CN101148546A - Light absorbing dyestuff composition - Google Patents
Light absorbing dyestuff composition Download PDFInfo
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- CN101148546A CN101148546A CNA2007101538435A CN200710153843A CN101148546A CN 101148546 A CN101148546 A CN 101148546A CN A2007101538435 A CNA2007101538435 A CN A2007101538435A CN 200710153843 A CN200710153843 A CN 200710153843A CN 101148546 A CN101148546 A CN 101148546A
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- light absorbing
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B69/00—Dyes not provided for by a single group of this subclass
- C09B69/02—Dyestuff salts, e.g. salts of acid dyes with basic dyes
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B23/00—Methine or polymethine dyes, e.g. cyanine dyes
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B57/00—Other synthetic dyes of known constitution
- C09B57/10—Metal complexes of organic compounds not being dyes in uncomplexed form
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
- C09J133/04—Homopolymers or copolymers of esters
- C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C09J133/10—Homopolymers or copolymers of methacrylic acid esters
Abstract
A light absorbing function capable of easily and high effective gifting absorption special wavelength light to the component materials such as plasma display screen is provided in the present invention, and the function deteriorating with age is fully prohibited light absorption dye composition. The light absorption dye composition contains light stabilization cyanine dye and bond, wherein the light stabilization cyanine dye is such as substituted benzenedithiol metal matches anion and cyanine dye cation reverse anion combination.
Description
Technical field
The present invention relates to have the light absorbing dyestuff composition of binding property and near-infrared absorbing function.
Background technology
In recent years, the light absorbing material that contains the photoabsorption composition is used in every field.For example, the light absorbing material of main absorption near infrared ray scope covers ultrared near-infrared absorption film and near-infrared absorbing plate, is that the agricultural of purpose is with the photosensitive lithographic plate of near-infrared absorption film, use laser etc. and utilize the recording medium etc. of near-infrared absorbing heat to be widely used with the selective use sunlight with optical filter, energy-conservation usefulness as used for plasma display screen near infrared ray barrier film, semiconductor light-receiving device.In addition, the main light absorbing material that absorbs the visible light scope is a purpose to improve purity of color, and the optical filter of using as picture display devices such as plasma panel, liquid crystal indicator, electroluminescent display, cathode tube display unit, fluorescent display tube and field emission escopes etc. is widely used.
In these light absorbing materials, used various light to have the light absorbing dyestuff of good light receptivity to specific wavelength.Light absorbing material can be by for example following method manufacturing: this light absorbing dyestuff is dissolved in makes dye solution in the solvent, with this solution coat on transparency carriers such as glass, resin and dry.For example, in above-mentioned used for plasma display screen near infrared ray barrier film, used the light absorbing dyestuff that in the wavelength region of about 800～1100nm, has the good light absorption characteristic, in addition, use in the optical filter at described picture display device, used the light absorbing dyestuff that under near near the wavelength the 490nm and the 550nm etc., has the good light absorption characteristic, these dye-coating in after drying such as polyethylene terephthalate (PET) films, can have been made membranaceous light absorbing material.The light absorbing material that obtains like this can be as required with the various films with other function, are bonded in the component materials etc. of regulation with tackiness agent and use.
At this, simply turn to purpose, the infrared ray-absorbable binder composition that has proposed to have following feature: the infrared absorbent (with reference to patent documentation 1) that contains resin of binding property and have very big absorbing wavelength at 700～1100nm place with the thin layerization of these light absorbing materials and its manufacturing engineering.
But as the light absorbing dyestuff that uses in the light absorbing material, good because of light absorpting ability, cheap widely used cyanine based dye is mixing with tackiness agent when using, its light absorpting ability through the time deterioration remarkable, lack practicality, thereby remain improvement.
[patent documentation 1] spy opens the 2001-207142 communique
Summary of the invention
Problem of the present invention is to provide a kind of like this light absorbing dyestuff composition: can be easily efficiently the component materials of article on plasma display screen etc. give the photoabsorption function that absorbs special wavelength light, and this function through the time deterioration fully suppressed.
The invention provides light absorbing dyestuff composition as described below.
(1) contains the light absorbing dyestuff composition of Photostabilised cyanine based dye and tackiness agent.
(2) according to (1) described light absorbing dyestuff composition, wherein Photostabilised cyanine based dye is the cationic counter ion combination of substituted benzene dithiol metal complex negatively charged ion and cyanine based dye.
(3) according to (2) described light absorbing dyestuff composition, wherein the substituted benzene dithiol metal complex negatively charged ion is the substituted benzene dithiol metal complex negatively charged ion shown in the general formula (1);
(in the formula, R
1And R
2Independent respectively, the alkyl of expression carbon number 1～6, alkylamino, replacement or unsubstituted morpholino base, replacement or unsubstituted piperidino, replacement or unsubstituted 1-pyrrolidyl, replacement or the unsubstituted thiomorpholine of carbon number 1～8 are for base, replacement or unsubstituted 1-piperazinyl or replacement or unsubstituted phenyl.M represents transition metal atoms.)
(4) according to each described light absorbing dyestuff composition in (1)～(3), wherein tackiness agent is (methyl) acrylate copolymer.
Embodiment
Below describe the present invention in detail.
Among the present invention, (methyl) vinylformic acid is meant acrylic or methacrylic acid, and (methyl) acrylate is meant acrylate or methacrylic ester.
Light absorbing dyestuff composition of the present invention contains Photostabilised cyanine based dye and tackiness agent.
Among the present invention, so-called Photostabilised cyanine based dye, be meant the cationic counter ion combination of phenylene dimercaptan metal complexes negatively charged ion and cyanine based dye, the perhaps mixture of metal complexes and cyanine based dye, the purpose of its proposition are to remedy and are extensive use of as light absorbing dyestuff but to the shortcoming of the significant cyanine based dye of photo absorption performance deterioration of light.
As phenylene dimercaptan metal complexes negatively charged ion and the cationic counter ion combination of cyanine based dye, can enumerate the cationic counter ion combination of unsubstituting phenenyl dithiol metal complex negatively charged ion and cyanine based dye, and substituted benzene dithiol metal complex negatively charged ion and the cationic counter ion combination of cyanine based dye.
As unsubstituting phenenyl dithiol metal complex negatively charged ion and the cationic counter ion combination of cyanine based dye, for example can enumerate, the spy opens the following formula (2) that the 2000-121807 communique puts down in writing and the counter ion combination of (3) etc.
As substituted benzene dithiol metal complex negatively charged ion and the cationic counter ion combination of cyanine based dye, for example can enumerate, the counter ion combination of the following formula (4) that Te Kaiping 6-338059 communique is put down in writing, and substituted benzene dithiol metal complex negatively charged ion shown in the following general formula (1) and the cationic counter ion combination of cyanine based dye etc.
In the general formula (1), R
1And R
2Independent respectively, the alkyl of expression carbon number 1～6, alkylamino, replacement or unsubstituted morpholino base, replacement or unsubstituted piperidino, replacement or unsubstituted 1-pyrrolidyl, replacement or the unsubstituted thiomorpholine of carbon number 1～8 are for base, replacement or unsubstituted 1-piperazinyl or replacement or unsubstituted phenyl.M represents transition metal atoms.
In addition, in as mixture Photostabilised cyanine based dye, metal complexes and cyanine based dye, as metal complexes, there is no particular restriction, for example can enumerate, the spy opens two sulphur alkene (dithiolene) metal complexess of record in the 2001-234000 communique etc. and the phenylene dimercaptan metal complexes corresponding with above-mentioned phenylene dimercaptan metal complexes negatively charged ion etc.
In these Photostabilised cyanine based dyes, preferably use the cationic counter ion combination of phenylene dimercaptan metal complexes negatively charged ion and cyanine based dye.In these counter ion combinations, angle from solvability solvent and good endurance, more preferably use the cationic counter ion combination of substituted benzene dithiol metal complex negatively charged ion and cyanine based dye, especially preferably use the cationic counter ion combination of substituted benzene dithiol metal complex negatively charged ion shown in the general formula (1) and cyanine based dye.Among the present invention, these Photostabilised cyanine based dyes may be used alone in combination of one kind or two or more kinds.
Below, be elaborated for substituted benzene dithiol metal complex negatively charged ion shown in the general formula (1) and the cationic counter ion combination of cyanine based dye, this counter ion combination can use in light absorbing dyestuff composition of the present invention as particularly preferred Photostabilised cyanine based dye.
In the general formula (1), R
1And R
2Independent respectively, the alkyl of expression carbon number 1～6, alkylamino, replacement or unsubstituted morpholino base, replacement or unsubstituted piperidino, replacement or unsubstituted 1-pyrrolidyl, replacement or the unsubstituted thiomorpholine of carbon number 1～8 are for base, replacement or unsubstituted 1-piperazinyl or replacement or unsubstituted phenyl.M represents transition metal atoms.
As the alkyl of carbon number 1～6, for example can enumerate methyl, ethyl, sec.-propyl, n-propyl, normal-butyl, sec-butyl, the tertiary butyl, n-pentyl, isopentyl, neo-pentyl, n-hexyl and isohexyl etc.
Alkylamino as carbon number 1～8, for example can enumerate, the N-methylamino, the N-ethylamino, N-sec.-propyl amino, N-n-propyl amino, N-normal-butyl amino, N, the N-dimethylamino, N, N-methylethyl amino, N, the N-diethylamino, N, N-ethyl sec.-propyl amino, N, N-ethyl isohexyl amino, N, N-ethyl n-hexyl amino, N, the different heptyl amino of N-methyl, N, N-methyl n-heptyl amino, N, the N-diisopropylaminoethyl, N, N-di amino, N, N-di-n-butyl amino, N, N-diisobutyl amino, N, N-two sec-butyl amino, N, N-di-t-butyl amino etc.
As replacing or unsubstituted morpholino base, for example can enumerate, morpholino base, 2-methylmorpholine for base, 3-methylmorpholine for base, 4-methylmorpholine for base, 2-ethyl morpholine for base, 4-n-propyl morpholino base, 3 normal-butyl morpholino bases, 2, the 4-thebaine is for base, 2, and the 6-thebaine is for base and 4-phenylmorpholine Dai Ji etc.
As replacing or unsubstituted piperidino, for example can enumerate, piperidino, 2-methyl (piperidino), 3-methyl (piperidino), 4-methyl (piperidino), 2-ethyl (piperidino), 4-n-propyl (piperidino), 3-normal-butyl (piperidino), 2,4-dimethyl (piperidino), 2,6-dimethyl (piperidino) and 4-phenyl (piperidino) etc.
As replacing or unsubstituted 1-pyrrolidyl, for example can enumerate, 1-pyrrolidyl, 2-methyl (1-pyrrolidyl), 3-methyl (1-pyrrolidyl), 4-methyl (1-pyrrolidyl), 2-ethyl (1-pyrrolidyl), 4-n-propyl (1-pyrrolidyl), 3-normal-butyl (1-pyrrolidyl), 2,4-dimethyl (1-pyrrolidyl), 2,5-dimethyl (1-pyrrolidyl) and 4-phenyl (1-pyrrolidyl) etc.
As replace or unsubstituted thiomorpholine for base, for example can enumerate, thiomorpholine for base, 2-methyl thiomorpholine for base, 3-methyl thiomorpholine for base, 4-methyl thiomorpholine for base, 2-ethylenebis dithiocarbamate morpholino base, 4-n-propyl thiomorpholine for base, 3-normal-butyl thiomorpholine for basic, 2, the 4-dimethyl sulphide is for morpholino base, 2, and the 6-dimethyl sulphide is for morpholino base and 4-phenyl thiomorpholine Dai Ji etc.
As replacing or unsubstituted 1-piperazinyl, for example can enumerate, 1-piperazinyl, 2-methyl (1-piperazinyl), 3-methyl (1-piperazinyl), 4-methyl (1-piperazinyl), 2-ethyl (1-piperazinyl), 4-n-propyl (1-piperazinyl), 3-normal-butyl (1-piperazinyl), 2,4-dimethyl (1-piperazinyl), 2,6-dimethyl (1-piperazinyl), 4-phenyl (1-piperazinyl) and 2-pyrimidyl (1-piperazinyl) etc.
As replacing or unsubstituted phenyl; for example can enumerate; phenyl; the 2-aminomethyl phenyl; the 3-aminomethyl phenyl; the 4-aminomethyl phenyl; 2; the 6-3,5-dimethylphenyl; the 4-ethylphenyl; 2-n-propyl phenyl; the 4-n-butylphenyl; the 2-chloro-phenyl-; the 4-chloro-phenyl-; 2; the 4-dichlorophenyl; the 2-bromophenyl; the 4-bromophenyl; 2-chloro-4-bromophenyl; the 4-aminophenyl; 2; the 4-diamino-phenyl; 2, the 4-dinitrophenyl; the 2-acetylphenyl; the 4-acetylphenyl; the 2-hydroxy phenyl; the 4-hydroxy phenyl; the 2-p-methoxy-phenyl; the 4-p-methoxy-phenyl; 2-methylthio group phenyl and 4-methylthio group phenyl etc.
These R
1And R
2In the compound of expression, from the good viewpoint of the solvability of counter ion combination to organic solvent that this substituted benzene dithiol metal complex negatively charged ion constitutes, preferred R
1And R
2Independent respectively is N, N-diethylamino, morpholino base, 1-pyrrolidyl, piperidino, 1-piperazinyl or phenyl.
In the general formula (1),, can enumerate nickle atom, copper atom and cobalt atom etc. as the object lesson of the transition metal atoms shown in the M.
Substituted benzene dithiol metal complex negatively charged ion shown in the general formula (1) is derived by substituted benzene dithiol metal complex.This substituted benzene dithiol metal complex can to open the identical method of the disclosed method of flat 10-45767 communique synthetic with for example opening flat 9-309886 communique, spy with the spy.That is, sulfohydrates such as replacing halogeno-benzene and Sodium sulfhydrate is reacted in the presence of sulphur or iron powder in polar organic solvent, form the iron complex of substituted benzene dithiol.Make the iron complex of gained substituted benzene dithiol and the halide reaction of transition metal, then by with ammonium salt or reactant salt, can obtain substituted benzene dithiol metal complex.
Come together to constitute cyanine based dye positively charged ion with the substituted benzene dithiol metal complex negatively charged ion of general formula (1) expression as the counter ion combination of preferred light stabilization cyanine based dye, there is no particular restriction, for example, use suitable commercially available cyanine based dye, when making this counter ion combination of aftermentioned, derive.
As the object lesson of commercially available cyanine based dye, can enumerate trade(brand)name " ST798 " of for example trade(brand)name of FEW Chemicals corporate system " S0813 ", " S0889 ", " S0941 ", " S0946 " and " S0824 " and Siber corporate system etc.May be used alone in combination of one kind or two or more kinds by these cyanine based dye deutero-cyanine based dye positively charged ions.
In order to obtain the cationic counter ion combination of described substituted benzene dithiol metal complex negatively charged ion and cyanine based dye, for example, described substituted benzene dithiol metal complex and described cyanine based dye are reacted in organic solvent, then, after removing the positively charged ion that derives from described substituted benzene dithiol metal complex and deriving from the negatively charged ion plasma of described cyanine based dye, gained crystal drying is got final product.
The usage ratio of cyanine based dye, with respect to 1 mole of substituted benzene dithiol metal complex, preferred 0.8～1.2 mole, more preferably 0.9～1.1 mole.If the usage ratio deficiency of cyanine based dye may reduce yield for 0.8 mole.In addition, if the usage ratio of cyanine based dye surpasses 1.2 moles, just not having the effect that matches with usage quantity, is uneconomic therefore.
As the organic solvent that uses in the described reaction, for example can enumerate N, dinethylformamide, acetonitrile, tetrahydrofuran (THF), acetone, methyl ethyl ketone etc.In these solvents, preferably use N, dinethylformamide, acetonitrile.
The usage quantity of these organic solvents with respect to substituted benzene dithiol metal complex 100 weight parts, is preferably 1000～100000 weight parts, more preferably 4000～20000 weight parts.If usage quantity less than 1000 weight parts of organic solvent then may not evenly mix.In addition, volumetric efficiency reduces if the usage quantity of organic solvent surpasses 100000 weight parts, is uneconomic therefore.
From the viewpoint of the decomposition that suppresses the cyanine based dye, temperature of reaction is preferably 0～60 ℃, more preferably 10～50 ℃.Reaction times is different with temperature of reaction, is reflected at the moment end usually.
In the above-mentioned reaction, substituted benzene dithiol metal complex and cyanine based dye are dissolved in organic solvent, but the counter ion combination that generates along with the carrying out of reaction part separate out, reaction solution becomes pulpous state.
As from the reaction solution that obtains, removing positively charged ion that derives from substituted benzene dithiol metal complex and the anionic method that derives from the cyanine based dye, there is no particular restriction, can enumerate for example following method: in reaction solution, add the ion that dissolves positively charged ion that derives from substituted benzene dithiol metal complex and the negatively charged ion that derives from the cyanine based dye etc. but the solvent that does not dissolve target compound counter ion combination, cooling makes the counter ion combination separate out after-filtration.In addition, from fully removing these ionic viewpoints, preferably with the counter ion combination recrystallization of gained.
As such solvent, for example can enumerate water, methyl alcohol, ethanol, propyl alcohol etc.Wherein, from removing ionic viewpoint not efficiently, preferably make water and methyl alcohol.
The usage quantity of described solvent with respect to substituted benzene dithiol metal complex 100 weight parts, is preferably 1000～100000 weight parts, more preferably 5000～20000 weight parts.
In addition, the mixture that uses substituted benzene dithiol metal complex and cyanine based dye is during as Photostabilised cyanine based dye, manufacture method as this mixture, for example, with respect to 1 mole of substituted benzene dithiol metal complex, add 0.8～1.2 mole of cyanine based dye, mix getting final product according to well-established law.
Light absorbing dyestuff composition of the present invention contains the Photostabilised cyanine based dye and the tackiness agent that as above make.
There is no particular restriction for the tackiness agent that uses in the light absorbing dyestuff composition of the present invention, for example can enumerate, (methyl) acrylate copolymer, polyvinyl chloride, Resins, epoxy, oxetane resin, urethane, vinyl acetate copolymer, styrene-propene acid copolymer, polyester, polymeric amide, polyolefine, styrene-butadiene copolymer are rubber, isoprene-isobutylene rubber and silicone resin etc.Wherein, from the angle of the transparency and good endurance, preferred (methyl) acrylate copolymer, Resins, epoxy, oxetane resin and the polyester of using more preferably uses (methyl) acrylate copolymer.In addition, when using glass as the substrate of the described light absorbing dyestuff composition of coating, thereby the diffusions such as alkali from this glass stripping make the Photostabilised cyanine based dye deterioration that is contained in this light absorbing dyestuff composition sometimes, but can be by using (methyl) acrylate copolymer, Resins, epoxy, oxetane resin and polyester as tackiness agent to prevent or alleviating this situation.
As (methyl) acrylate copolymer, for example can enumerate, as monomeric (methyl) alkyl acrylate be selected from intramolecularly and contain the multipolymer of any one at least in the monomer that the monomer of hydroxyl and intramolecularly contain carboxyl, amide group, amino arbitrary functional group.
As the example of (methyl) alkyl acrylate, can enumerate (methyl) methyl acrylate, (methyl) ethyl propenoate, (methyl) propyl acrylate, (methyl) n-butyl acrylate, (methyl) isobutyl acrylate, (methyl) tert-butyl acrylate, (methyl) 2-EHA, (methyl) vinylformic acid n-octyl, (methyl) Isooctyl acrylate monomer, (methyl) lauryl acrylate and (methyl) vinylformic acid stearyl etc.
The monomeric example that contains hydroxyl as intramolecularly, can enumerate (methyl) vinylformic acid 2-hydroxy methacrylate, (methyl) vinylformic acid 4-hydroxyl butyl ester, (methyl) vinylformic acid 2-hydroxy propyl ester, (methyl) vinylformic acid 2-hydroxyl butyl ester, the own ester of (methyl) vinylformic acid 6-hydroxyl, 1,4 cyclohexane dimethanol list (methyl) acrylate, chloro-2-hydroxypropyl acrylate, Diethylene Glycol list (methyl) acrylate, vinyl carbinol etc.
Contain the monomeric example of carboxyl, amide group, amino arbitrary functional group as intramolecularly, can enumerate the monomer that (methyl) vinylformic acid, (methyl) vinylformic acid 2-carboxyl ethyl ester, (methyl) vinylformic acid 3-carboxyl propyl ester, (methyl) vinylformic acid 4-carboxyl butyl ester, methylene-succinic acid, Ba Dousuan, toxilic acid, fumaric acid and maleic anhydride etc. contain carboxyl; (methyl) acrylamide, N, N-dimethyl (methyl) acrylamide, N-sec.-propyl (methyl) acrylamide, N, N-diethyl (methyl) acrylamide, acryloyl morpholine, N-vinyl acetamide, diacetone (methyl) acrylamide, N, N-dimethylamino-propyl (methyl) acrylamide, vinyl pyrrolidone, methylol (methyl) acrylamide, methoxy ethyl (methyl) acrylamide etc. contain the monomer of amide group; N, N-dimethylaminoethyl (methyl) acrylate, N, N-diethyllaminoethyl (methyl) acrylamide, N, N-dimethylamino-propyl (methyl) acrylamide, morpholino base ethyl (methyl) acrylate etc. contain amino monomer etc.
In addition, obtain to add other monomer the described monomer of (methyl) acrylate copolymer except being used to.As other monomeric example, can enumerate (methyl) alkoxyalkyl acrylates such as (methyl) vinylformic acid methoxyl group ethyl ester and (methyl) vinylformic acid ethoxy ethyl ester; (methyl) glycidyl acrylate etc. contains (methyl) acrylate of epoxy group(ing); (methyl) vinylformic acid acetoacetoxy groups ethyl ester etc. contains (methyl) acrylate of acetoacetyl; Aromatic monomers such as vinylbenzene, vinyl toluene and Vinyl toluene; Methacryloxypropyl methoxy silane, vinyl acetate, vinylchlorid and (methyl) vinyl cyanide etc.
The tackiness agent that uses in the light absorbing dyestuff composition of the present invention can use separately more than a kind or 2 kinds to be used in combination.
In addition, the tackiness agent that uses in the light absorbing dyestuff composition of the present invention, from having the binding property this point usually under the temperature near room temperature, preferred glass transition temperature (Tg) is below 10 ℃ usually, more preferably below 0 ℃, particularly preferably in below-10 ℃.
Among the present invention, described tackiness agent can use general commercially available product.Object lesson as the commercial binder, for example can enumerate, with acrylate copolymer as trade(brand)name " N-2147 " of trade(brand)name " SZ6232 ", " SZ6233 ", " SZ6234 ", " SZ6471 ", " SZ6472 " and The Nippon Synthetic Chemical Industry Co., Ltd's system of the NipponCarbide Industries corporate system of main component etc.In addition, as polyester as tackiness agent, can enumerate the trade(brand)name " Nichigo Polyester XI-0002 " of The Nippon Synthetic Chemical Industry Co., Ltd's system etc., as Resins, epoxy, can enumerate the trade(brand)name " Epicoat 828 " of Japan Epoxy Resin corporate system, " Epicoat 801N ", " Epicoat 1001 ", " Epicoat 834X90 ", " Epicoat 806 ", " Epicoat 4004P ", " Epicoat 1256 ", " Epicoat 152 ", " Epicoat1031S ", " Epicoat 872 ", " Epicoat 191P ", " Epicoat ST11 ", " EpicoatDC11 ", " Epicoat RC11 ", " Epicoat QX12 ", " Epicoat SL11 ", " Epicoat EMI24 ", " Epicoat IBMI12 ", " Epicoat YH300 ", " EpicoatDICY7 "; Nagase Chemtex corporate system trade(brand)name " Denacol EX-212L ", " Denacol EX-214L ", " Denacol EX-216L ", " Denacol EX-321L ", " Denacol EX-850L "; The trade(brand)name " CELLOXIDE 2021P " of NOF Corp's system trade(brand)name " EPIOL G-100 ", " EPIOL E-100 ", " EPIOL E-400 ", " EPIOL E-1000 ", " EPIOLP-200 " and DAICEL CHEMICAL INDUSTRIES corporate system etc., as oxetane resin, can enumerate the trade(brand)name " ARON OXETANE OXT-221 " of Toagosei Co., Ltd's system etc.
For light absorbing dyestuff composition of the present invention; although contain tackiness agent but still can fully suppress its light absorpting ability through the time deterioration reason unclear as yet; though exist in the tackiness agent-the OH base ,-COOH base etc. can reduce the light absorpting ability of cyanine based dye usually, considers it may is by using Photostabilised cyanine based dye to alleviate this effect.
In the scope of not damaging effect of the present invention, light absorbing dyestuff composition of the present invention can also contain difficult volatility additives such as various dyestuffs, solidifying agent, curing catalysts, linking agent, tint correction dyestuff, flow agent, antistatic agent, thermo-stabilizer, antioxidant, dispersion agent, fire retardant, lubricant, softening agent or UV light absorber such as cyanine based dye except that described Photostabilised cyanine based dye and tackiness agent.
In the light absorbing dyestuff composition of the present invention, with respect to tackiness agent 100 weight parts, the usage quantity of Photostabilised cyanine based dye is preferably 0.001～50 weight part, and more preferably 0.01～20 weight part is preferably 0.1～10 weight part especially.If usage quantity less than 0.001 weight part of Photostabilised cyanine based dye, then light absorpting ability may be insufficient.In addition, if the usage quantity of Photostabilised cyanine based dye surpasses 50 weight parts, then may can not get the effect that matches with usage quantity and uneconomical.
There is no particular restriction for the manufacture method of light absorbing dyestuff composition of the present invention, for example can enumerate, and adds described Photostabilised cyanine based dye, tackiness agent, reaches the above-mentioned additive that adds as required, with well-established law blended method.In addition, can also add ketone equal solvents such as an amount of acetone, methyl ethyl ketone, methyl iso-butyl ketone (MIBK), cyclopentanone and pimelinketone described light absorbing dyestuff composition is made liquid, thereby mixing is carried out easily.
Light absorbing dyestuff composition of the present invention for example, can directly be coated the display surface of plasma panel etc. etc., perhaps can coat film etc. that antireflection film etc. has other function and go up and use as light absorbing material.The former the time, the substrate etc. that is used to form the film etc. of light absorbing material is unnecessary, and also needn't be to the painting process of enforcement light absorbing dyestuffs such as this substrate, needn't implement the painting process of tackiness agent to the coating surface that is coated with light absorbing dyestuff.In addition, during the latter, needn't implement the operation to the further coating adhesive of coating surface of light absorbing dyestuff, this operation was necessary as subsequent handling in the past.
As the coating process of light absorbing dyestuff composition of the present invention, for example can enumerate, rod is coated with method, spin-coating method, intaglio plate coating method, dip coating, rolling method etc.In addition, in painting process, more easily carry out, described in the manufacture method of light absorbing dyestuff composition, preferably use the described solvent of adding in said composition and become liquid light absorbing dyestuff composition in order to make coating operation.
In addition, in the light absorbing dyestuff composition of the present invention, when using described additive such as solidifying agent, slaking (Raising as the additive effect that is used for further improving this additive gives birth to) operation or postprocessing working procedures, for example, operation, heating and the illumination operation etc. that for some time is left standstill at room temperature dark place preferably are set behind described painting process.
The light absorbing dyestuff composition of the application of the invention, can be easily, efficiently component materials such as article on plasma display screen give through the time deterioration light absorpting ability that fully suppressed.
Below, enumerate embodiment and comparative example specifies the present invention, but the present invention is not subjected to the restriction of these embodiment.
Synthesis example 1
At 4-(morpholino alkylsulfonyl)-1, add N among the 2-dichlorobenzene 59.2g (0.2 mole), the Sodium sulfhydrate aqueous solution 33.6g (0.42 mole) of dinethylformamide 183g and 70 weight % was 65 ℃ of reactions 3 hours.In this solution, add iron powder 5.9g (0.11 mole) and sulphur powder 6.7g (0.21 mole), 90～95 ℃ of reactions 6 hours.Room temperature adds methyl alcohol 1080g in the gained reaction solution after, after adding the sodium methoxide solution 77.2g (counting 0.21 mole) of 28 weight % and stirring 1 hour with sodium methylate, add Copper dichloride dihydrate (II) 17.0g (0.1 mole), and then room temperature reaction 3 hours.Then add Tetrabutyl amonium bromide 32.2g (0.1 mole) in this reaction solution, at room temperature snare drum is gone into air limit reaction 2 hours.The reaction solution of gained is thus concentrated, carry out purifying, obtain the green substituted benzene dithiol metal complex D1 of target (with reference to following table 1) 36.6g by silica gel column chromatography.
Synthesis example 2
Use Copper dichloride dihydrate (II) 17.0g (0.1 mole) in Nickel dichloride hexahydrate (II) 23.8g (0.1 mole) the replacement synthesis example 1, in addition identical with synthesis example 1, obtain substituted benzene dithiol metal complex D2 (with reference to following table 1) 30.8g.
Synthesis example 3
Use 4-(piperdine sulfonyl)-1; 2-dichlorobenzene 58.8g (0.2 mole) replaces the 4-(morpholino alkylsulfonyl)-1 in the synthesis example 2; 2-dichlorobenzene 59.2g (0.2 mole), in addition identical with synthesis example 2, obtain substituted benzene dithiol metal complex D3 (with reference to following table 1) 28.6g.
The substituted benzene dithiol metal complex anionic structure corresponding with each substituted benzene dithiol metal complex of gained is shown in table 1.
[table 1]
Synthesis example 4
With 8.8g (0.01 mole) substituted benzene dithiol metal complex D2 and 7.1g (0.01 mole) cyanine based dye E1 (the following table 2 of reference, the trade(brand)name " S0813 " of FEW Chemicals corporate system) is dissolved in N, dinethylformamide 500g mixes, and keeps making it in 30 minutes reaction at 50 ℃.For remove ion not from the gained reaction solution, add methyl alcohol 600g, mix after then adding entry 900g, cooling is filtered.After this operation repetition 2 times,, obtain counter ion combination 11.1g with methanol wash and dry.
For gained counter ion combination, measure with chromatography of ions, do not detect TBuA ion and Tetrafluoroboric acid ion.
Synthesis example 5
Use the substituted benzene dithiol metal complex D2 in the substituted benzene dithiol metal complex D3 replacement synthesis example 4, in addition identical with synthesis example 4, obtain counter ion combination 11.3g.
For gained counter ion combination, measure with chromatography of ions, do not detect TBuA ion and Tetrafluoroboric acid ion.
Synthesis example 6
Use the substituted benzene dithiol metal complex D2 in the substituted benzene dithiol metal complex D1 replacement synthesis example 4, in addition identical with synthesis example 4, obtain counter ion combination 11.4g.
For gained counter ion combination, measure with chromatography of ions, do not detect TBuA ion and Tetrafluoroboric acid ion.
Synthesis example 7
Use cyanine based dye E2 (with reference to following table 2, the trade(brand)name " S0941 " of FEW Chemicals corporate system) to replace the cyanine based dye E1 in the synthesis example 4, in addition identical with synthesis example 4, obtain counter ion combination 11.3g.
For gained counter ion combination, measure with chromatography of ions, do not detect TBuA ion and Tetrafluoroboric acid ion.
Synthesis example 8
Use cyanine based dye E2 (with reference to following table 2, the trade(brand)name " S0941 " of FEW Chemicals corporate system) to replace the cyanine based dye E1 in the synthesis example 5, in addition identical with synthesis example 5, obtain counter ion combination 11.3g.
For gained counter ion combination, measure with chromatography of ions, do not detect TBuA ion and Tetrafluoroboric acid ion.
Synthesis example 9
Use cyanine based dye E2 (with reference to following table 2, the trade(brand)name " S0941 " of FEW Chemicals corporate system) to replace the cyanine based dye E1 in the synthesis example 6, in addition identical with synthesis example 6, obtain counter ion combination 11.3g.
For gained counter ion combination, measure with chromatography of ions, do not detect TBuA ion and Tetrafluoroboric acid ion.
Synthesis example 10
Use cyanine based dye E3 (with reference to following table 2, the trade(brand)name " S0946 " of FEW Chemicals corporate system) to replace the cyanine based dye E1 in the synthesis example 4, in addition identical with synthesis example 4, obtain counter ion combination 11.3g.
For gained counter ion combination, measure with chromatography of ions, do not detect TBuA ion and Tetrafluoroboric acid ion.
Synthesis example 11
Use cyanine based dye E3 (with reference to following table 2, the trade(brand)name " S0946 " of FEW Chemicals corporate system) to replace the cyanine based dye E1 in the synthesis example 5, in addition identical with synthesis example 5, obtain counter ion combination 11.3g.
For gained counter ion combination, measure with chromatography of ions, do not detect TBuA ion and Tetrafluoroboric acid ion.
Synthesis example 12
Use cyanine based dye E3 (with reference to following table 2, the trade(brand)name " S0946 " of FEW Chemicals corporate system) to replace the cyanine based dye E1 in the synthesis example 6, in addition identical with synthesis example 6, obtain counter ion combination 11.3g.
For gained counter ion combination, measure with chromatography of ions, do not detect TBuA ion and Tetrafluoroboric acid ion.
Synthesis example 13
Use cyanine based dye E4 (with reference to following table 2, the trade(brand)name " S0824 " of FEW Chemicals corporate system) to replace the cyanine based dye E1 in the synthesis example 6, in addition identical with synthesis example 6, obtain counter ion combination 9.1g.
For gained counter ion combination, measure with chromatography of ions, do not detect TBuA ion and high chloro acid ion.
[table 2]
Embodiment 1
After counter ion combination (the Photostabilised cyanine based dye) 32mg of synthesis example 4 gained is dissolved in cyclopentanone 12g, add tackiness agent (trade(brand)name " SZ6232 " of Nippon Carbide Industries corporate system) 6g, solidifying agent (trade(brand)name " CK-102 " of Nippon Carbide Industries corporate system) 37mg and curing catalysts (trade(brand)name " CK-901 " of Nippon Carbide Industries corporate system) 11mg, mix obtaining liquid light absorbing dyestuff composition.In order to estimate the characteristic of gained light absorbing dyestuff composition, it is coated on the polyester film with the rotary coating machine, 80 ℃ of dryings 3 minutes, after forming the filming of thickness 17 μ m, cover polyester film in this film coated surface, it is connected airtight, obtain estimating and use light absorbing material with roll.
Embodiment 2
Use is replaced among the embodiment 1 by the counter ion combination 32mg of synthesis example 4 gained by the counter ion combination 31mg of synthesis example 5 gained, and is in addition identical with embodiment 1, obtains liquid light absorbing dyestuff composition.And then identical with embodiment 1, form filming of thickness 15 μ m, obtain estimating and use light absorbing material.
Embodiment 3
Use is replaced among the embodiment 1 by the counter ion combination 32mg of synthesis example 4 gained by the counter ion combination 31mg of synthesis example 6 gained, and is in addition identical with embodiment 1, obtains liquid light absorbing dyestuff composition.And then identical with embodiment 1, form filming of thickness 15 μ m, obtain estimating and use light absorbing material.
Embodiment 4
After will being dissolved in methyl ethyl ketone 10g by counter ion combination (the Photostabilised cyanine based dye) 33mg of synthesis example 7 gained, add tackiness agent (trade(brand)name " SZ6232 " of Nippon Carbide Industries corporate system) 6g, solidifying agent (trade(brand)name " CK-102 " of Nippon Carbide Industries corporate system) 37mg and curing catalysts (trade(brand)name " CK-901 " of Nippon Carbide Industries corporate system) 11mg, mix obtaining liquid light absorbing dyestuff composition.In order to estimate the characteristic of gained light absorbing dyestuff composition, it is coated on the polyester film with the rotary coating machine, 80 ℃ of dryings 3 minutes, after forming the filming of thickness 15 μ m, cover polyester film in this film coated surface, it is connected airtight, obtain estimating and use light absorbing material with roll.
Embodiment 5
Use is by the counter ion combination 33mg by synthesis example 7 gained among the counter ion combination 32mg replacement embodiment 4 of synthesis example 8 gained, and is in addition identical with embodiment 4, obtains liquid light absorbing dyestuff composition.And then identical with embodiment 4, form filming of thickness 15 μ m, obtain estimating and use light absorbing material.
Embodiment 6
Use is by the counter ion combination 33mg by synthesis example 7 gained among the counter ion combination 32mg replacement embodiment 4 of synthesis example 9 gained, and is in addition identical with embodiment 4, obtains liquid light absorbing dyestuff composition.And then identical with embodiment 4, form filming of thickness 15 μ m, obtain estimating and use light absorbing material.
Embodiment 7
After will being dissolved in methyl ethyl ketone 10g by counter ion combination (the Photostabilised cyanine based dye) 31mg of synthesis example 10 gained, add tackiness agent (trade(brand)name " SZ6232 " of Nippon Carbide Industries corporate system) 6g, solidifying agent (trade(brand)name " CK-102 " of Nippon Carbide Industries corporate system) 36mg and curing catalysts (trade(brand)name " CK-901 " of Nippon Carbide Industries corporate system) 10mg, mix obtaining liquid light absorbing dyestuff composition.In order to estimate the characteristic of gained light absorbing dyestuff composition, it is coated on the polyester film with the rotary coating machine, 80 ℃ of dryings 3 minutes, after forming the filming of thickness 15 μ m, cover polyester film in this film coated surface, it is connected airtight, obtain estimating and use light absorbing material with roll.
Embodiment 8
Use is by the counter ion combination 31mg by synthesis example 10 gained among the counter ion combination 30mg replacement embodiment 7 of synthesis example 11 gained, and is in addition identical with embodiment 7, obtains liquid light absorbing dyestuff composition.And then identical with embodiment 7, form filming of thickness 15 μ m, obtain estimating and use light absorbing material.
Embodiment 9
Use is by the counter ion combination 31mg by synthesis example 10 gained among the counter ion combination 30mg replacement embodiment 7 of synthesis example 12 gained, and is in addition identical with embodiment 7, obtains liquid light absorbing dyestuff composition.And then identical with embodiment 7, form filming of thickness 15 μ m, obtain estimating and use light absorbing material.
Embodiment 10
After will being dissolved in cyclopentanone 12g by counter ion combination (the Photostabilised cyanine based dye) 61mg of synthesis example 4 gained, add tackiness agent (trade(brand)name " SZ6233 " of Nippon Carbide Industries corporate system) 6g, solidifying agent (trade(brand)name " CK-102 " of Nippon Carbide Industries corporate system) 35mg and curing catalysts (trade(brand)name " CK-901 " of Nippon Carbide Industries corporate system) 11mg, mix obtaining liquid light absorbing dyestuff composition.In order to estimate the characteristic of gained light absorbing dyestuff composition, it is coated on the polyester film with the rotary coating machine, 80 ℃ of dryings 3 minutes, after forming the filming of thickness 15 μ m, cover polyester film in this film coated surface, it is connected airtight, obtain estimating and use light absorbing material with roll.
Embodiment 11
Use is by the counter ion combination 61mg by synthesis example 4 gained among the counter ion combination 59mg replacement embodiment 10 of synthesis example 5 gained, and is in addition identical with embodiment 10, obtains liquid light absorbing dyestuff composition.And then identical with embodiment 10, form filming of thickness 15 μ m, obtain estimating and use light absorbing material.
Embodiment 12
Use is by the counter ion combination 61mg by synthesis example 4 gained among the counter ion combination 59mg replacement embodiment 10 of synthesis example 6 gained, and is in addition identical with embodiment 10, obtains liquid light absorbing dyestuff composition.And then identical with embodiment 10, form filming of thickness 15 μ m, obtain estimating and use light absorbing material.
Embodiment 13
After will being dissolved in methyl ethyl ketone 10g by counter ion combination (the Photostabilised cyanine based dye) 49mg of synthesis example 7 gained, add tackiness agent (trade(brand)name " SZ6233 " of Nippon Carbide Industries corporate system) 6g, solidifying agent (trade(brand)name " CK-102 " of Nippon Carbide Industries corporate system) 30mg and curing catalysts (trade(brand)name " CK-901 " of Nippon Carbide Industries corporate system) 10mg, mix obtaining liquid light absorbing dyestuff composition.In order to estimate the characteristic of gained light absorbing dyestuff composition, it is coated on the polyester film with the rotary coating machine, 80 ℃ of dryings 3 minutes, after forming the filming of thickness 15 μ m, cover polyester film in this film coated surface, it is connected airtight, obtain estimating and use light absorbing material with roll.
Embodiment 14
Use is by the counter ion combination 49mg by synthesis example 7 gained among the counter ion combination 47mg replacement embodiment 13 of synthesis example 8 gained, and is in addition identical with embodiment 13, obtains liquid light absorbing dyestuff composition.And then identical with embodiment 13, form filming of thickness 16 μ m, obtain estimating and use light absorbing material.
Embodiment 15
The counter ion combination 48mg of use synthesis example 9 gained replaces the counter ion combination 49mg by synthesis example 7 gained among the embodiment 13, and is in addition identical with embodiment 13, obtains liquid light absorbing dyestuff composition.And then identical with embodiment 13, form filming of thickness 16 μ m, obtain estimating and use light absorbing material.
Embodiment 16
After counter ion combination (the Photostabilised cyanine based dye) 38mg of synthesis example 10 gained is dissolved in methyl ethyl ketone 10g, add tackiness agent (trade(brand)name " SZ6233 " of Nippon Carbide Industries corporate system) 6g, solidifying agent (trade(brand)name " CK-102 " of Nippon Carbide Industries corporate system) 33mg and curing catalysts (trade(brand)name " CK-901 " of Nippon Carbide Industries corporate system) 10mg, mix obtaining liquid light absorbing dyestuff composition.In order to estimate the characteristic of gained light absorbing dyestuff composition, it is coated on the polyester film with the rotary coating machine, 80 ℃ of dryings 3 minutes, after forming the filming of thickness 15 μ m, cover polyester film in this film coated surface, it is connected airtight, obtain estimating and use light absorbing material with roll.
Embodiment 17
Use is by the counter ion combination 38mg by synthesis example 10 gained among the counter ion combination 37mg replacement embodiment 16 of synthesis example 11 gained, and is in addition identical with embodiment 16, obtains liquid light absorbing dyestuff composition.And then identical with embodiment 16, form filming of thickness 17 μ m, obtain estimating and use light absorbing material.
Embodiment 18
Use is by the counter ion combination 38mg by synthesis example 10 gained among the counter ion combination 38mg replacement embodiment 16 of synthesis example 12 gained, and is in addition identical with embodiment 16, obtains liquid light absorbing dyestuff composition.And then identical with embodiment 16, form filming of thickness 17 μ m, obtain estimating and use light absorbing material.
Embodiment 19
After will being dissolved in cyclopentanone 8g by counter ion combination (the Photostabilised cyanine based dye) 24mg of synthesis example 4 gained, add tackiness agent (trade(brand)name " SZ6234 " of Nippon Carbide Industries corporate system) 9.6g and solidifying agent (trade(brand)name " CK-117 " of Nippon Carbide Industries corporate system) 65mg, mix obtaining liquid light absorbing dyestuff composition.In order to estimate the characteristic of gained light absorbing dyestuff composition, it is coated on the polyester film with the rotary coating machine, 80 ℃ of dryings 3 minutes, after forming the filming of thickness 15 μ m, cover polyester film in this film coated surface, it is connected airtight, obtain estimating and use light absorbing material with roll.
Embodiment 20
Use is by the counter ion combination 24mg by synthesis example 4 gained among the counter ion combination 25mg replacement embodiment 19 of synthesis example 5 gained, and is in addition identical with embodiment 19, obtains liquid light absorbing dyestuff composition.And then identical with embodiment 19, form filming of thickness 15 μ m, obtain estimating and use light absorbing material.
Embodiment 21
Use is by the counter ion combination 24mg by synthesis example 4 gained among the counter ion combination 23mg replacement embodiment 19 of synthesis example 6 gained, and is in addition identical with embodiment 19, obtains liquid light absorbing dyestuff composition.And then identical with embodiment 19, form filming of thickness 15 μ m, obtain estimating and use light absorbing material.
Embodiment 22
After will being dissolved in methyl ethyl ketone 6.4g by counter ion combination (the Photostabilised cyanine based dye) 29mg of synthesis example 10 gained, add tackiness agent (trade(brand)name " SZ6234 " of Nippon Carbide Industries corporate system) 9.6g and solidifying agent (trade(brand)name " CK-117 " of Nippon Carbide Industries corporate system) 51mg, mix obtaining liquid light absorbing dyestuff composition.In order to estimate the characteristic of gained light absorbing dyestuff composition, it is coated on the polyester film with the rotary coating machine, 80 ℃ of dryings 3 minutes, after forming the filming of thickness 18 μ m, cover polyester film in this film coated surface, it is connected airtight, obtain estimating and use light absorbing material with roll.
Embodiment 23
Use is by the counter ion combination 29mg by synthesis example 10 gained among the counter ion combination 30mg replacement embodiment 22 of synthesis example 11 gained, and is in addition identical with embodiment 22, obtains liquid light absorbing dyestuff composition.And then identical with embodiment 22, form filming of thickness 18 μ m, obtain estimating and use light absorbing material.
Embodiment 24
Use is by the counter ion combination 29mg by synthesis example 10 gained among the counter ion combination 28mg replacement embodiment 22 of synthesis example 12 gained, and is in addition identical with embodiment 22, obtains liquid light absorbing dyestuff composition.And then identical with embodiment 22, form filming of thickness 18 μ m, obtain estimating and use light absorbing material.
Embodiment 25
After will being dissolved in methyl ethyl ketone 11.2g by counter ion combination (the Photostabilised cyanine based dye) 30mg of synthesis example 10 gained, add tackiness agent (trade(brand)name of The Nippon Synthetic Chemical Industry Co., Ltd's system " Nichigo Polyester XI-0002 ") 4.8g, solidifying agent (trade(brand)name of NipponPolyurethane Industry corporate system " Coronate L-55E ") 40mg and curing catalysts (di-n-butyltin dilaurate; Tokyo HuaCheng Industry Co., Ltd's system) 12mg mixes obtaining liquid light absorbing dyestuff composition.In order to estimate the characteristic of gained light absorbing dyestuff composition, it is coated on the polyester film with the rotary coating machine, 80 ℃ of dryings 3 minutes, after forming the filming of thickness 10 μ m, in this film coated surface stacked coated glass sheets, with roll it is connected airtight, obtain estimating and use light absorbing material.
Embodiment 26
After will being dissolved in methyl ethyl ketone 10g by counter ion combination (the Photostabilised cyanine based dye) 15.5mg of synthesis example 13 gained, add tackiness agent (trade(brand)name " SZ6232 " of Nippon Carbide Industries corporate system) 6g, solidifying agent (trade(brand)name " CK-102 " of Nippon Carbide Industries corporate system) 26mg and curing catalysts (trade(brand)name " CK-901 " of Nippon Carbide Industries corporate system) 15mg, mix obtaining liquid light absorbing dyestuff composition.In order to estimate the characteristic of gained light absorbing dyestuff composition, it is coated on the polyester film with the rotary coating machine, 80 ℃ of dryings 3 minutes, after forming the filming of thickness 17 μ m, cover polyester film in this film coated surface, it is connected airtight, obtain estimating and use light absorbing material with roll.
Embodiment 27
After will being dissolved in methyl ethyl ketone 8g by counter ion combination (the Photostabilised cyanine based dye) 15mg of synthesis example 10 gained, add tackiness agent (trade(brand)name " SZ6472 " 6g of Nippon Carbide Industries corporate system, trade(brand)name " CELLOXIDE-2021P " 2.4g of DAICEL CHEMICAL INDUSTRIES corporate system and the trade(brand)name of Toagosei Co., Ltd's system " ARON OXETANE OXT-221 " 0.24g), solidifying agent (trade(brand)name " CK-102 " of Nippon CarbideIndustries corporate system) 24mg and curing catalysts (trade(brand)name " CYRACURE-UVI-6992 " 0.16g of trade(brand)name " CK-901 " 12mg of NipponCarbide Industries corporate system and Dow ChemicalJapan corporate system) mix obtaining liquid light absorbing dyestuff composition.In order to estimate the characteristic of gained light absorbing dyestuff composition, it is coated on the polyester film with the rotary coating machine, 80 ℃ of dryings 3 minutes, after forming the filming of thickness 25 μ m, in this film coated surface stacked coated glass sheets, with roll it is connected airtight, solidify, obtain estimating and use light absorbing material with USHIO Electric Co., Ltd system conveyor type ultraviolet curing device.
Embodiment 28
After will being dissolved in methyl ethyl ketone 8g by counter ion combination (the Photostabilised cyanine based dye) 15mg of synthesis example 10 gained, add tackiness agent (trade(brand)name " SZ6472 " 6g of Nippon Carbide Industries corporate system, trade(brand)name " Epicoat828 " 2.4g of Japan Epoxy Resin corporate system and system trade(brand)name " the ARON OXETANE OXT-221 " 0.24g of Toagosei Co., Ltd), solidifying agent (trade(brand)name " CK-102 " of Nippon Carbide Industries corporate system) 24mg and curing catalysts (trade(brand)name " SI-45L " 0.05g of trade(brand)name " CK-901 " 12mg of Nippon Carbide Industries corporate system and three new KCC systems) mix obtaining liquid light absorbing dyestuff composition.In order to estimate the characteristic of gained light absorbing dyestuff composition, it is coated on the polyester film with the rotary coating machine, 80 ℃ of dryings 3 minutes, after forming the filming of thickness 24 μ m, in this film coated surface stacked coated glass sheets, with roll it is connected airtight, solidified 1 hour, obtain estimating and use light absorbing material at 80 ℃.
Embodiment 29
After will being dissolved in methyl ethyl ketone 8g by counter ion combination (the Photostabilised cyanine based dye) 15mg of synthesis example 10 gained, add tackiness agent (trade(brand)name " SZ6472 " 6g of Nippon Carbide Industries corporate system, trade(brand)name " CELLOXIDE-2021P " 2.4g of DAICEL CHEMICAL INDUSTRIES corporate system and the trade(brand)name of Toagosei Co., Ltd's system " ARON OXETANE OXT-221 " 0.24g), solidifying agent (trade(brand)name " CK-102 " of Nippon CarbideIndustries corporate system) 24mg and curing catalysts (trade(brand)name " SI-45L " 0.05g of trade(brand)name " CK-901 " 12mg of NipponCarbide Industries corporate system and three new KCC systems) mix obtaining liquid light absorbing dyestuff composition.In order to estimate the characteristic of gained light absorbing dyestuff composition, it is coated on the polyester film with the rotary coating machine, 80 ℃ of dryings 3 minutes, after forming the filming of thickness 16 μ m, in this film coated surface stacked coated glass sheets, with roll it is connected airtight, solidified 1 hour, obtain estimating and use light absorbing material at 80 ℃.
Comparative example 1
, in addition identical among the use cyanine based dye E235mg replacement embodiment 4 with embodiment 4 by the counter ion combination 33mg of synthesis example 7 gained, obtain light absorbing dyestuff composition.But said composition is dissolving fully not.Use said composition and then identical, form filming of thickness 15 μ m, obtain estimating and use light absorbing material with embodiment 4.
Comparative example 2
Use cyanine based dye E3 35mg to replace among the embodiment 7 by the counter ion combination 31mg of synthesis example 10 gained, in addition identical with embodiment 7, obtain the liquid composition of light absorbing dyestuff.And then identical with embodiment 7, form filming of thickness 15 μ m, obtain estimating and use light absorbing material.
Comparative example 3
Use cyanine based dye E46mg to replace among the embodiment 26 by the counter ion combination 15.5mg of synthesis example 13 gained, in addition identical with embodiment 26, obtain the liquid composition of light absorbing dyestuff.And then identical with embodiment 26, form filming of thickness 18 μ m, obtain estimating and use light absorbing material.
Comparative example 4
Use cyanine based dye E310mg to replace among the embodiment 29 by the counter ion combination 15mg of synthesis example 10 gained, in addition identical with embodiment 29, obtain the liquid composition of light absorbing dyestuff.And then identical with embodiment 29, form filming of thickness 16 μ m, obtain estimating and use light absorbing material.
[evaluation of light absorbing material]
For the light absorbing material of embodiment 1～26 and comparative example 1～3 gained, for the research light absorpting ability through the time change and to carry out following model trial.At first, for each light absorbing material, (measure wavelength: 550nm, absorbancy 1000nm) is as absorbancy before the slaking at specific wavelength to use spectrophotometric determination., at room temperature dark place leave standstill each light absorbing material 7 day slaking after, measure absorbancy according to the method described above equally, as absorbancy after the slaking thereafter.Further, for each light absorbing material after the slaking, use light stability testing apparatus (trade(brand)name " LT-120 " of NAGANO SCIENCE corporate system) to measure respectively according to method same as described above with the absorbancy (A) of 5000lx irradiation after 100 hours, use minienvironment tester (trade(brand)name of TABAIESPEC corporate system " SU-240 ") to be determined at 80 ℃ of absorbancys (B) after leaving standstill 100 hours, and use minienvironment tester (trade(brand)name " SU-220 " of TABAI ESPEC corporate system) to be determined at 60 ℃, leave standstill the absorbancy (C) after 100 hours under the 90%RH.
Then, for these absorbancys of above-mentioned gained, calculate: absorbancy residual rate C (%) after absorbancy residual rate B (%) and (the preceding absorbancy of absorbancy (C)/slaking) * 100=test after absorbancy residual rate A (%), (absorbancy before absorbancy (B)/slaking) * 100=test after absorbancy residual rate (%), (the preceding absorbancy of absorbancy (A)/slaking) * 100=test after (the preceding absorbancy of absorbancy/slaking after the slaking) * 100=slaking.These be the results are shown in table 3 and table 4.
[table 3]
| Absorbancy residual rate (%) after the slaking | Test back absorbancy residual rate (%) | |||
| A | B | C | ||
| Measure wavelength | 1000nm | 1000nm | 1000nm | 1000nm |
| Embodiment 1 | 94 | 85 | 89 | 89 |
| Embodiment 2 | 90 | 83 | 85 | 85 |
| Embodiment 3 | 95 | 86 | 90 | 90 |
| Embodiment 4 | 100 | 98 | 100 | 100 |
| Embodiment 5 | 98 | 98 | 98 | 96 |
| Embodiment 6 | 100 | 99 | 100 | 100 |
| Embodiment 7 | 100 | 98 | 100 | 100 |
| Embodiment 8 | 99 | 98 | 99 | 99 |
| Embodiment 9 | 100 | 99 | 100 | 100 |
| Embodiment 10 | 96 | 90 | 94 | 95 |
| Embodiment 11 | 96 | 94 | 95 | 95 |
| Embodiment 12 | 99 | 98 | 99 | 98 |
| Embodiment 13 | 100 | 98 | 99 | 100 |
| Embodiment 14 | 98 | 97 | 98 | 97 |
| Embodiment 15 | 100 | 100 | 100 | 100 |
| Embodiment 16 | 100 | 95 | 98 | 100 |
| Embodiment 17 | 99 | 98 | 99 | 98 |
| Embodiment 18 | 100 | 100 | 100 | 100 |
| Embodiment 19 | 88 | 74 | 82 | 79 |
| Embodiment 20 | 86 | 73 | 80 | 78 |
| Embodiment 21 | 88 | 76 | 82 | 81 |
| Embodiment 22 | 95 | 91 | 95 | 95 |
| Embodiment 23 | 94 | 90 | 94 | 93 |
| Embodiment 24 | 97 | 92 | 97 | 96 |
| Embodiment 25 | 99 | 95 | 77 | 87 |
| Comparative example 1 | 71 | 65 | 53 | 49 |
| Comparative example 2 | 98 | 98 | 66 | 21 |
[table 4]
| Absorbancy residual rate (%) after the slaking | Test back absorbancy residual rate (%) | |||
| A | B | C | ||
| Measure wavelength | 550nm | 550nm | 550nm | 550nm |
| Embodiment 26 | 100 | 97 | 98 | 100 |
| Comparative example 3 | 96 | 86 | 74 | 82 |
In addition, for the light absorbing material of embodiment 27～29 and comparative example 4 gained, for the research light absorpting ability through the time change and to carry out following model trial.At first, for each light absorbing material, use spectrophotometric determination specific wavelength (measure wavelength: absorbancy 1000nm), as absorbancy before the test.Then, for each light absorbing material, use light stability testing apparatus (trade(brand)name " LT-120 " of NAGANO SCIENCE corporate system) to measure respectively according to method same as described above with the absorbancy (A) of 5000lx irradiation after 100 hours, use minienvironment tester (trade(brand)name " SU-240 " of TABAI ESPEC corporate system) to be determined at 80 ℃ of absorbancys (B) after leaving standstill 100 hours, and use minienvironment tester (trade(brand)name " SU-220 " of TABAI ESPEC corporate system) to be determined at the absorbancy (C) that leaves standstill under 60 ℃, 90%RH after 100 hours.
Then, for these absorbancys of above-mentioned gained, calculate: (absorbancy before absorbancy (A)/test) * 100=test back absorbancy residual rate A (%), (absorbancy before absorbancy (B)/test) * 100=test back absorbancy residual rate B (%) and (absorbancy before absorbancy (C)/test) * 100=test back absorbancy residual rate C (%).With these the table 5 that the results are shown in.
[table 5]
| Test back absorbancy residual rate (%) | |||
| A | B | C | |
| Measure wavelength | 1000nm | 1000nm | 1000nm |
| Embodiment 27 | 67 | 94 | 87 |
| Embodiment 28 | 84 | 87 | 93 |
| Embodiment 29 | 61 | 71 | 72 |
| Comparative example 4 | 59 | 49 | 70 |
Show by the result shown in table 3 and the table 4, the light absorbing material of embodiment 1～26 gained is compared with the light absorbing material of comparative example 1～3 gained, absorbancy residual rate after the slaking among absorbancy residual rate and the test back absorbancy residual rate A～C is all high, thereby the decline of its light absorpting ability of light absorbing material of embodiment 1～26 gained is fully suppressed as can be known.In addition, show by the result shown in the table 5, the light absorbing material of embodiment 27～29 gained is compared with the light absorbing material of comparative example 4 gained, absorbancy residual rate among the absorbancy residual rate A～C of test back is all high, thereby the decline of its light absorpting ability of light absorbing material of embodiment 27～29 gained is fully suppressed as can be known.
Claims (4)
1. the light absorbing dyestuff composition that contains Photostabilised cyanine based dye and tackiness agent.
2. light absorbing dyestuff composition according to claim 1 is characterized in that, described Photostabilised cyanine based dye is the cationic counter ion combination of substituted benzene dithiol metal complex negatively charged ion and cyanine based dye.
3. light absorbing dyestuff composition according to claim 2 is characterized in that, described substituted benzene dithiol metal complex negatively charged ion is the substituted benzene dithiol metal complex negatively charged ion shown in the general formula (1),
In the formula, R
1And R
2Alkylamino, replacement or unsubstituted morpholino base, replacement or unsubstituted piperidino, replacement or unsubstituted 1-pyrrolidyl, replacement or the unsubstituted thiomorpholine of alkyl, carbon number 1～8 of representing carbon number 1～6 respectively independently is for base, replacement or unsubstituted 1-piperazinyl or replacement or unsubstituted phenyl; M represents transition metal atoms.
4. according to each described light absorbing dyestuff composition in the claim 1～3, it is characterized in that described tackiness agent is (methyl) acrylate copolymer.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2006258024 | 2006-09-22 | ||
| JP2006258024 | 2006-09-22 | ||
| JP2006-258024 | 2006-09-22 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101148546A true CN101148546A (en) | 2008-03-26 |
| CN101148546B CN101148546B (en) | 2013-02-06 |
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2007101538435A Expired - Fee Related CN101148546B (en) | 2006-09-22 | 2007-09-13 | Light absorbing dyestuff composition |
Country Status (3)
| Country | Link |
|---|---|
| KR (1) | KR20080027141A (en) |
| CN (1) | CN101148546B (en) |
| TW (1) | TW200815537A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101402594A (en) * | 2007-10-02 | 2009-04-08 | 住友精化株式会社 | Substituted benzene dithiol metal complex and photoabsorption pigment composition containing the same |
| CN102134248A (en) * | 2011-01-06 | 2011-07-27 | 南京大学 | Multi-sulfo-disulfide alkene nickel coordination compound and preparation method and application thereof |
| CN104559323A (en) * | 2013-10-09 | 2015-04-29 | 住友化学株式会社 | Dye compound and colored curable resin composition |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20100291706A1 (en) * | 2009-05-15 | 2010-11-18 | Millipore Corporation | Dye conjugates and methods of use |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1513175A (en) * | 2001-03-28 | 2004-07-14 | 拜尔公司 | Optical data carrier that contains merocyanine dye as light-absorbing compound in the information layer |
| WO2002089128A1 (en) * | 2001-03-28 | 2002-11-07 | Bayer Aktiengesellschaft | An optical data storage medium containing a diaza hemicyanine dye as the light-absorbing compound in the information layer |
-
2007
- 2007-08-27 TW TW096131657A patent/TW200815537A/en unknown
- 2007-09-13 CN CN2007101538435A patent/CN101148546B/en not_active Expired - Fee Related
- 2007-09-14 KR KR1020070093794A patent/KR20080027141A/en not_active Application Discontinuation
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101402594A (en) * | 2007-10-02 | 2009-04-08 | 住友精化株式会社 | Substituted benzene dithiol metal complex and photoabsorption pigment composition containing the same |
| CN102134248A (en) * | 2011-01-06 | 2011-07-27 | 南京大学 | Multi-sulfo-disulfide alkene nickel coordination compound and preparation method and application thereof |
| CN102134248B (en) * | 2011-01-06 | 2013-01-30 | 南京大学 | Multi-sulfo-disulfide alkene nickel coordination compound and preparation method and application thereof |
| CN104559323A (en) * | 2013-10-09 | 2015-04-29 | 住友化学株式会社 | Dye compound and colored curable resin composition |
| CN104559323B (en) * | 2013-10-09 | 2017-09-29 | 东友精细化工有限公司 | Dye composition and colored curable resin composition |
Also Published As
| Publication number | Publication date |
|---|---|
| KR20080027141A (en) | 2008-03-26 |
| TW200815537A (en) | 2008-04-01 |
| CN101148546B (en) | 2013-02-06 |
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