention, has the near-infrared absorbing ability based on the salt between positively charged ion and four (pentafluorophenyl group) borate ion of indoles.
In the product of commercially available acquisition more specifically, can use the ADS812MI conduct of for example producing to contain the cationic dyestuff of representing by general formula (a) based on cyanine by American Dye Source Inc.; The S0712 conduct of being produced by FEW Chemicals GmbH contains the cationic dyestuff of being represented by general formula (b) based on cyanine; The S0726 conduct of being produced by FEW Chemicals GmbH contains the cationic dyestuff of being represented by general formula (c) based on cyanine; The ADS780MT conduct of being produced by American Dye Source Inc. contains the cationic dyestuff of being represented by general formula (d) based on cyanine; The S0006 conduct of being produced by FEW Chemicals GmbH contains the cationic dyestuff of being represented by general formula (e) based on cyanine; The S0081 conduct of being produced by FEW Chemicals GmbH contains the cationic dyestuff of being represented by general formula (f) based on cyanine; The S0773 conduct of being produced by FEW Chemicals GmbH contains the cationic dyestuff of being represented by general formula (g) based on cyanine; The S0772 conduct of being produced by FEW Chemicals GmbH contains the cationic dyestuff of being represented by general formula (h) based on cyanine; With the S0734 that produces by FEW Chemicals GmbH as containing by the cationic dyestuff based on cyanine of general formula (i) expression etc.
Can be used for the compound based on phthalocyanine of the present invention and be not particularly limited,, can use known compound based on phthalocyanine as long as it has good near-infrared absorbing ability.Can preferably include by the compound of following formula (X) expression or the compound of representing by following formula (Y).
Compound by formula (X) expression based on phthalocyanine:
In formula (X), A 1To A 16Represent functional group and represent hydrogen atom independently of one another; halogen atom; hydroxyl; the hydroxyl alkylsulfonyl; carboxyl; thiol group; the alkyl that can substitutedly contain 1 to 20 carbon atom; the alkoxyl group that can substitutedly contain 1 to 20 carbon atom; the aryl that can substitutedly have 6 to 20 carbon atoms; the aryloxy that can substitutedly have 6 to 20 carbon atoms; the aralkyl that can substitutedly have 7 to 20 carbon atoms; the aralkoxy that can substitutedly have 7 to 20 carbon atoms; the alkyl sulfenyl that can substitutedly have 1 to 20 carbon atom; the artyl sulfo that can substitutedly have 6 to 20 carbon atoms; the aromatic alkyl sulfurio that can substitutedly have 7 to 20 carbon atoms; the alkyl sulphonyl that can substitutedly have 1 to 20 carbon atom; the aryl sulfonyl that can substitutedly have 6 to 20 carbon atoms; the aralkyl alkylsulfonyl that can substitutedly have 7 to 20 carbon atoms; the acyl group that can substitutedly have 1 to 20 carbon atom; the alkoxy carbonyl that can substitutedly have 2 to 20 carbon atoms; the aryloxycarbonyl that can substitutedly have 6 to 20 carbon atoms; the aromatic alkoxy carbonyl that can substitutedly have 2 to 20 carbon atoms; the alkyl carbonyl oxy that can substitutedly have 2 to 20 carbon atoms; the aryl-carbonyl oxygen that can substitutedly have 6 to 20 carbon atoms; the aralkyl carbonyl oxygen base that can substitutedly have 8 to 20 carbon atoms; the heterocyclic group that can substitutedly have 2 to 20 carbon atoms; can substituted amino; can substituted amino-sulfonyl and can substituted aminocarboxyl.Functional group A 1To A 16Can be same to each other or different to each other, and same in the situation of same type, and they can be identical or different, and functional group itself can be bonded together by linking group.M 1Represent atoms metal or oxygen metal that 2 hydrogen atoms, divalent metal atom, trivalent or tetravalence replace.In this manual; " acyl group " is meant as by Daily Industrial Newspaper Co.; Ltd. " the General Dictionary of Scientific Technical Terminology " of Chu Baning; the similar definition of describing in 17 pages of the third edition; and specifically be meant by removing hydroxyl to be obtained from the organic acid group, and represent (wherein R represents aliphatic group, alicyclic group or aromatic group) by formula: RCO-.
(in the situation when being functional group except amino when end)
In formula (X), as functional group A 1To A 16Halogen atom comprise fluorine atom, chlorine atom, bromine atoms and iodine atom.As the alkyl that can substitutedly have 1 to 20 carbon atom, can comprise straight chain, side chain or cyclic alkyl for example methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, sec-butyl, the tertiary butyl, n-pentyl, n-hexyl, cyclohexyl, n-heptyl, n-octyl and 2-ethylhexyl, yet it is not limited to this.As the alkoxyl group that can substitutedly have 1 to 20 carbon atom, can comprise straight chain, side chain or cyclic alkoxy for example methoxyl group, oxyethyl group, positive propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, tert.-butoxy, n-pentyloxy, positive hexyloxy, cyclohexyloxy, positive heptan oxygen base, n-octyloxy and 2-ethyl hexyl oxy, yet it is not limited to this.Aryl as can substitutedly having 6 to 20 carbon atoms can comprise phenyl, naphthyl etc., yet it is not limited to this.Aryloxy as can substitutedly having 6 to 20 carbon atoms can comprise phenoxy group, naphthyloxy etc., yet it is not limited to this.Aralkyl as can substitutedly having 7 to 20 carbon atoms can comprise benzyl, styroyl, diphenyl methyl etc., yet it is not limited to this.As the aralkoxy that can substitutedly have 7 to 20 carbon atoms, can comprise benzyloxy, styroyl oxygen base, diphenyl methyl oxygen base etc., yet it is not limited to this.As the alkyl sulfenyl that can substitutedly have 1 to 20 carbon atom, can comprise straight chain, side chain or cyclic alkyl sulfenyl for example methyl sulfenyl, ethyl sulfenyl, n-propyl sulfenyl, sec.-propyl sulfenyl, normal-butyl sulfenyl, isobutyl-sulfenyl, sec-butyl sulfenyl, tertiary butyl sulfenyl, n-pentyl sulfenyl, n-hexyl sulfenyl, cyclohexyl sulfenyl, n-heptyl sulfenyl, n-octyl sulfenyl and 2-ethylhexyl sulfenyl, yet it is not limited to this.As the artyl sulfo that can substitutedly have 6 to 20 carbon atoms, can comprise phenyl sulfenyl, naphthyl sulfenyl etc., yet it is not limited to this.As the aromatic alkyl sulfurio that can substitutedly have 7 to 20 carbon atoms, can comprise benzyl sulfenyl, styroyl sulfenyl, diphenyl methyl sulfenyl etc., yet it is not limited to this.As the alkyl sulphonyl that can substitutedly have 1 to 20 carbon atom; can comprise straight chain, side chain or cyclic alkyl alkylsulfonyl for example methyl sulphonyl, ethylsulfonyl, n-propyl alkylsulfonyl, sec.-propyl alkylsulfonyl, normal-butyl alkylsulfonyl, isobutyl-alkylsulfonyl, sec-butyl alkylsulfonyl, tertiary butyl alkylsulfonyl, n-pentyl alkylsulfonyl, n-hexyl alkylsulfonyl, cyclohexyl alkylsulfonyl, n-heptyl alkylsulfonyl, n-octyl alkylsulfonyl and 2-ethylhexyl alkylsulfonyl, yet it is not limited to this.As the aryl sulfonyl that can substitutedly have 6 to 20 carbon atoms, can comprise phenyl sulfonyl, naphthyl alkylsulfonyl etc., yet it is not limited to this.As can substituted aralkyl alkylsulfonyl, can comprise benzyl alkylsulfonyl, styroyl alkylsulfonyl, diphenyl methyl alkylsulfonyl etc., yet it be not limited to this.As the acyl group that can substitutedly have 1 to 20 carbon atom, can comprise straight chain, side chain or cyclic alkyl carbonyl for example methyl carbonyl, ethyl carbonyl, n-propyl carbonyl, sec.-propyl carbonyl, normal-butyl carbonyl, isobutyl-carbonyl, sec-butyl carbonyl, tertiary butyl carbonyl, n-pentyl carbonyl, n-hexyl carbonyl, cyclohexyl-carbonyl, n-heptyl carbonyl, n-octyl carbonyl and 2-ethylhexyl carbonyl; Aryl carbonyl is benzyloxycarbonyl group and phenylcarbonyl group for example; With aromatic alkyl carbonyl benzoyl for example, yet it is not limited to this.As the alkoxy carbonyl that can substitutedly have 2 to 20 carbon atoms, can comprise methoxycarbonyl, ethoxy carbonyl, positive propoxy carbonyl, isopropoxy carbonyl, n-butoxy carbonyl, isobutoxy carbonyl, sec-butoxy carbonyl, tert-butoxycarbonyl, n-pentyloxy carbonyl, positive hexyloxy carbonyl, cyclohexyloxy carbonyl, positive heptan oxygen base carbonyl, n-octyloxy carbonyl, 2-ethyl hexyl oxy carbonyl etc., yet it is not limited to this.Aryloxycarbonyl as can substitutedly having 7 to 20 carbon atoms can comprise phenyloxycarbonyl, naphthyl carbonyl etc., yet it is not limited to this.As the aromatic alkoxy carbonyl that can substitutedly have 8 to 20 carbon atoms, can comprise benzyloxycarbonyl, styroyl oxygen base carbonyl, diphenyl methyl oxygen base carbonyl etc., yet it is not limited to this.As the alkyl carbonyl oxy that can substitutedly have 2 to 20 carbon atoms, can comprise acetoxyl group, ethyl oxy carbonyl, n-propyl carbonyl oxygen base, sec.-propyl carbonyl oxygen base, normal-butyl carbonyl oxygen base, isobutyl-carbonyl oxygen base, sec-butyl carbonyl oxygen base, tertiary butyl carbonyl oxygen base, n-pentyl carbonyl oxygen base, n-hexyl carbonyl oxygen base, cyclohexyl carbonyl oxygen base, n-heptyl carbonyl oxygen base, 3-heptyl carbonyl oxygen base, n-octyl carbonyl oxygen base etc., yet it is not limited to this.Aryl-carbonyl oxygen as can substitutedly having 7 to 20 carbon atoms can comprise benzoyloxy etc., yet it is not limited to this.Aralkyl carbonyl oxygen base as can substitutedly having 8 to 20 carbon atoms can comprise benzyl carbonyl oxygen base etc., yet it is not limited to this.Heterocyclic group as can substitutedly having 2 to 20 carbon atoms can comprise pyrryl, imidazolyl, piperidyl, morpholinyl etc., yet it is not limited to this.
In addition, as the functional group A that if necessary may reside in the formula (X) 1To A 16It is alkyl; alkoxyl group; aryl; aryloxy; aralkyl; aralkoxy; the alkyl sulfenyl; artyl sulfo; aromatic alkyl sulfurio; alkyl sulphonyl; aryl sulfonyl; the aralkyl alkylsulfonyl; acyl group; alkoxy carbonyl; aryloxycarbonyl; aromatic alkoxy carbonyl; alkyl carbonyl oxy; aryl-carbonyl oxygen; substituting group on aralkyl carbonyl oxygen base and the heterocyclic group; can comprise for example halogen atom; acyl group; alkyl; phenyl; alkoxyl group; haloalkyl; halogenated alkoxy; nitro; amino; alkylamino; alkyl-carbonyl-amino; arylamino; aryl-amino-carbonyl; carbonyl; alkoxy carbonyl; alkyl amino-carbonyl; the alkoxyl group alkylsulfonyl; the alkyl sulfenyl; formamyl; aryloxycarbonyl; cyano group and heterocyclic group, however it is not limited to this.These substituting groups can a plurality of existence and when they during with a plurality of the existence, they can be same to each other or different to each other, even and they also can be identical or different in the situation of same type.Itself can be bonded together these substituting groups by linking group.
(in the situation when end is amido functional group)
As the functional group A in the formula (X) 1To A 16, can substituted amino, can substituted amino-sulfonyl and can substituted aminocarboxy substituting group, can comprise hydrogen atom; Straight chain, side chain or cyclic alkyl be methyl, ethyl, n-propyl, normal-butyl, sec-butyl, n-pentyl, n-hexyl, 2-ethylhexyl and cyclohexyl for example; Aryl is phenyl, naphthyl for example; Aralkyl is benzyl and styroyl for example; Ethanoyl; Straight chain, side chain or cyclic alkyl carbonyl be ethyl carbonyl, n-propyl carbonyl, sec.-propyl carbonyl, normal-butyl carbonyl, isobutyl-carbonyl, sec-butyl carbonyl, tertiary butyl carbonyl, n-pentyl carbonyl, n-hexyl carbonyl, cyclohexyl-carbonyl, n-heptyl carbonyl, 3-heptyl carbonyl, n-octyl carbonyl for example; Aryl carbonyl is benzoyl and naphthyl carbonyl for example; Aromatic alkyl carbonyl is benzyloxycarbonyl group etc. for example, yet it is not limited to this and these substituting group and can further be substituted base and replaces.These substituting groups can 0,1 or 2 existence, and when having two substituting groups, they can be same to each other or different to each other, even and in the situation of same type, they also can be identical or different, and functional group itself can be bonded together by linking group.
As can further being present in as can substituted amino; can substituted amino-sulfonyl and can substituted aminocarboxy substituent alkyl; aryl; aralkyl; alkyl-carbonyl; substituting group on aryl carbonyl and the aromatic alkyl carbonyl; can comprise for example halogen atom; acyl group; alkyl; phenyl; alkoxyl group; haloalkyl; halogenated alkoxy; nitro; amino; alkylamino; alkyl-carbonyl-amino; arylamino; aryl-amino-carbonyl; carbonyl; alkoxy carbonyl; alkyl amino-carbonyl; the alkoxyl group alkylsulfonyl; the alkyl sulfenyl; formamyl; aryloxycarbonyl; cyano group and heterocyclic group, however it is not limited to this.These substituting groups can a plurality of existence and when they during with a plurality of the existence, they can be same to each other or different to each other, even and in the situation of same type, they also can be identical or different, and substituting group itself can be bonded together by linking group.
In addition, as metal M 1The example of divalent metal, can comprise Cu (II), Co (II), Zn (II), Fe (II), Ni (II), Ru (II), Rh (II), Pd (II), Pt (II), Mn (II), Mg (II), Ti (II), Be (II), Ca (II), Ba (II), Cd (II), Hg (II), Pb (II), Sn (II) etc., yet it is not limited to this.Be substituted the example of atoms metal as trivalent, can comprise Al-F, Al-Cl, Al-Br, Al-I, Fe-Cl, Ga-F, Ga-Cl, Ga-I, Ga-Br, In-F, In-Cl, In-Br, In-I, Tl-F, Tl-Cl, Tl-Br, Tl-I, Al-C 6H 5, Al-C 6H 4(CH 3), In-C 6H 5, In-C 6H 4(CH 3), In-C 6H 5, Mn (OH), Mn (OC 6H 5), Mn[OSi (CH 3) 3], Ru-Cl etc., yet it is not limited to this.Be substituted the example of atoms metal as tetravalence, can comprise CrCl 2, SiF 2, SiCl 2, SiBr 2, SiI 2, ZrCl 2, GeF 2, GeCl 2, GeBr 2, GeI 2, SnF 2, SnCl 2, SnBr 2, TiF 2, TiCl 2, TiBr 2, Ge (OH) 2, Mn (OH) 2, Si (OH) 2, Sn (OH) 2, Zr (OH) 2, Cr (R 1) 2, Ge (R 1) 2, Si (R 1) 2, Sn (R 1) 2, Ti (R 1) 2{ R 1Expression alkyl, phenyl, naphthyl and its derivative }, Cr (OR 2) 2, Ge (OR 2) 2, Si (OR 2) 2, Sn (OR 2) 2, Ti (OR 2) 2{ R 2Expression alkyl, phenyl, naphthyl, trialkylsilkl, dialkyl group alkoxysilyl and its derivative }, Sn (SR 3) 2, Ge (SR 3) 2{ R 3Expression alkyl, phenyl, naphthyl and its derivative } etc., yet it is not limited to this.As the example of oxygen metal (oxymetal), can comprise VO, MnO, TiO etc., yet it is not limited to this.
Compound by formula (Y) expression based on phthalocyanine
Figure A20068000306000291
In formula (Y), B 1To B 24Represent functional group and represent hydrogen atom independently of one another; halogen atom; hydroxyl; the hydroxyl alkylsulfonyl; hydroxy-acid group; thiol group; the alkyl that can substitutedly have 1 to 20 carbon atom; the alkoxyl group that can substitutedly have 1 to 20 carbon atom; the aryl that can substitutedly have 6 to 20 carbon atoms; the aryloxy that can substitutedly have 6 to 20 carbon atoms; the aralkyl that can substitutedly have 7 to 20 carbon atoms; the aralkoxy that can substitutedly have 7 to 20 carbon atoms; the alkyl sulfenyl that can substitutedly have 1 to 20 carbon atom; the artyl sulfo that can substitutedly have 6 to 20 carbon atoms; the aromatic alkyl sulfurio that can substitutedly have 7 to 20 carbon atoms; the alkyl sulphonyl that can substitutedly have 1 to 20 carbon atom; the aryl sulfonyl that can substitutedly have 6 to 20 carbon atoms; the aralkyl alkylsulfonyl that can substitutedly have 7 to 20 carbon atoms; the acyl group that can substitutedly have 1 to 20 carbon atom; the alkoxy carbonyl that can substitutedly have 2 to 20 carbon atoms; the aryloxycarbonyl that can substitutedly have 6 to 20 carbon atoms; the aromatic alkoxy carbonyl that can substitutedly have 2 to 20 carbon atoms; the alkyl carbonyl oxy that can substitutedly have 2 to 20 carbon atoms; the aryl-carbonyl oxygen that can substitutedly have 6 to 20 carbon atoms; the aralkyl carbonyl oxygen base that can substitutedly have 8 to 20 carbon atoms; the heterocyclic group that can substitutedly have 2 to 20 carbon atoms; can substituted amino and can substituted amino-sulfonyl and can substituted aminocarboxyl.The B of functional group 1To B 24Can be same to each other or different to each other, even and in the situation of same type, they also can be identical or different, and functional group itself can be bonded together by linking group.M 2Represent 2 substituted atoms metals of hydrogen atom, divalent metal atom, trivalent or tetravalence or oxygen metal.(in the situation when being functional group except amino when end)
In formula (Y), as the B of functional group 1To B 24Halogen atom comprise fluorine atom, chlorine atom, bromine atoms and iodine atom.As the alkyl that can substitutedly have 1 to 20 carbon atom, can comprise straight chain, side chain or cyclic alkyl for example methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, sec-butyl, the tertiary butyl, n-pentyl, n-hexyl, cyclohexyl, n-heptyl, n-octyl and 2-ethylhexyl, yet it is not limited to this.As the alkoxyl group that can substitutedly have 1 to 20 carbon atom, can comprise straight chain, side chain or cyclic alkoxy for example methoxyl group, oxyethyl group, positive propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, tert.-butoxy, n-pentyloxy, positive hexyloxy, cyclohexyloxy, positive heptan oxygen base, n-octyloxy and 2-ethyl hexyl oxy, yet it is not limited to this.Aryl as can substitutedly having 6 to 20 carbon atoms can comprise phenyl, naphthyl etc., yet it is not limited to this.Aryloxy as can substitutedly having 6 to 20 carbon atoms can comprise phenoxy group, naphthyloxy etc., yet it is not limited to this.Aralkyl as can substitutedly having 7 to 20 carbon atoms can comprise benzyl, styroyl, diphenyl methyl etc., yet it is not limited to this.As the aralkoxy that can substitutedly have 7 to 20 carbon atoms, can comprise benzyloxy, styroyl oxygen base and diphenyl methyl oxygen base etc., yet it is not limited to this.As the alkyl sulfenyl that can substitutedly have 1 to 20 carbon atom, can comprise straight chain, side chain or cyclic alkyl sulfenyl for example methyl sulfenyl, ethyl sulfenyl, n-propyl sulfenyl, sec.-propyl sulfenyl, normal-butyl sulfenyl, isobutyl-sulfenyl, sec-butyl sulfenyl, tertiary butyl sulfenyl, n-pentyl sulfenyl, n-hexyl sulfenyl, cyclohexyl sulfenyl, n-heptyl sulfenyl, n-octyl sulfenyl and 2-ethylhexyl sulfenyl, yet it is not limited to this.As the artyl sulfo that can substitutedly have 6 to 20 carbon atoms, can comprise phenyl sulfenyl, naphthyl sulfenyl etc., yet it is not limited to this.As the aromatic alkyl sulfurio that can substitutedly have 7 to 20 carbon atoms, can comprise benzyl sulfenyl, styroyl sulfenyl, diphenyl methyl sulfenyl etc., yet it is not limited to this.As the alkyl sulphonyl that can substitutedly have 1 to 20 carbon atom; can comprise straight chain, side chain or cyclic alkyl alkylsulfonyl for example methyl sulphonyl, ethylsulfonyl, n-propyl alkylsulfonyl, sec.-propyl alkylsulfonyl, normal-butyl alkylsulfonyl, isobutyl-alkylsulfonyl, sec-butyl alkylsulfonyl, tertiary butyl alkylsulfonyl, n-pentyl alkylsulfonyl, n-hexyl alkylsulfonyl, cyclohexyl alkylsulfonyl, n-heptyl alkylsulfonyl, n-octyl alkylsulfonyl and 2-ethylhexyl alkylsulfonyl, yet it is not limited to this.As the aryl sulfonyl that can substitutedly have 6 to 20 carbon atoms, can comprise phenyl sulfonyl, naphthyl alkylsulfonyl etc., yet it is not limited to this.As can substituted aralkyl alkylsulfonyl, can comprise benzyl alkylsulfonyl, styroyl alkylsulfonyl, diphenyl methyl alkylsulfonyl etc., yet it be not limited to this.As the acyl group that can substitutedly have 1 to 20 carbon atom, can comprise straight chain, side chain or cyclic alkyl carbonyl for example methyl carbonyl, ethyl carbonyl, n-propyl carbonyl, sec.-propyl carbonyl, normal-butyl carbonyl, isobutyl-carbonyl, sec-butyl carbonyl, tertiary butyl carbonyl, n-pentyl carbonyl, n-hexyl carbonyl, cyclohexyl-carbonyl, n-heptyl carbonyl, n-octyl carbonyl and 2-ethylhexyl carbonyl; Aryl carbonyl is benzyloxycarbonyl group, phenylcarbonyl group for example; With aromatic alkyl carbonyl benzoyl for example, yet it is not limited to this.As the alkoxy carbonyl that can substitutedly have 2 to 20 carbon atoms, can comprise methoxycarbonyl, ethoxy carbonyl, positive propoxy carbonyl, isopropoxy carbonyl, n-butoxy carbonyl, isobutoxy carbonyl, sec-butoxy carbonyl, tert-butoxycarbonyl, n-pentyloxy carbonyl, positive hexyloxy carbonyl, cyclohexyloxy carbonyl, positive heptan oxygen base carbonyl, n-octyloxy carbonyl, 2-ethyl hexyl oxy carbonyl etc., yet it is not limited to this.Aryloxycarbonyl as can substitutedly having 7 to 20 carbon atoms can comprise phenyloxycarbonyl, naphthyl carbonyl etc., yet it is not limited to this.As the aromatic alkoxy carbonyl that can substitutedly have 8 to 20 carbon atoms, can comprise benzyloxycarbonyl, styroyl oxygen base carbonyl, diphenyl methyl oxygen base carbonyl etc., yet it is not limited to this.As the alkyl carbonyl oxy that can substitutedly have 2 to 20 carbon atoms, can comprise acetoxyl group, ethyl oxy carbonyl, n-propyl carbonyl oxygen base, sec.-propyl carbonyl oxygen base, normal-butyl carbonyl oxygen base, isobutyl-carbonyl oxygen base, sec-butyl carbonyl oxygen base, tertiary butyl carbonyl oxygen base, n-pentyl carbonyl oxygen base, n-hexyl carbonyl oxygen base, cyclohexyl carbonyl oxygen base, n-heptyl carbonyl oxygen base, 3-heptyl carbonyl oxygen base, n-octyl carbonyl oxygen base etc., yet it is not limited to this.Aryl-carbonyl oxygen as can substitutedly having 7 to 20 carbon atoms can comprise benzoyloxy etc., yet it is not limited to this.Aralkyl carbonyl oxygen base as can substitutedly having 8 to 20 carbon atoms can comprise benzyl carbonyl oxygen base etc., yet it is not limited to this.Heterocyclic group as can substitutedly having 2 to 20 carbon atoms can comprise pyrryl, imidazolyl, piperidyl, morpholinyl etc., yet it is not limited to this.
As the B of functional group that if necessary may reside in the formula (Y) 1To B 24It is alkyl; alkoxyl group; aryl; aryloxy; aralkyl; aralkoxy; the alkyl sulfenyl; artyl sulfo; aromatic alkyl sulfurio; alkyl sulphonyl; aryl sulfonyl; the aralkyl alkylsulfonyl; acyl group; alkoxy carbonyl; aryloxycarbonyl; aromatic alkoxy carbonyl; alkyl carbonyl oxy; aryl-carbonyl oxygen; substituting group on aralkyl carbonyl oxygen base and the heterocyclic group; for example can comprise halogen atom; acyl group; alkyl; phenyl; alkoxyl group; haloalkyl; halogenated alkoxy; nitro; amino; alkylamino; alkyl-carbonyl-amino; arylamino; aryl-amino-carbonyl; carbonyl; alkoxy carbonyl; alkyl amino-carbonyl; the alkoxyl group alkylsulfonyl; the alkyl sulfenyl; formamyl; aryloxycarbonyl; cyano group; heterocyclic group etc., however it is not limited to this.These substituting groups can a plurality of existence and when they during with a plurality of the existence, they can be same to each other or different to each other, even and in the situation of same type, they also can be identical or different, and functional group itself can be bonded together by linking group.
(in the situation when end is amido functional group)
As the B of functional group in the formula (Y) 1To B 24Can substituted amino, can substituted amino-sulfonyl and can substituted aminocarboxy substituting group, can comprise hydrogen atom; Straight chain, side chain or cyclic alkyl be methyl, ethyl, n-propyl, normal-butyl, sec-butyl, n-pentyl, n-hexyl, 2-ethylhexyl and cyclohexyl for example; Aryl is phenyl and naphthyl for example; Aralkyl is benzyl, styroyl for example; Straight chain, side chain or cyclic alkyl carbonyl be ethanoyl, ethyl carbonyl, n-propyl carbonyl, sec.-propyl carbonyl, normal-butyl carbonyl, isobutyl-carbonyl, sec-butyl carbonyl, tertiary butyl carbonyl, n-pentyl carbonyl, n-hexyl carbonyl, cyclohexyl-carbonyl, n-heptyl carbonyl, 3-heptyl carbonyl and n-octyl carbonyl for example; Aryl carbonyl is benzoyl and naphthyl carbonyl for example; Aromatic alkyl carbonyl is benzyloxycarbonyl group etc. for example, yet it is not limited to this and these substituting group and can further be substituted base and replaces.These substituting groups can 0,1 or 2 existence, and they can be same to each other or different to each other when having two substituting groups, even and they also can be identical or different in the situation of same type, and functional group itself can be bonded together by linking group.
As can further being present in for can substituted amino; can substituted amino-sulfonyl and can substituted aminocarboxy substituent alkyl; alkyl; aryl; aralkyl; alkyl-carbonyl; aryl carbonyl; substituting group on the aromatic alkyl carbonyl etc.; can comprise for example halogen atom; acyl group; alkyl; phenyl; alkoxyl group; haloalkyl; halogenated alkoxy; nitro; amino; alkylamino; alkyl-carbonyl-amino; arylamino; aryl-amino-carbonyl; carbonyl; alkoxy carbonyl; alkyl amino-carbonyl; the alkoxyl group alkylsulfonyl; the alkyl sulfenyl; formamyl; aryloxycarbonyl; cyano group and heterocyclic group, however it is not limited to this.These substituting groups can 0,1 or 2 exist and when they during with a plurality of the existence, they can be same to each other or different to each other, even and they also can be identical or different in the situation of same type, and functional group itself can be bonded together by linking group.
In addition, as metal M 2The example of divalent metal, can comprise Cu (II), Co (II), Zn (II), Fe (II), Ni (II), Ru (II), Rh (II), Pd (II), Pt (II), Mn (II), Mg (II), Ti (II), Be (II), Ca (II), Ba (II), Cd (II), Hg (II), Pb (II), Sn (II) etc., yet it is not limited to this.Be substituted the example of atoms metal as trivalent, can comprise for example Al-F, Al-Cl, Al-Br, Al-I, Fe-Cl, Ga-F, Ga-Cl, Ga-I, Ga-Br, In-F, In-Cl, In-Br, In-I, Tl-F, Tl-Cl, Tl-Br, Tl-I, Al-C 6H 5, Al-C 6H 4(CH 3), In-C 6H 5, In-C 6H 4(CH 3), In-C 6H 5, Mn (OH), Mn (OC 6H 5), Mn[OSi (CH 3) 3], Ru-Cl etc., yet it is not limited to this.Be substituted the example of atoms metal as tetravalence, can comprise CrCl 2, SiF 2, SiCl 2, SiBr 2, SiI 2, ZrCl 2, GeF 2, GeCl 2, GeBr 2, GeI 2, SnF 2, SnCl 2, SnBr 2, TiF 2, TiCl 2, TiBr 2, Ge (OH) 2, Mn (OH) 2, Si (OH) 2, Sn (OH) 2, Zr (OH) 2, Cr (R 1) 2, Ge (R 1) 2, Si (R 1) 2, Sn (R 1) 2, Ti (R 1) 2{ R 1Expression alkyl, phenyl, naphthyl and its derivative }, Cr (OR 2) 2, Ge (OR 2) 2, Si (OR 2) 2, Sn (OR 2) 2, Ti (OR 2) 2{ R 2Expression alkyl, phenyl, naphthyl, trialkylsilkl, dialkyl group alkoxysilyl and its derivative }, Sn (SR 3) 2, Ge (SR 3) 2{ R 3Expression alkyl, phenyl, naphthyl or derivatives thereof } etc., yet it is not limited to this.As the example of oxygen metal, can comprise VO, MnO, TiO etc., yet it is not limited to this.
Particularly, can comprise trade(brand)name EXCOLOR IR-10A, EXCOLORIR-12 and EXCOLOR IR-14 or TX-EX-906B, TX-EX-910B and TX-EX-902K (all by Nippon Shokubai Co., Ltd. produces).
Can depend on and use and the suitable amount of selecting to be formulated in the near-infrared absorbing dyestuff in the near-infrared-absorbing material of the present invention.Based on the solid content of resin, it can be for 0.1 to 10wt%, and preferred 1 to 8wt%.In this case, the compounding amount that is lower than the ion near-infrared absorbing dyestuff of 0.1wt% was low dyestuff compounding amount, and may not obtain enough near-infrared absorbing abilities.On the contrary, the amount that surpasses 10wt% can not provide the effect suitable with this addings and so uneconomical, may lose the transparency of visible region on the contrary in addition.
(4) resin
Near-infrared-absorbing material of the present invention can further comprise resin.Can be used for resin of the present invention and be not particularly limited, as long as it is the resin that can be used as optical material usually.Resin with high as far as possible transparency is preferred, more specifically, can comprise based on polyolefin resin for example polyethylene, polypropylene, carboxylation polyolefine, chlorinatedpolyolefins and cyclic olefin polymer; Polystyrene, based on the polymkeric substance of polyacrylic ester, based on the polymkeric substance of polymethacrylate; Based on the polymkeric substance of vinyl for example polyvinyl acetate, vinyl halides based polyalcohol and polyvinyl alcohol; Based on the resin of polymeric amide nylon for example; Resin based on urethane; Based on the resin of polyester PET for example; Polycarbonate; Resin based on epoxy; Based on the resin of polyvinyl acetal butyral resin etc. for example.
In the middle of these, can preferably use melting or dissolved resin.In this case, when owing to can fusion and have high Tg when using this resinoid, obtain can moulding near-infrared-absorbing material.For example, by with near-infrared absorbing dye ligand system to wherein, can fusion and resin with the Tg that is not less than 80 ℃ plastic material can be provided.The appropriate resin example comprise methacrylate polymers for example the multipolymer, polycarbonate, butyral resin, cyclopolyolefin polymkeric substance, ARTON of polymethylmethacrylate, vinylformic acid α-hydroxyl methyl esters (producing), Zeonor (producing), O-PET by Zeon Corp. by JSR Corp. (by Kanebo, Ltd. production), Sumipex is (by Sumitomo Chemical Co., Ltd. production), Optorez (by Hitachi Chemical Co., Ltd. produces).
By near-infrared-absorbing material is therewith dissolved, soluble resin can provide coating material.The suitable example that is used for the resin of coating material comprises the polymkeric substance based on methacrylic ester, ARTON (being produced by JSR Corp.), Zeonor (being produced by Zeon Corp.) and O-PET (by Kanebo, Ltd. production).The especially preferred methacrylic ester of straight chain, side chain or the how alicyclic alkyl by will having 1 to 10 carbon atom polymkeric substance that obtains of methyl methacrylate, methacrylic tert-butyl acrylate, cyclohexyl methacrylate and isobornyl methacrylate copolymerization for example.Resin can be polymkeric substance of only being made up of a kind of methacrylate monomer or the multipolymer of being made up of multiple methacrylate monomer.In addition, its can be by with aforesaid methacrylate monomer be different from the polymkeric substance that this monomeric monomer copolymerization obtains.As other monomers, can also use aromatic monomer for example vinylbenzene and vinyl toluene; Maleimide monomer is phenyl maleimide and cyclohexyl maleimide for example; The monomer that contains carboxyl is methacrylic acid and vinylformic acid for example; The acrylate that contains 1 to 15 carbon atom; Monomer with hydroxyl is hydroxyethyl methylacrylate and Hydroxyethyl acrylate etc. for example.The monomeric amount of using except methacrylate monomer is lower than 50wt%, preferably is lower than 30wt%, and further preferably is lower than 10wt%.Particularly, can comprise Sumipex (by Sumitomo Chemical Co., Ltd. produces), Optorez (by Hitachi Chemical Co., Ltd. produces) and HALSHYBRIDIR (by Nippon Shokubai Co., Ltd. produces) etc.Second-order transition temperature (Tg) is higher than the dyestuff deterioration that 85 ℃ resin can suppress to be caused by heat or moisture effectively.
Have sufficiently high weather resistance although have the resin of high Tg, it is when being used for for example having cracked defective easily when film is used.In order to suppress the cracking of resin, the weight-average molecular weight that preferably is converted to polystyrene is not less than 50,000, and further preferably is not less than 100,000.
And be difficult to cracking in order to make, polymer architecture is branched structure rather than linear structure preferably.By adopting branched structure, even when resin has high molecular weight, its viscosity also step-down and processing becomes easy.In order to obtain branched polymer, can use macromonomer, polyfunctional monomer, multifunctional initiator and multifunctional chain-transfer agent.As macromonomer, can use AA-6, AA-2, AS-6, AB-6, AK-5 (all producing) etc. by Toagosei Co.Ltd..As polyfunctional monomer, can use LIGHT-ESTER EG, LIGHT-ESTER1,4BG, LIGHT-ESTERNP, LIGHT-ESTER TMP (all by KYOEISHA CHEMICALCo., Ltd. produces).As multifunctional initiator, can use Pertetra A and BTTB-50 (all producing), Trigonox 17-40MB and PERKADOX 12-XL25 (all producing) etc. by Kayaku Akuzo Corp. by NOF Corp..As multifunctional chain-transfer agent, can use tetramethylolmethane four (3-mercaptopropionic acid ester), trimethylolpropane tris (3-mercaptopropionic acid ester), tetramethylolmethane four (sulfo-glycol ether ester) (all by Sakai Chemical Industry Co., Ltd. produces) etc.In order to obtain to have the resin of branched structure, because therefore polymerization easily can especially preferably use multifunctional initiator.The Pertetra A and the PERKADOX 12-XL25 that many side chains can be provided and react under mild conditions can especially preferably use.
Even Tg is not higher than 85 ℃, near-infrared-absorbing material of the present invention also can provide good weather resistance.Although do not limit the kind of resin especially, can use acrylic resin and vibrin.In order to obtain anti-cracking and high-durability, the Tg of resin is preferably 65 to 85 ℃, more preferably 70 to 80 ℃.
Resin can be pressure-sensitive adhesive or tackiness agent or its mixture.Owing to use the near-infrared-absorbing material of pressure-sensitive adhesive or tackiness agent can be bonded in other functional membranes, therefore can be convenient and make spectral filter of the present invention economically.
The resin that is suitable as pressure-sensitive adhesive comprises based on acrylic acid or the like, based on silicone, based on resin of SBR etc.Particularly preferred resin comprises by using the polymkeric substance that polymerization obtains as main ingredient such as ethyl propenoate, butyl acrylate, 2-EHA, vinylformic acid n-octyl.More specifically, can enumerate " ACRYSETAST " (by Nippon Shokubai Co., Ltd. produces).Tg preferably is not less than-80 ℃ and be not higher than 0 ℃.In addition, the pressure-sensitive adhesive that advantageously uses will be by having for example resin based on acrylic acid or the like that obtains of cyclohexyl and isobornyl (methyl) acrylic ester copolymer of alicyclic alkyl.Be not particularly limited although be used for the amount of (methyl) acrylate with alicyclic alkyl of its copolymerization, this resin is preferred so that the Tg of resin falls into the amount use that is not less than-80 ℃ and is not higher than 0 ℃ scope.
Can also for example (methyl) acrylic ester copolymer of carboxyl of acidic-group will be had.In this case, being intended to improve wet fastness, will can be to make the acid number of resin preferably fall into not to be higher than 30 by the amount of (methyl) acrylate of copolymerization, more preferably no higher than 15 and most preferably be not higher than 5 scope.In this manual, during " acid number " is meant and the required amount of 1g (solid content) resin in the potassium hydroxide of mg.
As the resin that is suitable as tackiness agent, can comprise normally used based on silicone, based on carbamate, based on the resin of acrylic acid or the like with based on polyolefinic resin for example vinyl-vinyl acetate copolymer, carboxylation polyolefine, chlorinatedpolyolefins etc.
When pressure-sensitive adhesive or tackiness agent during as resin, preferably will be contained the cationic salt of aniline, pyridine and quinoline as the anionic salt that contains formula (1).As the near-infrared absorbing dyestuff, the preferred use has the diimmonium dyestuff of four (pentafluorophenyl group) borate anion as counter anion.
Can depend on the quantity of application and dyestuff or solvent and select to be formulated in the amount of the resin in the near-infrared-absorbing material of the present invention aptly.
(5) additive
The dyestuff that shows maximum absorption wavelength in the visible region of 380 to 780nm wavelength can be added in the near-infrared-absorbing material of the present invention.As this class dyestuff, can be extensive use of conventional known dyestuff, for example based on cyanin, based on tetraazatetradecane porphyrin, based on Azulene (azulenium), based on side's sour cyanines (squarylium), based on ditan, based on triphenyl methane Ji Yu oxazine, based on azine, based on sulfo-pyrans (thiopyrylium), based on purpurine (viologen), azo-based, the azo-based metal complex, based on tetrazo, based on anthraquinone, based on perylene, based on indanthrone, based on nitroso-group, based on the metal mercaptide complex compound, based on indigo, the azo-based methine, based on xanthene, based on oxanol, based on indole aniline with based on the dyestuff of quinoline.For example, can comprise trade(brand)name ADEKA ARKLESTW-1367, ADEKA ARKLES SG-1574, ADEKA ARKLESTW-1317, ADEKA ARKLES FD-3351, ADEKA ARKLES Y944, all by Asahi Denka Co., Ltd. produces; With trade(brand)name NK-5451, NK-5532 and NK-5450, all by HAYASHIBARA BIOCHEMICAL LAB., INC. produces.
The amount that is formulated in the dyestuff in the near-infrared-absorbing material of the present invention can depend on to be used and selection aptly, and can be 0.1 to 10wt% based on the solid content of resin, and preferred 1 to 8wt%.
In addition, the amount that can also not weaken its performance with isocyanate compound, mercaptan compound, epoxy compounds, based on the compound of amine, based on compound, oxazoline compound, silane coupling agent and the resin curing agent of imines for example the UV solidifying agent be used for near-infrared-absorbing material of the present invention.Yet, more preferably do not use the near-infrared-absorbing material of solidifying agent, because be provided longer coating solution storage time and do not need to wear out.
In addition, the known additive that is used for film or coating agent near-infrared-absorbing material of the present invention be can be used for, dispersion agent, levelling agent, defoamer, viscosity modifier, matting agent, tackifier, static inhibitor, antioxidant, UV absorption agent, photostabilizer, quencher, solidifying agent, anti, slip(ping)agent etc. comprised.
(6) form of near-infrared-absorbing material
Near-infrared-absorbing material of the present invention can be the anion salt of the formula (1) of the solid of will respectively doing for oneself (for example powder and particle) form and the form of another kind of compound.With the mixture situation of fusible resin in, can be by this mixture being processed into arbitrary shape being not less than under the temperature of melt temperature heating.Press or extrusion shaping machine can be used for processing.
On base material, forming in the situation of near infrared ray absorption layer by coating method, preferably using solvent so that near-infrared-absorbing material dissolves, disperses and suspend and becomes liquid state.As spendable solvent in this case, for example can use aliphatic solvents for example hexanaphthene and methylcyclohexane; Aromatic solvent is toluene and dimethylbenzene for example; Based on the solvent of ketone for example acetone, methylethylketone and mibk; Based on the solvent of ester for example ethyl acetate and butylacetate; Based on the solvent of nitrile acetonitrile for example; Based on the solvent of alcohol for example methyl alcohol, ethanol and Virahol; Based on the solvent of ether for example tetrahydrofuran (THF) and dibutyl ether; Based on the solvent of glycol ethers for example ethylene glycol butyl ether, propylene glycol positive propyl ether, propylene glycol n-butyl ether and propylene glycol methyl ether acetate; Based on the solvent of acid amides for example methane amide and N, dinethylformamide; Based on the solvent of halogen for example methylene dichloride and chloroform.They can use separately or with mixed form.In order to improve the weather resistance of dyestuff, can advantageously use boiling point not to be higher than 100 ℃ solvent, for example methylethylketone and ethyl acetate.In addition, the outward appearance of coat film when applying in order to improve, can advantageously use boiling point is 100 to 150 ℃ solvent, for example toluene, mibk and butylacetate.In order to improve the anti-cracking of coat film, can advantageously use boiling point is 150 to 200 ℃ solvent for example ethylene glycol butyl ether, propylene glycol positive propyl ether, propylene glycol n-butyl ether and propylene glycol methyl ether acetate.
Near-infrared absorbing base material of the present invention can be with acting on film or the sheet material that optics, agricultural, building, vehicle and image recording are used, the display stands that is used for refrigerator and refrigerator, solar cell is the dyestuff sensitized solar cell for example, use the sensitive materials of semiconductor laser as light source, the information-recording material that for example is used for CD, anti-amblyopia material, the photo-thermal converting material is sensitized paper and tackiness agent for example.Especially, this class information-recording material, photo-thermal converting material for example sensitized paper and pressure-sensitive adhesive/tackiness agent of using and be preferably the blooming or the sheet material that are used for for example PDP and CCD, being used for CD for example.
(7) near-infrared absorbing base material (film and laminated film form)
A third aspect of the present invention relates to the near-infrared absorbing base material that comprises near-infrared-absorbing material of the present invention.Near-infrared absorbing base material of the present invention can be by being that film or be laminated on the transparent substrate by the coat film that will contain near-infrared-absorbing material obtains with the near-infrared absorbing forming materials.
This transparent substrate is not particularly limited, as long as it can be used as optical material and substantially transparent usually.As object lesson, can comprise glass; Olefin polymer is cyclopolyolefin, amorphous cyclopolyolefin polymkeric substance for example; Methacrylic polymer is polymethylmethacrylate for example; Vinyl polymer is vinyl-acetic ester, vinyl halides base material for example; Polyester is PET for example; Polycarbonate; Polyvinyl acetal is butyral resin for example; Polyarylether resin etc.In addition, can be by for example Corona discharge Treatment, flame treating, Cement Composite Treated by Plasma, glow discharge processing, surface roughening (roughening) processing and the chemical treatment or apply that anchoring applies agent or undercoat carries out surface treatment with transparent substrate of conventional known method.In addition, can in matrix resin, mix known additive, heat-resisting and anti-aging reagent, slip(ping)agent and static inhibitor.By for example injection moulding of use known method, T mould molding, rolling press moulding and compressed moulding or by being dissolved in the casting process in the organic solvent, can be with its moulding film forming or sheet form.The matrix of forming this class transparent substrate can be not tensile or tensile, perhaps can with other base material laminations.
Be used for obtaining the transparent substrate of near-infrared absorption film, can preferably use the PET film, can advantageously use easy binding type PET film especially by coating method.Particularly, can comprise COSMOSHINE A4300 (by Toyobo, Ltd. produces), Lumirror U34 (producing) and Melinex 705 (producing) etc. by TeijinDuPont Films Japan Ltd. by Toray Ind.Inc..In addition, can also the functions of use film for example TAC (tri acetyl cellulose) film, anti-reflective film, antiglare film, shock absorption film, emi shielding film and UV gamma absorption film etc.By using these, can make the spectral filter that is used for plasma display or optical-semiconductor element expediently.The preferred film that uses.
In the middle of these, glass, PET film, easy binding type PET film, TAC film, anti-reflective film and emi shielding film are suitable to transparent substrate.
In the situation when for example glass is as transparent substrate with inorganic substrate,, can preferably use base material with low alkalinity component concentration in view of the weather resistance of near-infrared absorbing dyestuff.As near-infrared-absorbing material, the base material that has a high alkalinity component concentration when use is for example during soda-lime glass, preferably will have positively charged ion for example the salt of aniline, pyridine and quinoline be used for containing the anionic salt of formula (1).In addition, as the near-infrared absorbing dyestuff, the preferred use has the diimmonium dyestuff of four (pentafluorophenyl group) borate anion as counter anion.
The thickness of near-infrared absorbing base material of the present invention is generally the approximate extents of 0.1 μ m to 10mm.Yet it can depend on that target suitably measures.Can also depend on target and suitably measure the content that is contained in the near-infrared absorbing dyestuff in the near-infrared absorbing base material.
The method of producing near-infrared absorbing base material of the present invention is not particularly limited, and for example can adopt following method.For example can comprise (a) by near-infrared-absorbing material of the present invention is mixed in the resin, subsequently with the method for mixture heating up and moulding; (b) method by in the presence of polymerizing catalyst, near-infrared-absorbing material of the present invention and monomer or oligopolymer cast poymerization being produced resin board or film; (c) near-infrared-absorbing material of the present invention is coated to method on the transparent substrate; (d) be coated to near-infrared-absorbing material of the present invention on the strippable base material and subsequently coated fabric placed method on the transparent substrate; (e) near-infrared-absorbing material of the present invention is coated on the transparent substrate, subsequently coated fabric is placed on another transparent substrate and laminate solidified method.
As preparation method (a), although mold temperature and film forming (making resin board) condition may depend on the resinous type of use and change a little, but can comprise this method usually, it comprises: with near-infrared-absorbing material of the present invention join in toner or the particle (pellet), under 150 to 350 ℃ with mixture heating up with dissolving and by forcing machine with liquid molding to produce resin board or to make film (preparation resin board).
In by near-infrared-absorbing material of the present invention in the presence of polymerizing catalyst and monomer or the cast polymerized production method of oligopolymer (b), mixture can be packed in the mould, be cured reaction then, mixture flowed in mould be cured then up to obtaining hard product.Many resins can comprise acrylic resin, two (allyl carbonate) resins of glycol ether, Resins, epoxy, phenol-formaldehyde resin, polystyrene resin, silicone resin etc. by this method moulding and this resinoid object lesson.In the middle of these, be preferred by means of the casting process of methyl methacrylate mass polymerization, it can provide hardness, thermotolerance and chemical resistant properties good acrylic resin sheet material.
As polymerizing catalyst, can use the known initiator that is used for the free radical thermopolymerization, for example can comprise superoxide such as benzoyl peroxide, peroxidation right-chlorobenzoyl and peroxide carbonic acid diisopropyl ester, and azo-compound azobis isobutyronitrile for example.The amount of using be generally based on amount of the mixture 0.01 to 5wt%.Heating temperature during thermopolymerization is generally 40 to 200 ℃, and polymerization time is generally 30 minutes to 8 hours approximate range.Except thermopolymerization, can also adopt by means of the light polymerization process that adds Photoepolymerizationinitiater initiater or sensitizer.
As preparation method (c), can comprise near-infrared-absorbing material of the present invention is coated to method on the transparent substrate, near-infrared-absorbing material of the present invention is fixed on the fine particle, then fine particle is scattered in method on the coating material paint transparent substrate wherein etc.
In with the situation of near-infrared absorbing coated materials on base material, can adopt known coating machine.For example, can comprise knife coater for example comma coating machine, slit die coating machine, give the lacquer coating machine for example lip be coated with machine, kiss and be coated with for example for example reverse coating machine, flow coating machine, spraying machine, doctor knife coater etc. of microflute roll-coater, engraved roll coater, roller coating machine of machine.Before applying, can for example Corona discharge Treatment and Cement Composite Treated by Plasma be carried out surface treatment with base material by known method.As drying and curing, for example warm air, far infrared rays and UV solidify can to adopt known method.After dry and curing, can twine this film with known protective membrane.
As preparation method (d), can comprise and be coated to near-infrared-absorbing material of the present invention on the strippable base material and subsequently coating material is arranged in the method on the transparent substrate and near-infrared-absorbing material of the present invention is fixed on the fine particle, subsequently fine particle is scattered in the strippable base material of coating material paint wherein and the base material that applies placed method on the transparent substrate etc.
In the situation of producing by this method, the preferred use has the near-infrared-absorbing material of pressure-sensitive adhesive as resin.If necessary, can further tackifier and solidifying agent be mixed in the near-infrared-absorbing material.
As strippable base material, can use to be coated with on it, based on the base material of fluorine with based on the base material of alkene based on silicone, based on alkene, based on oil with based on the paper or the film of the stripper of fluorine etc.As transparent substrate and coating machine, can use similarly above-mentioned those.
As preparation method (e), can comprise near-infrared-absorbing material of the present invention is coated on the transparent substrate, subsequently coated fabric is placed on another transparent substrate and with laminate solidified method etc.
In the situation of producing by this method, the preferred use has the near-infrared-absorbing material of pressure-sensitive adhesive as resin.If necessary, solidifying agent can be mixed in the near-infrared-absorbing material.As transparent substrate and coating machine, can use similarly above-mentioned those.
Although will add the amount of the near-infrared absorbing dyestuff in the near-infrared absorbing base material of the present invention can depend on thickness, the absorption intensity of the resin board that will produce or film, the transmitance of visible light etc. and change, but in (e), near-infrared absorbing dyestuff of the present invention can use based on 0.01 to 20wt% the amount of being generally of adhesive resin weight in method (a).
Near-infrared-absorbing material of the present invention can be changed into the constituent materials of good spectral filter with transparent and good near-infrared absorbing ability high in the visible region.Owing to compare higher weather resistance particularly thermotolerance and wet fastness with conventional near-infrared-absorbing material, even therefore store or use outward appearance and the near-infrared absorbing ability of also can keeping for a long time.In addition, because sheet material or film produce easily, so it can be used for plasma display or optical-semiconductor element.In addition, it can also be used for needs and filters ultrared spectral filter or film for example diathermic wall, sun glasses and optical recording material etc.
(8) be used for the spectral filter of plasma display
The spectral filter that can advantageously near-infrared-absorbing material of the present invention be used as plasma display.Therefore, a fourth aspect of the present invention relates to the spectral filter that is used for plasma display that uses near-infrared-absorbing material of the present invention.This spectral filter has in the visible region and is not less than 40%, preferably be not less than 50%, further preferably be not less than 60% total light transmittance and be not higher than 30%, preferably be not higher than 15% and further preferably be not higher than near infrared ray transmitance under 5% 800 to the 1000nm wavelength.
Except the near infrared ray absorption layer that comprises near-infrared-absorbing material, spectral filter of the present invention can also be equipped with for example glass of electromagnetic interference shield layer, anti-reflecting layer, anti-dazzle (the anti-sudden strain of a muscle) layer, anti-scraping layer, color adaptation layer and supporting substrate.
Can select the composition of each layer of spectral filter arbitrarily, yet, this spectral filter preferably has the two-layer at least combination of being made up of one deck at least of anti-reflecting layer and antiglare layer and near infrared ray absorption layer, and more preferably by further electromagnetic interference shield layer and its combination being had at least 3 layers spectral filter.
Anti-reflecting layer or antiglare layer can be the top layers on people's contact surface, and can select the combination of near infrared ray absorption layer and electromagnetic interference shield layer arbitrarily.In addition, between these 3 layers, can insert for example anti-scraping layer of other layers, color adaptation layer, impact absorbing layer, supporting substrate and transparent substrate.
Can use each layer of pressure-sensitive adhesive or adhesives, and near infrared ray absorption layer itself can be served as pressure-sensitive adhesive or tackiness agent.Especially, because by being not less than-80 ℃ and be not higher than 0 ℃ pressure-sensitive adhesive or near-infrared-absorbing material of the present invention that tackiness agent mixes to obtain can show good cohesiveness to another transparent substrate with Tg, so can easily produce the spectral filter that is used for plasma display of the present invention by means of other layers grade being bonded on anti-reflecting layer, antiglare layer, impact absorbing layer and the electromagnetic interference shield layer by this near-infrared-absorbing material.During each layer, it can be carried out physical treatment for example corona treatment and Cement Composite Treated by Plasma in bonding, perhaps can for example polymkeric substance, polyester and the Mierocrystalline cellulose of polymine, Ji Yu oxazoline apply agent as anchoring with known high polar polymer.
The spectral filter of using for plasma display preferably is provided with anti-reflecting layer or antiglare layer, so that the visual zone of seeing easily to be provided on the foremost layer of people's contact side.
Anti-reflecting layer can suppress lip-deep reflection and therefore prevent exterior light for example fluorescence present from the teeth outwards.Anti-reflecting layer can be by the inorganic substance film of metal oxide, fluorochemical, silicide, boride, carbide, nitride and sulfide for example, and perhaps for example acrylic resin and fluorocarbon resin are laminated to single or multiple lift and prepare the resin by will having different refractivity.In last situation, can adopt the method for using gas deposition or sputtering method on transparent substrate, to form the single or multiple lift antireflecting coating.In one situation of back, can adopt use knife coater for example comma coating machine, slit die coating machine, give the lacquer coating machine for example lip be coated with machine, engraved roll coater, flow coating machine, spraying machine and doctor knife coater lip-deep method with antireflecting coating paint transparent substrate.
Antiglare layer forms in the following manner: made China ink, this China ink be applied on arbitrary layer of spectral filter of the present invention by conventional coating method by the fine powder of silicon-dioxide, melamine resin, acrylic resin etc., then this coating of thermofixation or photocuring.In addition, the film after the non-glare treated can be bonded on the spectral filter.
Anti-scratch film can form in the following manner: by means of the known coating method of routine will for example urethane acrylate, epoxy acrylate and polyfunctional acrylic ester and Photoepolymerizationinitiater initiater be dissolved in or be scattered on arbitrary layer that the coating liquid that obtains in the organic solution is applied in spectral filter of the present invention, drying and photocuring then by making acrylate.
Can obtain to have the spectral filter of anti-reflecting layer or antiglare layer and near infrared ray absorption layer by the back side that is pressed in anti-reflecting layer or antiglare layer layer by layer that will comprise near-infrared absorbing base material of the present invention.As laminating method, can be membranaceous near-infrared-absorbing material of the present invention and anti-reflecting layer or antiglare layer is bonded to one another by pressure-sensitive adhesive, perhaps the solution of near-infrared-absorbing material of the present invention can be applied directly to the back side of anti-reflecting layer or antiglare layer.In the situation when on the back side that near infrared ray absorption layer is arranged at anti-reflecting layer or antiglare layer, preferably use the UV absorbing film as transparent substrate to suppress dyestuff because the deterioration of UV ray.
Preferably the electromagnetic interference shield layer is arranged on the spectral filter that is used for plasma display, to remove the hertzian wave that from panel, produces.
As the electromagnetic interference shield layer, for example can use by by means of technology such as etching or printing with wire netting be stamped in obtain with the resin leveling then on the film or by the metal vapour phase being deposited on the fibrous reticulum film that obtains in the embedded resin then.
Can obtain to have near infrared ray absorption layer and the two-layer spectral filter of electromagnetic interference shield layer by the mixture of making between EMI shield and the near-infrared-absorbing material.As the method for making this class mixture, can be membranaceous near-infrared-absorbing material of the present invention and electromagnetic interference shield layer is bonded to one another by pressure-sensitive adhesive, perhaps the solution of near-infrared-absorbing material of the present invention can be applied directly to the back side of electromagnetic interference shield layer.In addition, near-infrared-absorbing material can also be used as resin so that the wire netting on the film is flattened.In addition, near-infrared-absorbing material of the present invention can also be used the sedimentary fiber of metal vapour phase as resin to embed.
To comprise the near infrared ray absorption layer formed by near-infrared-absorbing material of the present invention and three spectral filters that bonding obtains of anti-reflecting layer or antiglare layer and electromagnetic interference shield layer as having near infrared ray absorption layer and anti-reflecting layer or antiglare layer and the trilaminar spectral filter of electromagnetic interference shield layer, can using.If necessary, for example glass or the functional membrane color adaptation film for example of supporting substrate that can bond.
For production process or the film of simplifying spectral filter constitutes, the preferred use has multi-functional composite membrane.For example, can be with following spectral filter as spectral filter, such as being bonded in the spectral filter that obtains on the electromagnetic interference shield layer by the composite membrane that uses pressure-sensitive adhesive will comprise near infrared ray absorption layer and anti-reflecting layer or antiglare layer; Or be bonded in the spectral filter that obtains on anti-reflecting layer or the antiglare layer by the composite membrane that uses pressure-sensitive adhesive will comprise near infrared ray absorption layer and electromagnetic interference shield layer; Or be bonded in the spectral filter that obtains on the near infrared ray absorption layer by the composite membrane that uses pressure-sensitive adhesive will comprise electromagnetic interference shield layer and anti-reflecting layer or antiglare layer.With regard to the composite membrane that comprises electromagnetic interference shield layer and anti-reflecting layer or antiglare layer, near-infrared-absorbing material can serve as pressure-sensitive adhesive.
Can be used for the spectral filter of plasma display and display apparatus is placed apart or it directly can be bonded in display apparatus with of the present invention.In the situation when placed apart, preferably use glass as supporting substrate with itself and display apparatus.In the situation when directly being bonded in it on display apparatus, preferably do not use the spectral filter of glass.
(9) plasma display.
Be placed on the plasma display by the spectral filter that lamination is had near-infrared-absorbing material of the present invention, can keep the excellent images quality for a long time.Therefore, a fifth aspect of the present invention relates to the plasma display that uses near-infrared-absorbing material of the present invention, near-infrared absorbing base material of the present invention or spectral filter of the present invention.Have the plasma display that directly is bonded in the spectral filter on the display apparatus lively picture quality can be provided.When spectral filter is directly bondd, preferably use toughened glass as being used for display apparatus or being mounted with the glass of the spectral filter of impact absorbing layer.
Pressure-sensitive adhesive as the display apparatus that is used to bond can comprise rubber for example styrene butadiene rubbers, polyisoprene rubber, polyisobutylene rubber, natural rubber, neoprene (neoprene) rubber, chloroprene (chloroprene) rubber and isoprene-isobutylene rubber; Polyalkyl acrylate is polymethyl acrylate, polyethyl acrylate and butyl polyacrylate etc. for example, and they can use separately, yet also can use the pressure-sensitive adhesive that adds piccolight, polybale, rosin ester etc. as pressure-sensitive adhesive.In addition, can use the pressure-sensitive adhesive shown in JP-A-2004-263084, yet it is not limited to this with shock absorption ability.
The thickness of pressure-sensitive adhesive layer can be generally 5 to 2000 μ m, and is preferably 10 to 1000 μ m.Also allow peelable film is arranged on the surface of pressure-sensitive adhesive layer to prevent that dust is bonded in pressure-sensitive adhesive layer and protection pressure-sensitive adhesive layer on the surface that is arranged in plasma display.In this case, between pressure-sensitive adhesive layer and peelable film, form the part that do not have the pressure-sensitive adhesive layer or form the non-sticky part by peripheral portion and peel off the initiation region to provide, the operability in the time of can easily implementing to bond by means of non-adhesive film is clipped in the middle at spectral filter.
Impact absorbing layer can protect display apparatus to avoid external impact.The spectral filter of supporting substrate is not adopted in preferred use.As the shock absorption material, can use vinyl-vinyl acetate copolymer shown in JP-A-2004-246365 and JP-A-2004-264416, acrylic polymers, polyvinyl chloride, based on carbamate with based on resin of silicone etc., yet it is not limited to this.
Embodiment
Explain the present invention particularly referring now to embodiment, yet these embodiment will never mean restriction the present invention." part " used herein is meant " weight part ".According to the transparency and the weather resistance in following method evaluation near-infrared absorbing ability, the visible region.
(1) estimates near-infrared absorbing ability (near infrared transmitance)
In order to measure visible-near-infrared spectrum, use UV-3100 (producing) and the transmitance of measurement under 1090nm or 835nm wavelength by ShimadzuCorp..
(2) transparency (transmitance of visible light) of evaluation visible region
In order to measure total light transmittance, use ∑ 90 systems (by Nippon DenshokuIndustries Co., Ltd. produces).
(3) estimate thermotolerance
Specimen is placed 100 ℃ baking oven 120 hours, measure before test and the optical transmission spectra in the Visible-to-Near InfaRed zone and aberration (L*a*b* in 2 ° of visuals field, illuminant-C) afterwards.In order to measure visible-near-infrared spectrum, use UV-3100 (producing) and the transmitance of measurement under 1090nm or 835nm wavelength to change (Δ T) by Shimadzu Corp..In order to measure aberration, the variation (Δ b*) of using SE2000 (by Nippon DenshokuIndustries Co., Ltd. produces) and measuring b*.
(4) estimate wet fastness
Specimen is placed the cell 120 hours of 80 ℃ and 95%RH, measure before test and the optical transmission spectra in the Visible-to-Near InfaRed zone and aberration (L*a*b* in 2 ° of visuals field, illuminant-C) afterwards.In order to measure visible-near-infrared spectrum, use UV-3100 (producing) and the transmitance of measurement under 1090nm or 835nm wavelength to change (Δ T) by Shimadzu Corp..In order to measure aberration, the variation (Δ b*) of using SE2000 (by NipponDenshoku Industries Co., Ltd. produces) and measuring b*.
(embodiment 1-1)
With 5 parts of N, N, N ', N '-four (right-two (normal-butyl) aminophenyl)-phenylene diimmonium hexafluoro antimonate (hereinafter being called " diimmonium SbF6 salt ") is dissolved in 95 parts of methylethylketones (hereinafter being called " MEK ") with preparation near-infrared absorbing dye solution 1.Then, 5 part of four (pentafluorophenyl group) Sodium Tetraborate (TEPBNa, by Nippon ShokubaiCo., Ltd. produces) is dissolved among 95 parts of MEK with preparation borate solution 1.Subsequently, by using HALSHYBRID IR-G205 (by Nippon Shokubai Co., Ltd. produce: solid content 29%) as resin, 69 parts of resins, 1,2 parts of borate solutions 1 of 4 parts of near-infrared absorbing dye solutions and 22 parts of MEK are mixed, obtain the coating material solid content and be 21% near-infrared-absorbing material solution A 1 (solid content ratio: resin/dyestuff/borate=100/1/0.5).
(embodiment 1-2)
Use doctor knife coater (No.34) that near-infrared absorbing material solution A1 is applied in easy binding type PET film (COSMOSHINE A4300, by Toyobo, Ltd. produce) on, in hot air drying machine, descended dry 3 minutes then at 150 ℃, obtain near-infrared absorbing base material A1.Estimate near infrared ray transmitance, total light transmittance and the thermotolerance of near-infrared absorbing base material A1, the results are shown in the table 1.In this case, under the 1090nm wavelength, measure the near infrared ray transmitance.
(embodiment 2-1)
Use HALSHYBRID IR-G205 (by Nippon Shokubai Co., Ltd. produce: solid content 29%) as resin, 69 parts of resins, 1,8 parts of borate solutions that obtain in embodiment 1-1 1 of 4 parts of near-infrared absorbing dye solutions and 17 parts of MEK are mixed, obtain the coating material solid content and be 21% near-infrared-absorbing material solution A 2 (solid content ratio: resin/dyestuff/borate=100/1/2).
(embodiment 2-2)
Be similar to and like that near-infrared absorbing material solution A2 applied drying then among the embodiment 1-2, obtain near-infrared absorbing base material A2.By use with embodiment 1-2 near infrared ray transmitance, total light transmittance and the thermotolerance of identical method evaluation near-infrared absorbing base material A2, the results are shown in the table 1.
(comparative example 1-1)
Use HALSHYBRID IR-G205 (by Nippon Shokubai Co., Ltd. produce: solid content 29%) as tackiness agent, 69 parts of tackiness agents, 4 parts of near-infrared absorbing dye solutions 1 and 23 parts of MEK are mixed, obtain the coating material solid content and be 21% near-infrared-absorbing material solution B 1 (solid content ratio: resin/dyestuff/borate=100/1/0).
(comparative example 1-2)
Be similar to and like that near-infrared absorbing material solution B1 applied drying then among the embodiment 1-2, obtain near-infrared absorbing base material B1.By use with embodiment 1-2 near infrared ray transmitance, total light transmittance and the thermotolerance of identical method evaluation near-infrared absorbing base material B1, the results are shown in the table 1.
Table 1
Resin (solid content ratio) Dyestuff (admittedly the ratio of measuring) Borate (solid content ratio) Near infrared ray transmitance (%) Total light transmittance (%) Thermotolerance Δ T (%) Thermotolerance Δ b *
Embodiment 1-2 (A1) X1 100 Y1 1.0 Z1 0.5 29.6 88.7 3.1 0.9
Embodiment 2-2 (A2) X1 100 Y1 1.0 Z1 2.0 32.0 88.7 1.2 0.5
Comparative example 1-2 (B1) X1 100 Y1 1.0 Do not have- 29.3 88.3 7.0 0.9
X1:HALSHYBRID IR-G205 (by Nippon Shokubai Co., Ltd. produces)
Y1:N, N, N ', N '-four (right-two (normal-butyl) aminophenyl)-to phenylene diimmonium hexafluoro antimonate
Z1: four (pentafluorophenyl group) Sodium Tetraborate
Find out from the result shown in the table 1, although near-infrared absorbing base material A1 of the present invention and A2 with wherein do not use boratory near-infrared absorbing base material B1 of the present invention to compare to have suitable near infrared ray transmitance and total light transmittance, but near-infrared absorbing base material A1 of the present invention and A2 are significantly less than near-infrared absorbing base material B1 in the variation of optical property after 120 hours under 100 ℃ (transmitance variation), and this shows that near-infrared-absorbing material of the present invention is difficult to deterioration.
(embodiment 3-1)
Under 25 ℃, 1.05 part of four (pentafluorophenyl group) Sodium Tetraborate (TEPBNa, by NipponShokubai Co., Ltd. produces) and 0.70 portion of diimmonium SbF6 salt are dissolved in 10 parts of methylethylketones (MEK).Subsequently, the gained solution of all measuring is once added in 500 parts of deionized waters and to descend to keep to leave standstill 1 hour at 25 ℃.To precipitate by filtered and recycled and dry under 80 ℃, obtain 0.83 part of black solid.
The black solid of gained is dissolved among the MEK and with fluorescent X-ray spectrum carries out ultimate analysis, find not detect antimony.In addition, demonstrate and identical peak, the peak of TEPB by being dissolved in the F-NMR that measures in the deuterated dimethyl sulfoxide (DMSO), but do not detect the peak that is obtained from SbF6.In addition, coincide with spectrum, therefore confirm to have kept the diimmonium structure as the diimmonium dyestuff of raw material by being dissolved in the Visible-to-Near InfaRed absorption spectrum measured among the MEK.
Confirm that by above result this black solid is four (pentafluorophenyl group) borate (being called " diimmonium TEPB salt " hereinafter) as the diimmonium of raw material.The Visible-to-Near InfaRed absorption spectrum of diimmonium TEPB salt is shown among Fig. 1, and the IR spectrum of the diimmonium TEPB salt of measuring by the KBr method is shown among Fig. 2.
(embodiment 3-2)
By 2 portions of diimmonium TEPB salt being dissolved among 98 parts of MEK preparation near-infrared absorbing dye solution 2.Use HALSHYBRID IR-G205 (by NipponShokubai Co., Ltd. produce: solid content 29%) as tackiness agent, 69 parts of tackiness agents, 2,11 parts of MEK of 17 parts of near-infrared absorbing dye solutions are mixed, obtain the coating material solid content and be 21% near-infrared-absorbing material solution A 3 (solid content ratio: resin/dyestuff/borate=100/1.7/0.0).
(embodiment 3-3)
Be similar to and like that near-infrared absorbing material solution A3 applied drying then among the embodiment 1-2, obtain near-infrared absorbing base material A3.By use with embodiment 1-2 in identical method evaluation near-infrared absorbing base material A3, the results are shown in the table 2.
(comparative example 2-1)
Use diimmonium SbF6 salt.The Visible-to-Near InfaRed absorption spectrum of the diimmonium SbF6 salt of measuring in MEK solution is shown among Fig. 3, and the IR spectrum of the diimmonium SbF6 salt of measuring by the KBr method is shown among Fig. 4.
(comparative example 2-2)
By 2 portions of diimmonium SbF6 salt being dissolved among 98 parts of MEK preparation near-infrared absorbing dye solution 3.Use HALSHYBRID IR-G205 (by NipponShokubai Co., Ltd. produce: solid content 29%) as tackiness agent, 69 parts of tackiness agents, 3,17 parts of MEK of 10 parts of near-infrared absorbing dye solutions are mixed, obtain the coating material solid content and be 21% near-infrared-absorbing material solution B 2 (solid content ratio: resin/dyestuff/borate=100/1.0/0.0).
(comparative example 2-3)
Be similar to and like that near-infrared absorbing material solution B2 applied drying then among the embodiment 1-2, obtain near-infrared absorbing base material B2.By use with embodiment 1-2 in identical method evaluation near-infrared absorbing base material B2, the results are shown in the table 2.
(comparative example 3-1)
Being dissolved in 0.51 part of sodium tetraphenylborate (under title Kalibor by Dojindo Lab. produce) and 0.70 portion of diimmonium SbF6 salt among 10 parts of MEK under 25 ℃ and keeping leaving standstill, precipitate to produce.Cleaning this solution and sedimentary while with 5 parts of MEK, the solution of all measuring is once being added in 500 parts of deionized waters and 25 ℃ of following maintenances left standstill 1 hour.To precipitate by filtered and recycled and at room temperature dry under vacuum, obtain 0.83 part of sorrel solid.
The sorrel solid of gained is dissolved among the MEK and with fluorescent X-ray spectrum carries out ultimate analysis, find not detect antimony.In addition, anionic mass spectrum shows the peak that comes from tetraphenyl borate salts.In addition, when being dissolved in solid among the MEK, the color of solution becomes green gradually and finds that the diimmonium SbF6 salt that the Visible-to-Near InfaRed absorption spectrum likens to raw material shows bigger absorption and shows littler absorption near infrared region in visible-range.
Confirmed by above result: although this sorrel solid is the tetraphenyl borate salts (being called " diimmonium BPh4 salt ") as the diimmonium of raw material, it is unstable and become ammonium salt easily.The Visible-to-Near InfaRed absorption spectrum of the diimmonium BPh4 salt of measuring in MEK solution is shown among Fig. 5, and the IR spectrum of the diimmonium BPh4 salt of measuring by the KBr method is shown among Fig. 6.
(comparative example 3-2)
By 2 portions of diimmonium BPh4 salt being dissolved among 98 parts of MEK preparation near-infrared absorbing dye solution 4.Use HAL SHYBRID IR-G205 (from NipponShokubai Co., Ltd.: solid content 29%) as tackiness agent, 4,16 parts of MEK mix with the dye solution of 69 parts of tackiness agents, 11 parts of gained, obtain the coating material solid content and be 21% near-infrared-absorbing material solution B 3 (solid content ratio: resin/dyestuff/borate=100/1.1/0).
(comparative example 3-3)
Be similar to and like that near-infrared absorbing material solution B3 applied among the embodiment 1-2 and dry, obtain near-infrared absorbing base material B3.By use with embodiment 1-2 in identical method evaluation near-infrared absorbing base material B3, the results are shown in the table 1.
Table 2
Resin (solid content ratio) Dyestuff (solid content ratio) Borate (solid content ratio) Near infrared ray transmitance (%) Total light transmittance (%) Thermotolerance Δ T (%) Thermotolerance Δ b *
Embodiment 1-2 (A1) X1 100 Y2 1.7 Do not have- 27.9 88.3 2.5 0.6
Embodiment 2-2 (A2) X1 100 Y3 1.0 Do not have- 23.7 88.1 6.5 1.3
Comparative example 1-2 (B1) X1 100 Y4 1.1 Do not have- 86.8 90.1 7.6 -2.3
X1:HALSHYBRID IR-G205 (by Nippon Shokubai Co., Ltd. produces)
Y2:N, N, N ', N '-four (right-two (normal-butyl) aminophenyl)-to phenylene diimmonium four (pentafluorophenyl group) borate
Y3:N, N, N ', N '-four (right-two (normal-butyl) aminophenyl)-to phenylene diimmonium hexafluoro antimonate
Y4:N, N, N ', N '-four (right-two (normal-butyl) aminophenyl)-to phenylene diimmonium tetraphenyl borate salts
Find out from the result shown in the table 2, although near-infrared absorbing base material A3 of the present invention with wherein use the near-infrared absorbing base material B2 do not contain borate anion of the present invention to compare to have suitable near infrared ray transmitance and total light transmittance based on the dyestuff of diimmonium, but near-infrared absorbing base material A3 of the present invention is significantly less than near-infrared absorbing base material B2 in the variation of optical property after 120 hours under 100 ℃ (transmitance changes and aberration changes), and this shows that near-infrared-absorbing material of the present invention is difficult to deterioration.
Also find out from the result shown in the table 2, although near-infrared absorbing base material A3 of the present invention with wherein use the near-infrared absorbing base material B3 that forms by borate anion to compare to have suitable total light transmittance based on the dyestuff of diimmonium with the aryl that does not contain electron-withdrawing group, the near-infrared absorbing ability among the near-infrared-absorbing material A3 is significantly higher.In addition, be also noted that significantly less than near-infrared absorbing base material B3, this shows that near-infrared-absorbing material of the present invention is difficult to deterioration in the variation of optical property after 120 hours under 100 ℃ (transmitance changes and aberration changes) in near-infrared absorbing base material A3 of the present invention.
(embodiment 4-1)
407.0 parts of methyl methacrylates, 93.0 parts of n-butyl acrylates are mixed as monomer, obtain monomer mixture.6.0 parts of PERKAD0X 12-XL25 (deriving from Kayaku Akuzo Corp.) and 100 parts of toluene are mixed, obtain initiator solution.350 parts of monomer mixtures and 250 parts of toluene are added in the flask, and with thermometer, agitator, nitrogen inlet tube, reflux cooler and dropping funnel setting thereon.150 parts of monomer mixtures and 31.8 parts of initiator solutions are mixed and add dropping funnel.When nitrogen passed through with 20ml/ minute, consequently having the internal temperature of making reached 100 ℃ with the flask heating.74.2 parts of initiator solutions are added flask with the beginning polymerization.From packing polymerization starter into after 20 minutes, in 60 minutes, monomer in the dropping funnel and initiator solution are added.After adding, dropping funnel is added flask with 75 parts of toluene cleanings and with washing lotion.Subsequently, solution is worn out 60 minutes and add 150 parts of toluene as thinner.Solution is worn out 60 minutes again and add 150 parts of toluene as thinner.Then, solution is worn out 60 minutes again and add 150 parts of toluene as thinner.Solution is worn out 60 minutes again, temperature is risen to 110 ℃ then.Behind elevated temperature, solution is worn out 300 minutes again and add 100 parts of toluene as thinner.By being cooled to room temperature, obtain Resin A.Resin A has 34.4% solid content, 198,000 weight-average molecular weight and 77 ℃ Tg.
(embodiment 4-2)
By with 6 parts of N, N, N ', N '-four (right-two (normal-butyl) aminophenyl)-two (trifluoromethane sulfone) imide salts of phenylene diimmonium and 5 parts of EXCOLOR IR-10A (by Nippon Shokubai Co., Ltd. produces) are dissolved among 89 parts of MEK with preparation near-infrared absorbing dye solution 5.Then, 5 part of four (pentafluorophenyl group) borate 1-Methylimidazole is dissolved among 95 parts of MEK with preparation borate solution 2.Subsequently, 58 parts of Resin A, 5,10 parts of borate solutions 2 of 10 parts of near-infrared absorbing dye solutions and 24 parts of MEK are mixed, obtain the coating material solid content and be 21% near-infrared-absorbing material solution A 4 (solid content ratio: resin/dyestuff/borate=100/5.5/2.5).
(embodiment 4-3)
Use doctor knife coater (No.34) that near-infrared absorbing material solution A4 is applied in easy binding type PET film (COSMOSHINE A4300, by Toyobo, Ltd. produce) on, in hot air drying machine, descended dry 3 minutes then at 150 ℃, obtain near-infrared absorbing base material A4.Estimate near infrared ray transmitance, total light transmittance and the thermotolerance of near-infrared absorbing base material A4, the results are shown in the table 3.In this case, under the 1090nm wavelength, measure the near infrared ray transmitance.
(embodiment 5-1)
By with 5 parts of N, N-Dimethylcyclohexyl ammonium four (pentafluorophenyl group) borate is dissolved among 95 parts of MEK, preparation borate solution 3.Then, 58 parts of Resin A, 5,10 parts of borate solutions 3 of 10 parts of near-infrared absorbing dye solutions and 24 parts of MEK are mixed, obtain the coating material solid content and be 21% near-infrared-absorbing material solution A 5 (solid content ratio: resin/dyestuff/borate=100/5.5/2.5).
(embodiment 5-2)
Be similar to and like that near-infrared absorbing material solution A5 applied among the embodiment 4-3 and dry, obtain near-infrared absorbing base material A5.By use with embodiment 4-3 in identical method evaluation near-infrared absorbing base material A5, the results are shown in the table 3.
(comparative example 4-1)
58 parts of Resin A, 10 parts of near-infrared absorbing dye solutions 5 and 32 parts of MEK are mixed, obtain the coating material solid content and be 21% near-infrared-absorbing material solution B 4 (solid content ratio: resin/dyestuff/borate=100/5.5/0).
(comparative example 4-2)
Be similar to and like that near-infrared absorbing material solution B4 applied among the embodiment 4-3 and dry, obtain near-infrared absorbing base material B4.By use with embodiment 4-3 in identical method evaluation near-infrared absorbing base material B4, the results are shown in the table 3.
Table 3
Resin (solid content ratio) Dyestuff (solid content ratio) Borate (solid content ratio) Near infrared ray transmitance (%) Total light transmittance (%) Wet fastness Δ T (%) Wet fastness Δ b *
Embodiment 4-3 (A4) X2 100 Y5 5.5 Z2 2.5 1.0 65.3 0.6 2.3
Embodiment 5-2 (A5) X2 100 Y5 5.5 Z3 2.5 1.8 67.8 2.3 5.9
Comparative example 4-2 (B4) X2 100 Y5 5.5 Do not have- 1.4 65.9 5.7 11.6
X2: Resin A
Y5:N, N, N ', N '-four (right-two (normal-butyl) aminophenyl)-to the mixture of two (trifluoromethane sulfone) imide salts of phenylene diimmonium and EXCOLOR IR-10A (by Nippon ShokubaiCo., Ltd. produces)
Z2: four (pentafluorophenyl group) borate 1-Methylimidazole
Z3: four (pentafluorophenyl group) borate N, N-dimethyl hexamethylene ammonium
Find out from the result shown in the table 3, although comparing with the near-infrared absorbing base material B4 that does not wherein use borate anion of the present invention with A5, near-infrared absorbing base material A4 of the present invention has suitable near infrared ray transmitance and total light transmittance, but the variation of optical property after 120 hours under 80 ℃ and 95%RH among near-infrared absorbing base material A4 of the present invention and the A5 (transmitance changes and the aberration variation) is significantly less than near-infrared absorbing base material B4, and this shows that near-infrared-absorbing material of the present invention is difficult to deterioration.
(embodiment 6-1)
Weighing 2-EHA (478.2 parts), cyclohexyl methacrylate (120 parts) and Hydroxyethyl acrylate (1.8 parts) obtain monomer mixture as monomer and thoroughly mixing.Monomer mixture (240 parts) and ethyl acetate (147 parts) adding are equipped with in the flask of thermometer, agitator, nitrogen inlet tube, reflux cooler and dropping funnel.To be used for dropping liquid by monomer mixture (360 parts), ethyl acetate (16 parts) with as the monomer mixture that the NYPER BMT-K40 (0.72 part) of polymerization starter forms pack into dropping funnel and thorough mixing.When nitrogen was passed through with 20ml/ minute, the internal temperature of flask is risen to 84 ℃ and pack NYPER BMT-K40 (0.96 part) into beaker with the beginning polymerization as polymerization starter.From packing polymerization starter into after 10 minutes, begin to drip the monomer mixture that is used to drip of dropping funnel of packing into.In 90 minutes, evenly drip the monomer mixture that is used for dropping liquid.After dripping end, with ethyl acetate (50 parts) beaker of packing into.Then reaction soln was worn out 4.3 hours down at 82 ℃.After reaction finishes, add ethyl acetate (44.4 parts) and at last with reaction soln with dilution with toluene to obtain about 45% non-volatile content, obtain acrylic acid polymer solution.It is called as pressure-sensitive adhesive A.The Tg that calculates this pressure-sensitive adhesive A is 0 for-51 ℃ with acid number.
(embodiment 6-2)
By 2.5 portions of diimmonium SbF6 salt and 2.5 parts of EXCOLOR IR-10A (by Nippon Shoukubai Co., Ltd. produces) are dissolved among 95 parts of MEK preparation near-infrared absorbing dye solution 6.Then, use pressure-sensitive adhesive A as resin, 89 parts of pressure-sensitive adhesive A, 6,16 parts of borate solutions 1 of 16 parts of near-infrared absorbing dye solutions and 18 parts of MEK are mixed, obtain the coating material solid content and be 30% near-infrared-absorbing material solution A 6 (solid content ratio: resin/dyestuff/borate=100/2/2).
(embodiment 6-3)
Use doctor knife coater (No.50) that near-infrared absorbing material solution A6 is applied in easy binding type PET film (COSMOSHINE A4300, by Toyobo, Ltd. produce) on, and in hot air drying machine, descended dry 3 minutes at 150 ℃, be the coat film of 10 μ m to form thickness.Another easy binding type PET film of bonding on this film (COSMOSHINE A4300, by Toyobo, Ltd. produces) obtains near-infrared absorbing base material A6.The Visible-to-Near InfaRed line absorption spectrum of this near-infrared absorbing base material A6 is shown among Fig. 7.It is used as the specimen of thermal test.Estimate near infrared ray transmitance, total light transmittance and the thermotolerance of near-infrared absorbing base material A6, the results are shown in the table 4.In this case, under the 1090nm wavelength, measure the near infrared ray transmitance.
(comparative example 5-1)
By 89 parts of pressure-sensitive adhesive A, 16 parts of near-infrared absorbing dye solutions 6 and 31 parts of MEK being mixed, obtaining the coating material solid content is 30% near-infrared-absorbing material solution B 5 (solid content ratio: resin/dyestuff/borate=100/2/0).
(comparative example 5-2)
Be similar to embodiment 6-3 and change use near-infrared-absorbing material solution B 5 acquisition near-infrared absorbing base material B5 like that simultaneously into.The Visible-to-Near InfaRed absorption spectrum of this near-infrared absorbing base material B5 is shown among Fig. 8.Be similar to embodiment 6-3 and estimate this base material like that, the results are shown in the table 4.
(comparative example 6-1)
By 5 parts of sodium tetraphenylborates (being produced by Dojindo Lab.) are dissolved among 95 parts of MEK preparation borate solution 4 under title Kalibor.89 parts of pressure-sensitive adhesive A, 6,16 parts of borate solutions 4 of 16 parts of near-infrared absorbing dye solutions and 31 parts of MEK are mixed, obtain the coating material solid content and be 30% near-infrared-absorbing material solution B 6 (solid content ratio: resin/dyestuff/borate=100/2/2).
(comparative example 6-2)
Use near-infrared-absorbing material solution B 6, be similar to embodiment 6-3 and obtain near-infrared absorbing base material B6 like that.The Visible-to-Near InfaRed absorption spectrum of this near-infrared absorbing base material B6 is shown among Fig. 9.This base material B6 is used as the specimen that is used for thermal test.Be similar to embodiment 6-3 and estimate base material B6 like that, the results are shown in the table 4.
Table 4
Resin (solid content ratio) Dyestuff (solid content ratio) Borate (solid content ratio) Near infrared ray transmitance (%) Total light transmittance (%) Thermotolerance Δ T (%) Thermotolerance Δ b *
Embodiment 6-3 (A6) X3 100 Y6 2.0 Z1 2.0 14.9 71.6 3.5 2.4
Comparative example 5-2 (B5) X3 100 Y6 2.0 Do not have- 15.5 69.3 21.1 0.0
Comparative example 6-2 (B6) X3 100 Y6 2.0 Z4 2.0 77.6 77.1 10.5 1.0
X3: pressure-sensitive adhesive A
Y6:N, N, N ', N '-four (right-two (normal-butyl) aminophenyl)-to the mixture of phenylene diimmonium hexafluoro antimonate and EXCOLOR IR-10A (by Nippon Shokubai Co., Ltd. produces)
Z1: four (pentafluorophenyl group) Sodium Tetraborate
Z4: sodium tetraphenylborate
In the middle of the result shown in the table 4, at first by the result of near-infrared absorbing base material A6 of the present invention is not compared with wherein not using the result according to the near-infrared absorbing base material B5 of borate solution of the present invention, have near infrared ray transmitance and the total light transmittance that is equivalent to near-infrared absorbing base material B 5 although find near-infrared absorbing base material A6, but near-infrared absorbing base material A6 of the present invention is significantly less than near-infrared absorbing base material B5 in the variation of optical property after 120 hours under 100 ℃ (transmitance variation), and this shows that near-infrared-absorbing material of the present invention is difficult to deterioration.
In addition, compare by those of near-infrared absorbing base material B6 that the result of near-infrared absorbing base material A6 of the present invention and salt wherein are made up of the borate anion with the aryl that does not contain electron-withdrawing group, has suitable total light transmittance although find these absorbing materials, but the near infrared ray transmitance of near-infrared absorbing base material A6 of the present invention is significantly less than near-infrared absorbing base material B6, and this shows that near-infrared absorbing base material A6 can realize significantly higher filtration near infrared ray efficient.In addition, by the thermotolerance between near-infrared absorbing base material A6 of the present invention and the near-infrared absorbing base material B6 is compared, near-infrared absorbing base material A6 of the present invention was showing the optical property variation (transmitance variation) that is significantly less than near-infrared absorbing base material B6 after 120 hours under 100 ℃, this shows that near-infrared-absorbing material of the present invention shows less deterioration.
(embodiment 7-1)
In the four neck flasks that agitator, nitrogen inlet tube, dropping funnel, thermometer and cooling tube are housed, add 278 parts of 2-EHAs, 120 parts of cyclohexyl methacrylates, 2 parts of vinylformic acid 2-hydroxyl ethyl esters and 258 parts of ethyl acetate, and under nitrogen atmosphere with mixture heating up to 85 ℃.After internal temperature reached 85 ℃, the 0.8 part of NYPER BMT-K40 that packs into (being produced by NOF Corp.) and 8 parts of ethyl acetate were with initiated polymerization.After beginning 10 minutes, in 90 minutes, drip 417 parts of 2-EHAs, 180 parts of cyclohexyl methacrylates, 3 parts of vinylformic acid 2-hydroxyl ethyl esters, 0.6 part of NYPER BMT-K40 and 10 parts of ethyl acetate from reaction.At every turn after drip finishing separately 120,150,180 and 210 minutes, 1 part of azobis isobutyronitrile and 10 parts of ethyl acetate pack into to continue reaction 2 hours under refluxing, at last with ethyl acetate dilution to obtain 40% solid content, obtain pressure-sensitive adhesive B solution.The polymkeric substance that obtains has weight-average molecular weight 350,000, calculate Tg is 0 for-40 ℃ and acid number.
(embodiment 7-2)
By 4 portions of diimmonium TEPB salt and 2 parts of EXCOLOR IR-10A (by Nippon Shoukubai Co., Ltd. produces) are dissolved among 94 parts of MEK preparation near-infrared absorbing dye solution 7.With 10 parts of N, N-dimethyl-4-monomethylaniline four (pentafluorophenyl group) borate is dissolved among 90 parts of MEK then, preparation borate solution 5.Then, 50 parts of pressure-sensitive adhesive B solution, 10 parts of near-infrared absorbing dye solutions 7 and 10 parts of borate solutions 5 are mixed, obtain the coating material solid content and be 31% near-infrared-absorbing material solution A 7 (solid content ratio: resin/dyestuff/borate=100/3/5).
(embodiment 7-3)
Near-infrared absorbing material solution A7 is applied in easy binding type PET film (COSMOSHINE A4300, by Toyobo, Ltd. produce) on, so that the pressure-sensitive adhesive layer is 20 μ m at dried thickness, and following dry 2 minutes at 100 ℃ in hot air drying machine.By this pressure-sensitive adhesive film is bonded on the sheet glass, obtain near-infrared absorbing base material A7.It is used as the specimen that is used for anti-moisture test.Estimate near infrared ray transmitance, total light transmittance and the wet fastness of this base material A7, the results are shown in the table 5.In this case, under the 1090nm wavelength, measure the near infrared ray transmitance.
(embodiment 8-1)
By 10 parts of quinoline four (pentafluorophenyl group) borate being dissolved among 90 parts of MEK preparation borate solution 6.Then, 50 parts of pressure-sensitive adhesive B solution, 10 parts of near-infrared absorbing dye solutions 7 and 10 parts of borate solutions 6 are mixed, obtain the coating material solid content and be 31% near-infrared-absorbing material solution A 8 (solid content ratio: resin/dyestuff/borate=100/3/5).
(embodiment 8-2)
It is such to be similar to embodiment 7-3, changes into simultaneously using near-infrared-absorbing material solution A 8, obtains near-infrared absorbing base material A8.Be similar to and estimate this base material A8 among the embodiment 7-3 like that, the results are shown in the table 5.
(embodiment 9-1)
By 50 parts of pressure-sensitive adhesive B solution, 10 parts of near-infrared absorbing dye solutions 7 and 10 parts of ethyl acetate being mixed, obtaining the coating material solid content is 29% near-infrared-absorbing material solution A 9 (solid content ratio: resin/dyestuff/borate=100/3/0).
(embodiment 9-2)
Be similar to embodiment 7-3, change into simultaneously and use near-infrared-absorbing material solution A 9, obtain near-infrared absorbing base material A9 like that.It is used as the specimen that is used for anti-moisture test.Be similar to and estimate this base material A9 among the embodiment 7-3 like that, the results are shown in the table 5.
(comparative example 7-1)
By 4 portions of diimmonium SbF6 salt and 2 parts of EXCOLOR IR-10A (by Nippon Shoukubai Co., Ltd. produces) are dissolved among 94 parts of MEK preparation near-infrared absorbing dye solution 8.Then, 50 parts of pressure-sensitive adhesive B solution, 10 parts of near-infrared absorbing dye solutions 8 and 10 parts of ethyl acetate are mixed, obtain the coating material solid content and be 29% near-infrared-absorbing material solution B 7 (solid content ratio: resin/dyestuff/borate=100/3/0).
(comparative example 7-2)
Be similar to embodiment 7-3, change into simultaneously and use near-infrared-absorbing material solution B 7, obtain near-infrared absorbing base material B7 like that.This base material B7 is used as the specimen that is used for anti-moisture test.Be similar to and estimate this base material B7 among the embodiment 7-3 like that, the results are shown in the table 5.
Table 5
Resin (solid content ratio) Dyestuff (solid content ratio) Borate (solid content ratio) Near infrared ray transmitance (%) Total light transmittance (%) Wet fastness Δ T (%) Wet fastness Δ b *
Embodiment 7-3 (A7) X4 100 Y7 3.0 Z5 5 1.2 52.8 4.6 11.2
Embodiment 8-2 (A8) X4 100 Y7 3.0 Z6 5 2.8 55.8 0.8 4.7
Embodiment 9-2 (A9) X4 100 Y7 3.0 Do not have- 0.6 49.8 38.6 28.7
Comparative example 7-2 (B7) X4 100 Y8 3.0 Do not have- 42.8 58.2 32.4 0.5
X4: pressure-sensitive adhesive B
Y7:N, N, N ', N '-four (right-two (normal-butyl) aminophenyl)-to phenylene diimmonium four (pentafluorophenyl group) borate and EXCOLOR IR-10A (from Nippon ShokubaiCo., mixture Ltd.)
Y8:N, N, N ', N '-four (right-two (normal-butyl) aminophenyl)-to phenylene diimmonium hexafluoro antimonate and EXCOLOR IR-10A is (from Nippon Shokubai Co., mixture Ltd.)
Z5:N, N-dimethyl-4-monomethylaniline four (pentafluorophenyl group) borate
Z6: quinoline four (pentafluorophenyl group) borate
In the middle of the result shown in the table 5, at first by the result of near-infrared absorbing base material A9 is compared with the result of the near-infrared absorbing base material B7 that does not wherein use borate anion of the present invention, has the total light transmittance that is equivalent to near-infrared absorbing base material B7 although find near-infrared absorbing base material A9, but the near infrared ray transmitance of near-infrared absorbing base material A9 of the present invention is significantly less, and this shows that near-infrared absorbing base material A9 of the present invention can realize being significantly higher than the near infrared efficient of filtration of near-infrared absorbing base material B7.
In addition, the optical property of wherein using the near-infrared absorbing base material A7 of diimmonium dyestuff with borate anion of the present invention and borate of the present invention and A8 and near-infrared absorbing base material A9 of the present invention to have after 120 hours under 80 ℃ and 95%RH significantly less than near-infrared absorbing base material A6 changes (transmitance variation), even this shows that near-infrared-absorbing material of the present invention also is difficult to deterioration when being used for pressure-sensitive adhesive on the glass baseplate.
(embodiment 10)
1. polymerizable polysiloxane (M-1) is synthetic
To 300ml and pack in the four neck flasks of agitator, thermometer and cooling tube 144.5 parts of tetramethoxy-silicanes, 23.6 parts of γ-methacryloxypropyl trimethoxy silane, 19.0 parts of water, 30.0 parts of methyl alcohol and 5.0 parts of Amberlyst 15 (trade(brand)names are housed, Zeo-karb by Organo Corp. production), and under 65 ℃ the gained mixture is stirred 2 hours with reaction.After reaction mixture is cooled to room temperature, the outlet of distillation tower and cooling tube and connected effluent is installed replaces cooling tube, and under normal pressure, in 2 hours, the internal temperature of flask is risen to about 80 ℃, and keep identical temperature not flow out up to methyl alcohol.In addition, do not flow out up to methyl alcohol under the pressure of 2.67 * 10kPa mixture being remained under 90 ℃, further to react.Again mixture is cooled to room temperature,, obtains number-average molecular weight and be 1,700 polymerizable polysiloxane (M-1) then with Amberlyst 15 filterings.
2. organic polymer (P-1) is synthetic
260 parts of n-butyl acetates in the 1L flask that agitator, liquid droping port, thermometer and cooling tube are housed, pack into as organic solvent, introduce nitrogen and when stirring, the internal temperature of flask is risen to 110 ℃.In 3 hours, drip 12 parts of polymerizable polysiloxane (M-1), 19 parts of methacrylic tert-butyl acrylates, 94 parts of butyl acrylates, 67 parts of methacrylic acid 2-hydroxyl ethyl esters, 48 parts of perfluoro capryl ethyl-methyl acrylate (LIGHT-ESTER FM-108 then from liquid droping port, by KYOEISHA CHEMICAL Co., Ltd. produce) and 2.5 part 2,2 '-mixing solutions of azo pair (2-methylbutyronitrile).Even dripping the end back after continuing to stir 1 hour under the uniform temp, with 0.1 part of t-butyl peroxy-2-ethylhexanoate of twice adding in interval in 30 minutes, and made the mixture copolymerization in 2 hours by reheat, obtaining number-average molecular weight is 12,000 and weight-average molecular weight be the n-butyl acetate solution of 27,000 organic polymer (P-1).The solid content of gained solution is 48.2%.
3. the mixture dispersion liquid (S-1) of organic polymer and fine inorganic particles is synthetic
To 500ml and pack in advance in the four neck flasks of agitator, two liquid droping ports (liquid droping port A and liquid droping port B) and thermometer 200 parts of n-butyl acetates and 500 parts of methyl alcohol are housed, and internal temperature is adjusted to 40 ℃.Then, in 2 hours, drip by 10g organic polymer solution (P-1), 30 parts of tetramethoxy-silicanes and 5 parts of mixture solutions (material solution A) that n-butyl acetate is formed in n-butyl acetate when in flask, stirring, and drip by 5 part of 25% ammonia soln, 10 parts of deionized waters and 15 parts of mixture solutions (material solution B) that methyl alcohol is formed from liquid droping port B from liquid droping port A.After dripping end, the outlet of distillation tower and cooling tube and connected effluent is installed replaces cooling tube, and the internal temperature with flask under the pressure of 40kPa rises to 100 ℃, then ammonia, methyl alcohol and n-butyl acetate are removed solid content to obtain 30%, obtain being scattered in the dispersion liquid (S-1) in the n-butyl acetate, the dispersion liquid (S-1) of organic polymer and fine inorganic particles mixture has that the ratio of fine inorganic particles and organic polymer is 70/30 in the mixture.The median size of gained mixture is 23.9nm.By carrying out the ratio that ultimate analysis is determined at fine inorganic particles and organic polymer in the organic polymer that is compounded with fine inorganic particles at 130 ℃ of dispersion liquids that mixture had after dry 24 hours down an inorganic fine grain organic polymer under 1.33 * 10kPa pressure.In this case, the content of ash content being regarded as the organic polymer that is compounded with fine inorganic particles.In addition, by use dispersion liquid (S-1) with the mixture of 1 part of organic polymer of 99 parts of n-butyl acetates dilutions and fine inorganic particles, with transmission electron microscope with the particle in the solution take pictures, measure any 100 particulate diameters with acquisition mean value as median size.
4. reflectance coating
To passing through with 8 part of six vinylformic acid dipentaerythritol ester (DPE-6A, by KYOEISHA CHEMICAL Co., Ltd. produce) and 2 parts of pentaerythritol triacrylate (PE-3A, by KYOEISHA CHEMICAL Co., Ltd. produce) mix, and mixture is dissolved in the solution of 0.5 part of Photoepolymerizationinitiater initiater of adding in the solution that obtains among 40 parts of MEK (Irgacure 907, produced by Nippon Ciba Geigy K.K.) in 2 parts of MEK, is used for the coating liquid of hard coat with preparation.
By being compounded with the dispersion liquid (S-1) of the organic polymer of fine inorganic particles, 0.3 part of Desmodule N3200 (trade(brand)name with 9 parts, isocyanate curing agent, by Sumitomo Bayer Urethane Co., Ltd. produce) and 0.003 part of di-n-butyltin dilaurate and 110 parts of mibks mixing, preparation is used for the coating liquid of low-index layer.
The coating liquid that uses doctor knife coater will be used for hard coat is applied on the PET film that thickness is 188 μ m (COSMOSHINE A4300, by Toyobo, Ltd. produces), and drying is after 15 minutes down at 100 ℃, and the employing high voltage mercury lamp passes through 200mJ/cm 2The UV radiation exposure with coating curing, be the hard coat of 5 μ m to form thickness.Then, be applied in this hard coat, on the PET film, prepare anti-reflective film by the coating liquid that uses doctor knife coater will be used for low-index layer.
Use the surface roughening of steel wool with the opposition side of the anti-reflective film side of this film, and apply tusche to use UV-visible spectrometry (UV-3100, produce by ShimadzuCorp.) under 5 ° of input angles, measure reflection spectrum from minute surface for the surface of anti-reflective film side, and the reflectivity minimum value of reflectivity that becomes minimum wavelength and measure down therein.The reflectivity of the anti-reflective film that obtains under the 550nm wavelength is 0.45%.
5. spectral filter
By coater near-infrared absorbing material solution 7 being applied in the rear side of the anti-reflective film that obtains, is the thickness of pressure-sensitive adhesive layer of 20 μ m to obtain after drying, and in hot air drying machine 100 ℃ dry 2 minutes down.By this pressure-sensitive adhesive film being bonded on the sheet glass preparation spectral filter.The total light transmittance of this spectral filter, reflectivity and near infrared ray transmitance are good.
(embodiment 11-1)
5 parts of cationic hexafluorophosphates of indoles by formula (c) expression (S0728 is produced by FEW CHEMICALS GmbH, hereinafter is called " indoles PF6 salt ") are dissolved among 95 parts of MEK preparation near-infrared absorbing dye solution 9.Then, by using Resin A as resin, 125 parts of resins, 9,20 parts of borate solutions 1 of 3.3 parts of near-infrared absorbing dye solutions and 48 parts of MEK are mixed, obtain the coating material solid content and be 21% near-infrared-absorbing material solution A 11 (solid content ratio: resin/dyestuff/borate=100/0.43/2.5).
(embodiment 11-2)
Use doctor knife coater (No.34) that near-infrared absorbing material solution A11 is applied in easy binding type PET film (COSMOSHINE A4300, by Toyobo, Ltd. produce) on, and in hot air drying machine, descended dry 3 minutes at 150 ℃, near-infrared absorbing base material A11 obtained.Estimate near infrared ray transmitance, total light transmittance and the thermotolerance of near-infrared absorbing base material A11, the results are shown in the table 6.In this case, under the 835nm wavelength, measure the near infrared ray transmitance.
(embodiment 12-1)
Under 25 ℃, 2.11 part of four (pentafluorophenyl group) Sodium Tetraborate (TEPBNa, by NipponShokubai Co., Ltd. produces) and 0.80 portion of indoles PF6 salt are dissolved in 20 parts of tetrahydrofuran (THF)s (THF).Subsequently, under 40 ℃ by the solvent evaporation of rotatory evaporator with gained solution.To precipitate recovery, and under agitation add 800 parts of deionized waters and be scattered in wherein.To precipitate recovery and, obtain black solid by the gained dispersion liquid is filtered 80 ℃ of following dryings.
Coincide with spectrum by the gained black solid being dissolved in the Visible-to-Near InfaRed absorption spectrum measured among the MEK based on the dyestuff of indoles as raw material.In addition, in the IR of gained black solid spectrum and mass spectrum, detect the distinctive peak of TEPB negatively charged ion.Confirm that by above result this black solid is indoles cationic four (pentafluorophenyl group) borate (hereinafter being called " indoles TEPB salt ") by formula (c) expression.Be shown among Figure 10 by the Visible-to-Near InfaRed absorption spectrum that is dissolved in the indoles TEPB salt of measuring among the MEK, and the IR spectrum of the indoles TEPB salt of measuring by the KBr method is shown among Figure 11.And, be shown among Figure 12 by the Visible-to-Near InfaRed absorption spectrum that is dissolved in the TEPBNa that measures among the MEK, and the IR spectrum of the TEPBNa that measures by the KBr method is shown among Figure 13; Be shown among Figure 14 by the Visible-to-Near InfaRed absorption spectrum that is dissolved in the indoles PF6 salt of measuring among the MEK, and the IR spectrum of the indoles PF6 salt of measuring by the KBr method is shown among Figure 15.
(embodiment 12-2)
By 2 portions of indoles TEPB salt being dissolved among 98 parts of MEK preparation near-infrared absorbing dye solution 10.Use Resin A as resin, 63 parts of resins, 5.5 parts of near-infrared absorbing dye solutions 10 and 27 parts of MEK are mixed, obtain the coating material solid content and be 21% near-infrared-absorbing material solution A 12 (solid content ratio: resin/dyestuff/borate=100/0.5 5/0).
(embodiment 12-3)
Be similar to and like that near-infrared absorbing material solution A12 applied drying then among the embodiment 11-2, obtain near-infrared absorbing base material A12.By use with embodiment 11-2 in identical method evaluation near-infrared absorbing base material A12, the results are shown in the table 6.
(comparative example 8-1)
Use Resin A as resin, 125 parts of resins, 3.3 parts of near-infrared absorbing dye solutions 9 and 63 parts of MEK are mixed, obtain the coating material solid content and be 21% near-infrared-absorbing material solution B 8 (solid content ratio: resin/dyestuff/borate=100/0.43/0).
(comparative example 8-2)
Be similar to and like that near-infrared absorbing material solution B8 applied drying then among the embodiment 11-2, obtain near-infrared absorbing base material B8.By use with embodiment 11-2 in identical method evaluation near-infrared absorbing base material B8, the results are shown in the table 6.
Table 6
Resin (solid content ratio) Dyestuff (solid content ratio) Borate (solid content ratio) Near infrared ray transmitance (%) Total light transmittance (%) Thermotolerance Δ T (%) Thermotolerance Δ b *
Embodiment 11-2 (A11) X2 100 Y9 0.43 Z1 2.5 9.9 85.8 20.6 0.8
Embodiment 12-3 (A12) X2 100 Y10 0.55 Do not have- 10.2 85.8 23.0 -0.1
Comparative example 8-2 (B8) X2 100 Y9 0.43 Do not have- 16.7 86.2 35.7 1.5
X2: Resin A
Y9: by the cationic hexafluorophosphate of indoles of formula (c) expression
Y10: by indoles cationic four (pentafluorophenyl group) borate of formula (b) expression
Z1: four (pentafluorophenyl group) Sodium Tetraborate
Find out from the result shown in the table 6, although near-infrared absorbing base material A11 of the present invention and A12 with wherein do not use boratory near-infrared absorbing base material B8 of the present invention to compare to have suitable total light transmittance, but the near infrared ray transmitance of near-infrared absorbing base material A11 of the present invention, A12 and under 100 ℃ after 120 hours the variation of optical property be significantly less than near-infrared absorbing base material B8, this shows that near-infrared-absorbing material of the present invention is difficult to deterioration.
Industrial applicibility:
Because it is good that near-infrared-absorbing material of the present invention has high near-infrared absorbing ability and the transparency in the visible region and heat resistance and moisture-proof, so it can be used as for the filter of plasma scope and is used for the filter of optical-semiconductor element. It can also be used as the optical information recorder material.
The 2005-137561 that the 2005-137530 that the Japanese patent application No.2005-029504 that submitted on February 4th, 2005, on May 10th, 2005 submit to and on May 10th, 2005 submit to comprises that specification sheets, claims, accompanying drawing and summary are hereby incorporated by with their integral body.

Claims (20)

1. borate that is used for near-infrared-absorbing material, it has the negatively charged ion by following formula (1) expression:
[BR 1 mR 2 4-m] -(1)
R wherein 1Expression has the aryl of electron-withdrawing group; R 2Expression organic group, halogen group or hydroxyl; M is 1 to 4 integer.
2. the borate that is used for near-infrared-absorbing material according to claim 1, wherein, the electron-withdrawing group in the formula (1) is to be selected from by-C pF 2P+1(p is a natural number) ,-NO 2,-CN ,-F ,-Cl and-at least a substituting group in the group that Br forms.
3. the borate that is used for near-infrared-absorbing material according to claim 1 and 2, wherein, in formula (1) by R 1The aryl with electron-withdrawing group of expression is the phenyl with electron-withdrawing group.
4. according to each described borate that is used for near-infrared-absorbing material of claim 1 to 3, wherein, in formula (1) by R 1The aryl with electron-withdrawing group of expression is a pentafluorophenyl group.
5. according to each described borate that is used for near-infrared-absorbing material of claim 1 to 4, wherein, the negatively charged ion of being represented by formula (1) is four (pentafluorophenyl group) borate anion.
6. according to each described borate that is used for near-infrared-absorbing material of claim 1 to 5, it comprises negatively charged ion and organic cation by formula (1) expression.
7. according to each described borate that is used for near-infrared-absorbing material of claim 1 to 6, it comprises by the negatively charged ion of formula (1) expression and the positively charged ion with near-infrared absorbing ability.
8. the borate that is used for near-infrared-absorbing material according to claim 7, wherein, this positively charged ion is diimmonium positively charged ion or cationic at least a based on cyanine dyes.
9. according to each described borate that is used for near-infrared-absorbing material of claim 1 to 8, it comprises by the negatively charged ion of formula (1) expression with by the positively charged ion of following formula (2) expression or based on the positively charged ion of indoles:
Figure A2006800030600003C1
R wherein 3To R 10Represent hydrogen atom, halogen atom independently of one another, contain the alkyl of 1 to 10 carbon atom, perhaps contain 1 to 10 carbon atom and have substituent alkyl.
10. according to each described borate that is used for near-infrared-absorbing material of claim 1 to 6, it comprises by the negatively charged ion of formula (1) expression and the positively charged ion with the structure that is selected from ammonium, pyridine, aniline, imidazoles, tetramethyleneimine and quinoline.
11. a near-infrared-absorbing material, it comprises each described borate of claim 1 to 10 and near-infrared absorbing dyestuff.
12. near-infrared-absorbing material according to claim 11, wherein, this near-infrared absorbing dyestuff is at least a material that is selected from the group of being made up of following material: each described borate of claim 7 to 9, based on the dyestuff of diimmonium, based on the dyestuff of phthalocyanine, based on the dyestuff of cyanine, based on the dyestuff of the sour cyanines in side with based on the dyestuff of metal dithionite alcohol.
13. according to claim 11 or 12 described near-infrared-absorbing materials, it comprises the described borate of claim 10 and as each described borate of at least a claim 7 to 9 of near-infrared absorbing dyestuff.
14. according to each described near-infrared-absorbing material of claim 11 to 13, it further comprises at least a resin that is selected from the group of being made up of following resin: by having straight chain, side chain, alicyclic or encircle alicyclic alkyl more and have the resin that the methacrylic ester copolymerization of 1 to 10 carbon atom obtains; Second-order transition temperature is 65 to 85 ℃ a resin; Resin with branched structure; Pressure-sensitive adhesive and/or tackiness agent; Tg is not less than-80 ℃ and be not higher than 0 ℃ and acid number and be not higher than 30 resin.
15. a near-infrared absorbing base material, it comprises each described near-infrared-absorbing material of claim 11 to 14.
16. a near-infrared absorbing base material, it has each the described near-infrared-absorbing material of claim 11 to 14 that is arranged on the transparent substrate.
17. near-infrared absorbing base material according to claim 16, wherein, this transparent substrate is glass baseplate, PET film, easy binding type PET film, TAC film, anti-reflective film or emi shielding film.
18. a spectral filter that is used for plasma display, it uses each described near-infrared absorbing base material of claim 15 to 17.
19. a spectral filter that is used for optical-semiconductor element, it uses each described near-infrared absorbing base material of claim 15 to 17.
20. a plasma display, it uses each described near-infrared-absorbing material of claim 11 to 14, each described near-infrared absorbing base material of claim 15 to 17 or the described spectral filter of claim 18.
CNA2006800030602A 2005-02-04 2006-01-30 Borate and near-infrared ray absorption material Pending CN101107258A (en)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
JP029504/2005 2005-02-04
JP2005029504 2005-02-04
JP137530/2005 2005-05-10
JP137561/2005 2005-05-10

Publications (1)

Publication Number Publication Date
CN101107258A true CN101107258A (en) 2008-01-16

Family

ID=39000550

Family Applications (1)

Application Number Title Priority Date Filing Date
CNA2006800030602A Pending CN101107258A (en) 2005-02-04 2006-01-30 Borate and near-infrared ray absorption material

Country Status (1)

Country Link
CN (1) CN101107258A (en)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
TWI574971B (en) * 2012-07-27 2017-03-21 富士軟片股份有限公司 Near infrared absorptive composition, near infrared cut filter using the same, and camera module and method of manufacturing the same
CN107236258A (en) * 2010-05-11 2017-10-10 索尔维美国有限公司 The conjugated polymer and device of doping
CN107533171A (en) * 2015-05-12 2018-01-02 旭硝子株式会社 Optical filter and camera device
CN107851670A (en) * 2015-04-27 2018-03-27 密歇根州立大学董事会 The organic salt of the solar cell organic and transparent for high voltage
CN113811174A (en) * 2021-10-20 2021-12-17 齐盛时代(广州)科技有限公司 Transparent protective film for resisting high-power electromagnetic waves and production method thereof

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107236258A (en) * 2010-05-11 2017-10-10 索尔维美国有限公司 The conjugated polymer and device of doping
TWI574971B (en) * 2012-07-27 2017-03-21 富士軟片股份有限公司 Near infrared absorptive composition, near infrared cut filter using the same, and camera module and method of manufacturing the same
CN107851670A (en) * 2015-04-27 2018-03-27 密歇根州立大学董事会 The organic salt of the solar cell organic and transparent for high voltage
US11114623B2 (en) 2015-04-27 2021-09-07 Board Of Trustees Of Michigan State University Organic salts for high voltage organic and transparent solar cells
CN107533171A (en) * 2015-05-12 2018-01-02 旭硝子株式会社 Optical filter and camera device
CN107533171B (en) * 2015-05-12 2020-07-24 Ａｇｃ株式会社 Optical filter and imaging device
CN113811174A (en) * 2021-10-20 2021-12-17 齐盛时代(广州)科技有限公司 Transparent protective film for resisting high-power electromagnetic waves and production method thereof
CN113811174B (en) * 2021-10-20 2022-03-11 齐盛时代(广州)科技有限公司 Transparent protective film for resisting high-power electromagnetic waves and production method thereof

Similar Documents

Publication Publication Date Title
JP5033632B2 (en) Borate and near infrared absorbing materials
CN101679824B (en) Adhesive for sunlight shielding film and sunlight shielding film
US9359531B2 (en) Temporarily repositionable pressure sensitive adhesive blends
JP2010502563A (en) Salt for near-infrared absorbing composition and near-infrared absorbing adhesive composition
CN1989216A (en) (Meth)acrylate block copolymer pressure sensitive adhesives
CN1316263C (en) Optical filter and display using said filter
WO2006028006A1 (en) Diimmonium compound and use thereof
CN101163771A (en) Pressure-sensitive adhesive containing near infrared absorbing coloring matter
CN101107258A (en) Borate and near-infrared ray absorption material
CN102277099A (en) Pressure-sensitive adhesive composition, pressure-sensitive adhesive sheets and surface protecting film
CN103619977A (en) Adhesive agent composition, adhesive agent layer, and adhesive sheet
CN101921552A (en) Pressure-sensitive adhesive tape for optical member
CN104379688A (en) Paint and near infrared absorption filter
CN101511962A (en) Salt for near infrared ray absorbing composition and near infrared ray absorbing pressure sensitive adhesive composition
CN100527311C (en) Plasma display panel filter
CN102395642A (en) Near infrared ray-absorbable adhesive composition
KR100761646B1 (en) Wavelength-selective absorption filter
JP2010248461A (en) Near infrared ray-absorbable adhesive composition
CN101148546B (en) Light absorbing dyestuff composition
KR101145276B1 (en) Dyeing coating type rays of the sun reflection film using sublimate disperse dyes and matal chelate compound and method for manufacture thereof
CN108419438A (en) Coloured composition
CN104395409B (en) Porphyrazine pigment and application thereof
JP2011068780A (en) Near-infrared ray absorbing adhesive composition
KR20110116235A (en) Near-infrared absorbing pressure-sensitive adhesive composition
JP2005164972A (en) Optical filter and display using the same

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C12 Rejection of a patent application after its publication
RJ01 Rejection of invention patent application after publication

Open date: 20080116