CN1747943A

CN1747943A - Heteropolycyclic compound, and coloring matter, pigment, dye, color-changing material composition and color-changing film prepared therefrom

Info

Publication number: CN1747943A
Application number: CN 200480004044
Authority: CN
Inventors: 吉田胜平; 大山阳介; 蜂屋聪
Original assignee: Idemitsu Kosan Co Ltd; Techno Network Shikoku Co Ltd
Current assignee: Idemitsu Kosan Co Ltd; Techno Network Shikoku Co Ltd
Priority date: 2003-02-14
Filing date: 2004-02-12
Publication date: 2006-03-15
Also published as: JP2010116401A

Abstract

The present invention provides novel heteropolycyclic compounds having a specific structure; a color-changing material composition comprising a fluorescent dye comprising at least one of the above heteropolycyclic compounds, and (B) a binder material; a color-changing film comprising the heteropolycyclic compound; a coloring matter comprising the above heteropolycyclic compound, and a pigment or dye comprising the above heteropolycyclic compound, and a color-changing material composition which does not deteriorate in color-changing properties even after long-term use and can prevent unusable due to deposition of the coloring matter during storage; also provided are color-changing films prepared therefrom, as well as novel heteropolycyclic compounds, pigments and pigments or dyes for their realization.

Description

Assorted polynuclear compound, and pigment prepared therefrom, pigment, dyestuff, off-color material composition and optically variable films

Background of invention

This application relates to novel assorted polynuclear compound, and pigment prepared therefrom, pigment or dyestuff, off-color material composition and optically variable films, relate in particular to the off-color material composition, even said composition is after long-time the use, discoloration can not be damaged yet, and can prevent from also to relate to optically variable films prepared therefrom, and novel assorted polynuclear compound, pigment and pigment or the dyestuff of realizing them owing to can't using that pigment deposition in storage causes.

Correlation technique

Up to the present, the organic fluorescence pigment is except being used as dyestuff and pigment, also in extensive fields as pigment being used for the fluorescence switching film of multiple display unit, and as pigment be used for dye laser, anti-ly duplicate, the fluorescence membrane in solar energy converting and greenhouse.

The organic fluorescence pigment that urgent hope is used for above-mentioned application is controlled in the fluorescent wavelength ranges solid-state, and improves its luminous intensity.Yet the fluorescence intensity that is known that solid-state organic fluorescence pigment usually is with a little less than its fluorescence intensity at solution state is compared.Present situation is that this phenomenon is overlooked as concentration quenching, and its details fails detailed to know.This is because be difficult to make the packing of molecules structure in the lattice to make various changes in conventional organic fluorescence pigment, to study the influence that it applies the photoabsorption and the photoluminescent property of solid-state organic fluorescence pigment.

The inventor is at the preceding material that addresses the above problem found, by multiple organic low molecular compounds (organic guest molecule) is included in the novel fluorescence pigment with solid-state form, thereby give pigment to a great extent and have the ability that forms Runge-Kutta integration, the ability of this formation Runge-Kutta integration (for example can change inherent colour and fluorescence radiation, referring to " Chem.Lett. ", p.9 (1996), " Chem.Lett. ", p.837 (1999), " Chem.Lett. ", p.714 (2000), " Chem.Lett. " be (2001) and " J.Chem.PerkinTrans. " p.808, p.700-714 and p.708-714 vol.2, (2002)).Use has the above-mentioned fluorochrome that Runge-Kutta integration forms ability, by organic guest molecule is included in wherein, thereby it is possible making pigment molecular carry out various variation orientations and arrange on molecular level, and this makes the solid state optics character (color harmony photoluminescent property) that changes pigment to a great extent become possibility.

Therefore, the ABC that the utilization of above-mentioned characteristic can obtain the packed structures of relevant pigment molecular and its solid-state light absorbs, concern between the fluorescence radiation, this knowledge is not fully set forth clear as yet, and this makes that can prepare the fluorescence organic solid-state material with the optical property that can satisfy various demands becomes possibility.

Organic electroluminescent device (hereinafter referred to as organic EL) is complete solid state device, and can produce light and thin, but and the indicating meter of low-voltage driving, therefore, they are objects of active research in a plurality of fields at present.Especially, the maximum technical object by organic EL production indicating meter is an exploitation full color method.For producing this full color display, blueness, green and emitting red light need accurate the arrangement, three kinds of methods are arranged for this reason at present: three looks independent cladding process, colour filter method and color conversion method.

Wherein, compare with three looks independent cladding process, color conversion method is easier to produce large screen display, and this method compares with the colour filter method, has the advantage of littler luminous loss.Therefore, the inventor has studied the full color of organic EL by the color conversion method.

When using color conversion method production full color display, being used to make the blue light of emission to convert green and red optically variable films to needs critically molded.

In addition, optically variable films is by fluorochrome and be used for disperseing its resin to form, and is high-precision ground mold film, and itself need possess good processing properties this resin.For satisfying above-mentioned purpose, for example, in Japanese Patent Application Publication No.208944/1997, used off-color material composition by using basic resin such as vinylpyridine piperidine derivatives and amino-benzene ethene derivatives to prepare; The off-color material composition that uses the preparation of ethylenic copolymers of unsaturated carboxylic acids is disclosed in Japanese Patent Application Publication No.106888/1997; And the off-color material composition disclosed in Japanese Patent Application Publication No.119645/2000, said composition comprises compound and at least a fluorescent substance that is selected from fluorochrome and high-visibility pigment that contains unsaturated group, and wherein this compound that contains unsaturated group is reacted by the reaction product of polycarboxylic acid or its acid anhydrides and epoxy compounds and acrylic or methacrylic acid and obtains.

Yet, there is following point in above-mentioned off-color material composition: when containing the blue light illumination that the optically variable films of tonka bean camphor primary colours element as the pigment that absorbs blue light continue to be sent by organic EL, the tonka bean camphor primary colours are plain to be decomposed, thereby the blue light that can't fully absorb light source is to launch, and the discoloration variation, the pigment that perhaps depends on resin combination is owing to deposition in storage causes film to use.

Summary of the invention

Made the present invention for addressing the above problem, an object of the present invention is to provide a kind of novel assorted polynuclear compound, thereby this compound can be used as conventional organic pigment and organic fluorescence pigment or as having the Runge-Kutta integration ability of formation and photoluminescent property and can be by making the organic fluorescence pigment of the solid state optics character (color harmony photoluminescent property) that wherein contains organic guest molecule and change pigment to a great extent, and this compound can be suitable for multiple application, and pigment and pigment or dyestuff by the above-claimed cpd preparation are provided.In addition, an object of the present invention is to provide a kind of by using the off-color material composition of above-claimed cpd preparation, even said composition is after long-time the use, discoloration can not damage yet, and can prevent, and provide optically variable films prepared therefrom owing to can't using that pigment deposition in storage causes.

For achieving the above object, the inventor has carried out repeated further investigation, found that, above-mentioned purpose can by use have ad hoc structure, realize as fluorochrome as pigment and by the assorted polynuclear compound of following formula (III) to (VIII) representative by the assorted polynuclear compound of following formula (I) and formula (II) representative.

That is, the invention provides assorted polynuclear compound by the arbitrary representative of following formula (I) to (VIII):

Wherein, R ¹And R ²Representative independently of one another can have the heteroaryl that the alkyl of the substituent 1-10 of a having carbon atom, the aralkyl that can have the substituent 7-30 of a having carbon atom, the aryl that can have the substituent 6-20 of a having carbon atom maybe can have the substituent 5-20 of a having carbon atom, and they can be connected to each other with the formation ring texture or can have the phenyl ring of nitrogen-atoms to form ring texture with bonding;

X represention oxygen atom, sulphur atom ,-NH-or-NR ³-(R ³Representative can have the heteroaryl that the alkyl of the substituent 1-10 of a having carbon atom, the aryl that can have the substituent 6-20 of a having carbon atom maybe can have the substituent 5-20 of a having carbon atom);

Y represention oxygen atom, sulphur atom ,-NH-or-NR ⁴-(R ⁴Representative can have the alkyl of the substituent 1-10 of a having carbon atom, the aryl that can have the substituent 6-20 of a having carbon atom maybe can have the heteroaryl of the substituent 5-20 of a having carbon atom), condition is in formula (III) with (IV), Y represention oxygen atom, sulphur atom or-NR ⁴-; And

On behalf of the aryl that can have the substituent 6-20 of a having carbon atom, Ar maybe can have the heteroaryl of the substituent 5-20 of a having carbon atom.

In addition, the invention provides a kind of off-color material composition, said composition comprises (A) fluorochrome, this fluorochrome comprises at least a assorted polynuclear compound by formula (III) to (VIII) representative, and (B) adhesive material and the optically variable films that comprises above-mentioned off-color material composition is provided.

In addition, the invention provides the pigment that comprises above-mentioned assorted polynuclear compound, and the pigment or the dyestuff that contain above-mentioned assorted polynuclear compound.

The accompanying drawing summary

Fig. 1 is to be the synoptic diagram that is used for estimating the color organic EL component structure of embodiment and comparative example's discoloration.

Fig. 2 is for explaining the synoptic diagram of the evaluation method of discoloration among embodiment and the comparative example.

Fig. 3 is for explaining the synoptic diagram of the evaluation method of colourity sustainment rate among embodiment and the comparative example.

Numeral 1 is a substrate of glass; 2 is optically variable films; 3 is anode, and 4 is organic EL luminescent layer; And 5 be negative electrode.

The best mode that carries out an invention

Assorted polynuclear compound of the present invention is for having the novel assorted polynuclear compound by the structure of the arbitrary representative of following formula (I) to (VIII), and it is unexposed in existing document:

In formula (I) in (VIII), R ¹And R ²Representative independently of one another can have the heteroaryl that the alkyl of the substituent 1-10 of a having carbon atom, the aralkyl that can have the substituent 7-30 of a having carbon atom, the aryl that can have the substituent 6-20 of a having carbon atom maybe can have the substituent 5-20 of a having carbon atom, and they can be connected to each other with the formation ring texture or can have the phenyl ring of nitrogen-atoms to form ring texture with bonding.

Abovementioned alkyl can be arbitrarily straight chain, side chain and cyclic group, and the example comprises methyl, ethyl, n-propyl, sec.-propyl, various butyl, various amyl group, various hexyl, various octyl group, various decyl, cyclopentyl, cyclohexyl, ring octyl group, benzyl and styroyl.

The example of above-mentioned aralkyl comprises benzyl, the 1-styroyl, the 2-styroyl, 1-propyloxy phenyl base, 2-propyloxy phenyl base, phenyl-tertiary butyl, α-menaphthyl, 1-α-naphthalene ethyl, 2-Alpha-Naphthyl ethyl, 1-Alpha-Naphthyl sec.-propyl, 2-Alpha-Naphthyl sec.-propyl, β-menaphthyl, 1-β-naphthalene ethyl, 2-β-naphthalene ethyl, 1-betanaphthyl sec.-propyl, 2-betanaphthyl sec.-propyl, 1-pyrryl methyl, 2-(1-pyrryl) ethyl, to methyl-benzyl, between methyl-benzyl, adjacent methyl-benzyl, p-chlorobenzyl, the m-chloro benzyl, o-chlorobenzyl, to bromobenzyl, between bromobenzyl, adjacent bromobenzyl, to the iodine benzyl, between the iodine benzyl, to the iodine benzyl, to hydroxybenzyl, between hydroxybenzyl, adjacent hydroxybenzyl, PAB, between aminobenzyl, adjacent aminobenzyl, to nitrobenzyl, between nitrobenzyl, adjacent nitrobenzyl, to the cyano group benzyl, between the cyano group benzyl, o-cyanobenzyl, 1-hydroxyl-2-propyloxy phenyl base and 1-chloro-2-propyloxy phenyl base.

The example of above-mentioned aryl comprises phenyl, naphthyl, anthryl and pyrenyl.

The example of above-mentioned heteroaryl comprises 1-azepine-indolizine-2-base, 1-azepine-indolizine-3-base, 1-azepine-indolizine-5-base, 1-azepine-indolizine-6-base, 1-azepine-indolizine-7-base, 1-azepine-indolizine-8-base, 2-azepine-indolizine-1-base, 2-azepine-indolizine-3-base, 2-azepine-indolizine-5-base, 2-azepine-indolizine-6-base, 2-azepine-indolizine-7-base, 2-azepine-indolizine-8-base, 6-azepine-indolizine-1-base, 6-azepine-indolizine-2-base, 6-azepine-indolizine-3-base, 6-azepine-indolizine-5-base, 6-azepine-indolizine-7-base, 6-azepine-indolizine-8-base, 7-azepine-indolizine-1-base, 7-azepine-indolizine-2-base, 7-azepine-indolizine-3-base, 7-azepine-indolizine-5-base, 7-azepine-indolizine-6-base, 7-azepine-indolizine-7-base, 7-azepine-indolizine-8-base, 8-azepine-indolizine-1-base, 8-azepine-indolizine-2-base, 8-azepine-indolizine-3-base, 8-azepine-indolizine-5-base, 8-azepine-indolizine-6-base, 8-azepine-indolizine-7-base, 1-indolizine base, 2-indolizine base, 3-indolizine base, 5-indolizine base, 6-indolizine base, 7-indolizine base, 8-indolizine base, the 1-pyrryl, the 2-pyrryl, the 3-pyrryl, pyrazinyl, the 2-pyridyl, the 3-pyridyl, the 4-pyridyl, the 1-indyl, the 2-indyl, the 3-indyl, the 4-indyl, the 5-indyl, the 6-indyl, the 7-indyl, the 1-isoindolyl, the 2-isoindolyl, the 3-isoindolyl, the 4-isoindolyl, the 5-isoindolyl, the 6-isoindolyl, the 7-isoindolyl, the 2-furyl, the 3-furyl, the 2-benzofuryl, the 3-benzofuryl, the 4-benzofuryl, the 5-benzofuryl, the 6-benzofuryl, the 7-benzofuryl, the 1-isobenzofuran-base, the 3-isobenzofuran-base, the 4-isobenzofuran-base, the 5-isobenzofuran-base, the 6-isobenzofuran-base, the 7-isobenzofuran-base, the 2-quinolyl, the 3-quinolyl, the 4-quinolyl, the 5-quinolyl, the 6-quinolyl, the 7-quinolyl, the 8-quinolyl, the 1-isoquinolyl, the 3-isoquinolyl, the 4-isoquinolyl, the 5-isoquinolyl, the 6-isoquinolyl, the 7-isoquinolyl, the 8-isoquinolyl, the 2-quinoxalinyl, the 5-quinoxalinyl, the 6-quinoxalinyl, the 1-carbazyl, the 2-carbazyl, the 3-carbazyl, the 4-carbazyl, the 9-carbazyl, the 1-phenanthridinyl, the 2-phenanthridinyl, the 3-phenanthridinyl, the 4-phenanthridinyl, the 6-phenanthridinyl, the 7-phenanthridinyl, the 8-phenanthridinyl, the 9-phenanthridinyl, the 10-phenanthridinyl, the 1-acridyl, the 2-acridyl, the 3-acridyl, the 4-acridyl, the 9-acridyl, 1,7-phenanthroline-2-base, 1,7-phenanthroline-3-base, 1,7-phenanthroline-4-base, 1,7-phenanthroline-5-base, 1,7-phenanthroline-6-base, 1,7-phenanthroline-8-base, 1,7-phenanthroline-9-base, 1,7-phenanthroline-10-base, 1,8-phenanthroline-2-base, 1,8-phenanthroline-3-base, 1,8-phenanthroline-4-base, 1,8-phenanthroline-5-base, 1,8-phenanthroline-6-base, 1,8-phenanthroline-7-base, 1,8-phenanthroline-9-base, 1,8-phenanthroline-10-base, 1,9-phenanthroline-2-base, 1,9-phenanthroline-3-base, 1,9-phenanthroline-4-base, 1,9-phenanthroline-5-base, 1,9-phenanthroline-6-base, 1,9-phenanthroline-7-base, 1,9-phenanthroline-8-base, 1,9-phenanthroline-10-base, 1,10-phenanthroline-2-base, 1,10-phenanthroline-3-base, 1,10-phenanthroline-4-base, 1,10-phenanthroline-5-base, 2,9-phenanthroline-1-base, 2,9-phenanthroline-3-base, 2,9-phenanthroline-4-base, 2,9-phenanthroline-5-base, 2,9-phenanthroline-6-base, 2,9-phenanthroline-7-base, 2,9-phenanthroline-8-base, 2,9-phenanthroline-10-base, 2,8-phenanthroline-1-base, 2,8-phenanthroline-3-base, 2,8-phenanthroline-4-base, 2,8-phenanthroline-5-base, 2,8-phenanthroline-6-base, 2,8-phenanthroline-7-base, 2,8-phenanthroline-9-base, 2,8-phenanthroline-10-base, 2,7-phenanthroline-1-base, 2,7-phenanthroline-3-base, 2,7-phenanthroline-4-base, 2,7-phenanthroline-5-base, 2,7-phenanthroline-6-base, 2,7-phenanthroline-8-base, 2,7-phenanthroline-9-base, 2,7-phenanthroline-10-base, the 1-phenazinyl, the 2-phenazinyl, the 1-phenothiazinyl, the 2-phenothiazinyl, the 3-phenothiazinyl, the 4-phenothiazinyl, the lysivane base, the 1-phenoxazinyl, the 2-phenoxazinyl, the 3-phenoxazinyl, the 4-phenoxazinyl, the 10-phenoxazinyl, the 2-oxazolyl, the 4-oxazolyl, the 5-oxazolyl, 2-oxadiazole base, 5-oxadiazole base, 3-frazanyl, the 2-thienyl, the 3-thienyl, 2-methylpyrrole-1-base, 2-methylpyrrole-3-base, 2-methylpyrrole-4-base, 2-methylpyrrole-5-base, 3-methylpyrrole-1-base, 3-methylpyrrole-2-base, 3-methylpyrrole-4-base, 3-methylpyrrole-5-base, 2-tertiary butyl pyrroles-4-base, 3-(2-phenyl propyl) pyrroles-1-base, 2-methyl isophthalic acid-indyl, 4-methyl isophthalic acid-indyl, 2-methyl-3-indyl, 4-methyl 3-indyl, the 2-tertiary butyl-1-indyl, the 4-tertiary butyl-1-indyl, the 2-tertiary butyl-3-indyl and the 4-tertiary butyl-3-indyl.

Above-mentioned each group can have suitable substituents, and this substituting group comprises, for example, and alkyl, alkoxyl group, halogen atom, cyano group, alkoxy carbonyl, carboxyl, ester group, amide group, sulphur oxygen base (sulfoxyl), sulfoamido, nitro, aryl and heteroaryl.

The example of abovementioned alkyl, aryl and heteroaryl comprises above-described identical group.The example of halogen atom comprises fluorine atom, chlorine atom, bromine atoms and iodine atom.Alkoxyl group can be any straight chain, side chain and cyclic group, and their example comprises methoxyl group, oxyethyl group, positive propoxy, isopropoxy, various butoxy, various pentyloxy, various hexyloxy, various octyloxy, various last of the ten Heavenly stems oxygen base, cyclopentyloxy, cyclohexyloxy, benzyloxy and benzene oxyethyl group.Sulfoamido can be the sulphonamide or the unsubstituted sulphonamide of replacement, and amide group can be the acid amides or the unsubstituted acid amides of replacement.The substituting group of above-mentioned alkoxyl group, sulfoamido and amide group is included in as above R ¹And R ²In given identical group.In addition, the example of the alkoxyl group in the alkoxy carbonyl comprises aforesaid identical group.

By R ¹And R ²Be connected to each other and comprise with the common ring texture that forms of nitrogen-atoms, for example, 1-pyrrolidyl, piperidino-(1-position only) and morpholine.

By R ¹And R ²Be connected to each other and have the common ring texture that forms of phenyl ring of nitrogen-atoms to comprise with bonding, for example, following array structure:

In formula (I), (II) with (V) in (VIII), X represention oxygen atom, sulphur atom ,-NH-or-NR ₃-(R ³Representative can have the heteroaryl that the alkyl of the substituent 1-10 of a having carbon atom, the aryl that can have the substituent 6-20 of a having carbon atom maybe can have the substituent 5-20 of a having carbon atom).

By aforesaid R ³The example of the alkyl of representative, aryl and heteroaryl comprises above-mentioned at R separately ¹And R ²In given identical group, therefore substituting group also comprises identical group.

In formula (III) with (IV), Y represention oxygen atom, sulphur atom or-NR ₄-(R ⁴Representative can have the heteroaryl that the alkyl of the substituent 1-10 of a having carbon atom, the aryl that can have the substituent 6-20 of a having carbon atom maybe can have the substituent 5-20 of a having carbon atom), and at formula V in (IV), Y represention oxygen atom, sulphur atom ,-NH-or-NR ⁴-(R ⁴Same as described above).

By aforesaid R ⁴The alkyl of representative, the example of aryl and heteroaryl comprises above-mentioned at R ¹And R ²Therefore the middle identical group that is provided respectively, substituting group also comprise identical group.

In (VIII), on behalf of the aryl that can have the substituent 6-20 of a having carbon atom, Ar maybe can have the heteroaryl of the substituent 5-20 of a having carbon atom in formula (III).The example of aryl and heteroaryl comprises above-mentioned at R respectively ¹And R ²In given identical group, therefore substituting group also comprises identical group.

Object lesson by the compound of above-mentioned formula (I) representative comprises, for example, and by the represented compound of following formula (I-a):

Object lesson by the compound of above-mentioned formula (II) representative comprises, for example such compound is wherein presented the compound of the hexa-atomic structure of formula (II) representative by the formed ring of X in the compound represented by formula (I-a).

Compound of the present invention by formula (I) and formula (II) representative is a pigment, and can be suitably as all containing the dispersed dye of above-mentioned pigment, pigment, electrofax tinter, heat transfer pigment, nonlinear optical material such as optical modulation element, opto-electronic conversion pigment such as organic solar cell and the high-density optical record type pigment of spray ink Printing separately.In addition, they also can be used as and are used for preparation by the intermediate of formula V to the following compounds of the present invention of (VIII) representative.

Can be used as particular instance by formula (III-a) to the compound of formula (III-d) representative by the The compounds of this invention of formula (III) representative:

Can be used as particular instance by formula (IV-a) to the compound of formula (IV-d) representative by the The compounds of this invention of formula (IV) representative:

Can be used as particular instance by formula (V-a) to the compound of formula (V-c) representative by the The compounds of this invention of formula V representative:

Can be used as particular instance by formula (VI-a) to the compound of formula (VI-c) representative by the The compounds of this invention of formula (VI) representative:

Particular instance by the compound of above-mentioned formula (VII) representative comprises, for example such compound is wherein presented the compound of the hexa-atomic structure of formula (VII) representative by the formed ring of X in by the represented compound of above-mentioned formula (V-a) to (V-c).

Particular instance by the compound of above-mentioned formula (VIII) representative comprises, for example such compound is wherein presented the compound of the hexa-atomic structure of formula (VIII) representative by the formed ring of X in by the represented compound of above-mentioned formula (VI-a) to (VI-c).

The compounds of this invention by formula (III) to (VIII) representative is the organic fluorescence pigment, and can be suitably as all containing the dispersed dye of above-mentioned pigment, the pigment of spray ink Printing separately, electrofax tinter, heat transfer pigment, luminescent material such as organic electroluminescent element, nonlinear optical material such as optical modulation element, opto-electronic conversion pigment such as organic solar cell, fluorochrome such as organic EL dye laser, light modulated wavelength conversion pigment such as agricultural film, high-density optical record type pigment and be used for the fluorochrome of molecular recognition.In addition, some compounds have the ability that forms Runge-Kutta integration, and they can be derived is to comprise that cage closes the solid luminescence organic fluorescence pigment of complex compound, wherein can change the color harmony fluorescence radiation, wherein contains various organic guest molecules and can improve performance greatly by making in addition.

Closing complex compound by formula (III) to the The compounds of this invention of formula (VIII) representative and cage thereof can be used as the organic fluorescence pigment and is used for multiple use, for example, the fluorescence in multiple display equipment is regulated film, pigment laser apparatus, light toning, Conversion of energy, high-density optical record, indicating meter and is used for the fluorescent optical sensor of molecular recognition.

In above-mentioned application, the fluorescence in multiple display equipment is regulated film and be can be used for the electronic console device, for example, and PDP (plasma display), ELD (electroluminescent display), LED (photodiode) and VFD (fluorescent display tube).

Below, the preparation method of assorted polynuclear compound of the present invention is described.

Preparation method with the compound of formula (I) representative.

The of the present invention assorted polynuclear compound of formula (I) representative is 1, and 2-naphthoquinones radical derivative can basis, and for example, reaction formula (A) as follows when X is Sauerstoffatom is prepared:

Wherein M represents alkali metal atom, and R ¹And R ²With identical as mentioned above.

As shown in the reaction formula (A), substantially stoichiometric 1, the phenol (b) that a 2-naphthoquinones-4-sulfonic acid alkali metal salts (a) and a position replace, in the presence of catalyzer such as copper halide (II), under about 0-80 ℃ temperature, in suitable solvent such as acetate, react, obtain by formula (I-1) representative have a cumarone-1, the compound of 2-naphthoquinones skeleton, wherein X is a Sauerstoffatom.In this case, be by product by the represented compound of formula (c).

About preparation method by the The compounds of this invention of formula (II) representative, the catalyzer such as the nickelous chloride that have weak oxide intensity by use in above-mentioned reaction formula (A) react, obtained compound by formula (c) representative as principal constituent, then behind the compound that separates by formula (c) representative, in the presence of catalyzer with strong oxidizing intensity such as neutralized verdigris, under about 40-120 ℃ temperature, in solvent such as methyl-sulphoxide, carry out cyclization, obtain above-mentioned compound by formula (II) representative.

About by the formula (III) and (IV) preparation method of the The compounds of this invention of representative, they can make according to reaction formula as follows (B), for example, and when Y is Sauerstoffatom:

Wherein, R ¹, R ²With Ar with identical as mentioned above.

As described in the reaction formula (B), by formula (d) represented 1,2-naphthoquinone derivatives and basic stoichiometry or excessive a little aromatic aldehyde (e) and excessive ammonium acetate, in suitable solvent such as acetate, under about 50-100 ℃ temperature, react, obtain by the formula (III-1) and (IV-1) compound with naphthoxazole skeleton of representative.

About the formula V and (VI) preparation method of the compound of the present invention of representative, they can make according to reaction formula as follows (C), for example, and when X and Y are Sauerstoffatom:

R wherein ¹, R ²With Ar with identical as mentioned above.

Shown in reaction formula (C), under about 50-100 ℃ temperature, react in suitable solvent such as acetate by the compound of formula (I-1) representative and excessive a little aromatic aldehyde (f) and excessive ammonium acetate, obtain by the formula (V-1) and (VI-1) compound with cumarone Bing naphthoxazole skeleton of representative.

About by the formula (VII) and (VIII) preparation method of the The compounds of this invention of representative, they can replace the compound of formula (I-1) representative make by using the compound by formula (II) representative.

Off-color material composition of the present invention will be described below.

Off-color material composition of the present invention comprises (A) fluorochrome, and it comprises at least a above-mentioned assorted polynuclear compound by formula (III) to (VIII) representative, and (B) adhesive material.

The concentration of said components (A) need not specific qualification, based on the gross weight of the solid matter that contains in the off-color material composition, is preferably 0.1-10 weight %, more preferably 0.2-5 weight %.If concentration is 0.1 weight or higher, the light in the light source can fully be absorbed, and can change color.If be 10 weight or still less, its variable color efficient that can avoid causing owing to concentration quenching lowers, and can avoid highly meticulous pattern to form.

The adhesive material of component (B) is the light reaction resin more preferably.Here; the light reaction resin means the resin that photocuring reaction takes place; it comprises the resin that is mixed with polymerizable oligomer and/or monomer such as epoxy acrylate, urethane acrylate and polyether acrylate, and the resin that is mixed with allyl group alkylsulfonyl salt and epoxy compounds.

The adhesive material of component (B) is preferably thermosetting resin or thermoplastic resin.

Thermosetting resin comprises, for example, and Resins, epoxy, urethane resin, Synolac and polyimide resin, and Resins, epoxy and urethane resin be particularly preferred, because they have high-clarity and good pigment dispersiveness.

Thermoplastic resin comprises, for example, (methyl) acrylic resin, polystyrene resin, polycarbonate resin and vibrin, and (methyl) acrylic resin and polycarbonate be particularly preferred, because they have high-clarity and good pigment dispersiveness.

Off-color material composition of the present invention more preferably contains the basic fluorochrome of rhodamine (Rhodamine) such as rhodamine (Rhodamine) B and rhodamine (Rhodamine) 6G.

In addition, the adhesive material that uses among the present invention (B) preferably contains (C) methacrylic ester-Sipacril 2739OF, and the monomer and/or the oligopolymer that (D) have the ethylenic unsaturated group of optical polymerism.

Above-mentioned methacrylic ester-Sipacril 2739OF (C) is by structure representative as follows:

R is that replace or unsubstituted alkyl with 1-10 carbon atom, or that replace or unsubstituted aryl with 6-20 carbon atom, and comprises, for example, and benzyl, methyl, ethyl, cyclohexyl, cyclohexyl methyl and hydroxyethyl.R is preferably methyl or benzyl, because its solvability, development and film quality are isostatic.Term m and n are preferably 1 or bigger integer separately.According to Mw (weight-average molecular weight) meter, above-mentioned multipolymer preferably has 5,000-100,000 molecular weight, more preferably 10,000-50,000.If Mw is 5,000 or higher, the intensity of optically variable films can not reduce.If it is 100,000 or still less, the viscosity of this solution can be not excessive, and can form level and smooth optically variable films.

Copolymerization ratio q is preferably q=m/ (m+n)=0.5-0.95, more preferably 0.7-0.9.If copolymerization ratio is 0.5 or higher, film can be owing to developing solution expand in developing process, and pattern forms tolerance range and can not reduce.If it is 0.95 or still less, can become too little in the solvability of developing solution, and can prevent situation about can't develop.

Monomer and/or oligopolymer (D) with ethylenic unsaturated group of optical polymerism comprise (methyl) vinylformic acid 2-hydroxyl ethyl ester, (methyl) vinylformic acid 2-hydroxypropyl acrylate and the own ester of (methyl) vinylformic acid 2-hydroxyl.

The example of above-mentioned (methyl) acrylate comprises two (methyl) vinylformic acid glycol ester, two (methyl) vinylformic acid glycol ether ester, two (methyl) vinylformic acid Triethylene Glycol, two (methyl) vinylformic acid tetraethylene-glycol ester, two (methyl) vinylformic acid 1,4-butanediol ester, three (methyl) vinylformic acid trihydroxymethylpropanyl ester, two (methyl) vinylformic acid pentaerythritol ester, three (methyl) vinylformic acid pentaerythritol ester, four (methyl) vinylformic acid pentaerythritol ester, six (methyl) vinylformic acid dipentaerythritol ester and (methyl) vinylformic acid glyceryl ester.

In the present invention, the monomer of component (D) and/or oligopolymer can use separately or be used in combination with two kinds or more kinds of this component.Only otherwise damage the quality of off-color material composition of the present invention and optically variable films, these monomers and oligopolymer just can use, and its amount is generally 10-200 weight part/100 weight part methacrylic ester-Sipacril 2739OFs (C).As the amount of fruit component (D) is 200 weight parts or still less, bonding (tacking) performance after the Procuring just can not go wrong.

Except that component (A) with (B) or the component (A)-(D), off-color material composition of the present invention further preferably contains the compound that (E) has epoxide group, as top compound, can provide phenol phenolic varnish type epoxy compounds and cresols phenolic varnish type epoxy compounds.When optically variable films is made by the off-color material composition, can increase film strength by in the off-color material composition, adding above-claimed cpd.After the photopolymerization of component (D), heat that can to make that crosslinked product of optics and the compound (E) with epoxide group carry out further crosslinked to promote the degree of crosslinking of film.

Based on the total amount of off-color material composition, the content with compound (E) of epoxide group is preferably 0.1-15 weight %, more preferably 0.5-7 weight %.If it is 15 weight % or still less, the compound with epoxide group just can polymerization in the storage process of off-color material composition, and liquid viscosity can not change.If it is 0.1 weight % or more, can obtain satisfied effect.

If desired, can in off-color material composition of the present invention, add Photoepolymerizationinitiater initiater or photosensitizers, and Photoepolymerizationinitiater initiater and photosensitizers not only can be used for having the monomer of component (D) of ethylenic unsaturated group of optical polymerism and/or the optics curing reaction of oligopolymer, also can be used as other just polymerization starter of addible photopolymerization compounds if desired.For example, acetophenones, Benzophenones, st-yrax ethers, sulphur compound class, anthraquinone class, organo-peroxide and thio-alcohol can be suitably as above-mentioned Photoepolymerizationinitiater initiaters.Can provide its particular example, acetophenones comprises methyl phenyl ketone, 2,2-diethoxy acetophenone, p-methyl aceto phenone, to dimethylamino Propiophenone, dichloroacetophenone, Trichloroacetophenon and p-tert.-butyl acetophenone; Benzophenones comprises benzophenone, 2-chloro benzophenone and p, p '-two dimethylamino benzophenone; The st-yrax ethers comprises benzyl, st-yrax, benzoin methyl ether, benzoin isopropyl ether and benzoin isobutyl ether: the sulphur compound class comprises benzyl methyl ketal, thioxanthone, 2-clopenthixal ketone, 2,4-diethyl thioxanthone, 2-methyl thioxanthone and 2-isopropyl thioxanthone; The anthraquinone class comprises 2-ethyl-anthraquinone, prestox anthraquinone, 1,2-benzo anthraquinone and 2,3-phenylbenzene anthraquinone; The organic peroxy compound comprises Diisopropyl azodicarboxylate, benzoyl peroxide and cumene peroxide; And thio-alcohol comprises 2-mercaptobenzoxazole and 2-mercaptobenzothiazole.Above-mentioned Photoepolymerizationinitiater initiater and photosensitizers have only a class to use separately, and they can two kinds or multiple being used in combination.

In addition, also can adding itself can not be as Photoepolymerizationinitiater initiater and photosensitizers, thereby but can be by be used in combination the compound of the ability of strengthening Photoepolymerizationinitiater initiater and photosensitizers with above-claimed cpd.These compounds comprise, for example, tertiary amine such as trolamine, thus it can play a role by being used in combination with benzophenone.

The preferred usage quantity of above-mentioned Photoepolymerizationinitiater initiater and photosensitizers is the component (D) of 0-10 weight part/100 weight parts.If usage quantity is 10 weight parts or still less, light is easy to arrive inner and can not produces uncured portion.In addition, the bounding force between substrate and the resin is fine, and the fluorescence of pigment can not reduce yet.

In addition, in order to improve the fluorescent yield of fluorochrome, the oligopolymer or the polymkeric substance of transparent resin such as melamine resin, phenol resins, Synolac, urethane resin, vibrin and polyamide resin, polyvinyl alcohol, polyvinylpyrrolidone, Natvosol, carboxymethyl cellulose, aromatic sulfonamides resin, urea-formaldehyde resin and benzo guanamine resin can be joined in the off-color material composition of the present invention, and melamine resin and benzo guanamine resin are particularly preferred.As long as do not damage the performance of off-color material composition and optically variable films, above-mentioned resin just can use.With respect to the methacrylic ester-Sipacril 2739OF of per 100 parts by weight of component (C), its preferred usage quantity is 200 weight parts or still less, more preferably 100 weight parts or still less.If usage quantity is 200 weight parts or still less, bonding (tacking) performance after the Procuring just can not go wrong.

If desired, off-color material composition of the present invention can mix mutually with additive such as curing accelerator, thermal polymerization inhibitor, softening agent, filler, solvent, defoamer and levelling agent.Curing accelerator comprises, for example, and peroxybenzoic acid derivative, peracetic acid and benzophenone; Thermal polymerization inhibitor comprises, for example, and Resorcinol, hydroquinone monomethyl ether, pyrogallol, tert-butyl catechol and thiodiphenylamine; Softening agent comprises, for example, and terephthalic acid butyl ester, terephthalic acid dioctyl ester and three cresols (tricresyl); Filler comprises, for example, and glass fibre, silicon-dioxide, mica and aluminum oxide; And for example, phosphorus base, fluorine-based and acrylic compound can be used as defoamer and levelling agent suitably.

To describe optically variable films of the present invention below.

Optically variable films of the present invention comprises above-mentioned off-color material composition of the present invention, and above-mentioned off-color material composition is used for forming film, or forms optically variable films in the substrate by being coated in.Especially, by using the tolerance range that photolithography can be good to form optically variable films with ideal pattern.

According to the preparation method of optically variable films, be used for being dissolved in the solvent that solvent is used for the various components of off-color material composition and be preferably ketone, ester class or lactone.Ketone comprises methylethylketone, methyl iso-butyl ketone (MIBK) and pimelinketone, and the ester class comprises 2-acetoxyl group-1-ethyl propyl ether, methylcyclohexane, ethyl cellosolve, ethylene glycol butyl ether and cellosolve acetate.Lactone comprises gamma-butyrolactone etc.

Using photolithography to prepare in the optically variable films of the present invention, the solution that will be made by above-mentioned photosensitive colour-changing material compositions is coated on the surface of substrate with the form of solution usually, then by Procuring drying (prebake) solvent.Afterwards, photomask is put on the coated film that so obtains, and shine to solidify exposed portions with active light, then use weak alkaline aqueous solution wash-out unexposed portion to carry out development operation to form pattern, carry out the back bake operation of after drying then.

The off-color material composition solution is applied thereon substrate planar substrates preferably, and wherein the transparence at the light of the visible region of 400-700nm is 50% or more.Specifically, use substrate of glass and polymer sheet.Especially, glass, lead glass, sillico aluminate glass, borosilicate glass, barium borosilicate glass or the quartz of soda-lime glass, baric strontium can be used as substrate of glass suitably.Polymer sheet comprises polycarbonate, polyacrylic, polyethylene terephthalate, polyether sulfides or polysulfones.Except using known solution dipping method and spray method, the method that also can use any use roller coating machine land coater and spin coater is coated in the solution of off-color material composition of the present invention in the substrate.Form coated film by after applying, removing (prebake) solvent with ideal thickness.

This prebake is by operating with baking oven and hot plate heating.The Heating temperature of prebake and heat-up time can suitably be selected according to the solvent that uses, and for example carry out under 80-150 ℃ temperature 1-30 minute.Exposure after the prebake is operated by using exposure machine, expose by photomask, only corresponding to a part of protective coating of pattern by sensitization.Can suitably select exposure machine and exposing radiation condition, visible rays, UV ray, X ray and electron beam can be used as radiant light.Irradiation dose need not special qualification, and can be for example, 1-3000mJ/cm ²Scope in select.

In order to remove the protective coating of unexposed portion, after exposure, carry out the alkali development operation, and form desired pattern by this development operation.For example, the carbonate aqueous solution of basic metal and alkaline-earth metal can be used as the developing solution that is fit to above-mentioned alkali development operation.Especially, development operation is preferably used the carbonate that contains 1-3 weight % such as the weak alkaline aqueous solution of yellow soda ash, salt of wormwood and Quilonum Retard, at 10-50 ℃, carry out under preferred 20-40 ℃ the temperature, precision profile can accurately form by commercial developer and ultrasonic cleaner.

Development is carried out with aforesaid method, heat-treats (afterwards curing) then under the condition of 80-220 ℃ and 10-120 minute.Cure after this is to carry out in order to increase the optically variable films that forms pattern and the bounding force between the substrate.This operation is by carrying out as the baking oven in prebake and the heating of hot plate.

When adhesive material is thermoplastic resin or thermosetting resin, need not to carry out step of exposure.Thermal treatment (the afterwards cure) operation of thermosetting resin membrane after by prebake solidified.

Lambda1-wavelength is changed to the required film thickness of desired wavelength to be needed select optically variable films thickness of the present invention suitably, and this film thickness preferably falls in the scope of 1-100 μ m, more preferably 1-20 μ m.

Optically variable films of the present invention can be by the equipment colour filter obtaining desired wavelength, thus the control purity of color.For example; perylene base pigment, pigment lake, azo-group pigment, quinacridine ketone group pigment, anthraquinonyl pigment, anthryl pigment, dihydro isoindolyl pigment, isoindoline ketone group pigment, phthalocyanine base pigment, tritane base pigment, indanthrone base pigment, indophenols base pigment, cyanine base pigment and triazine dioxin pigment can suitably use separately or use with the form of the pigment of the mixture that comprises two or more pigment, or with by dissolving in adhesive resin or disperse the form of the solid matter that pigment obtains to use.

When reality was used optically variable films, the structure example that can set should look like this:

(1) light source/optically variable films

(2) light source/substrate/optically variable films

(3) light source/optically variable films/substrate

(4) light source/light transmits substrate/optically variable films/substrate

(5) light source/optically variable films/colour filter

(6) light source/substrate/optically variable films/colour filter

(7) light source/optically variable films/substrate/colour filter

(8) light source/substrate/optically variable films/substrate/colour filter

(9) light source/substrate/optically variable films/colour filter/substrate

(10) light source/optically variable films/colour filter/substrate

When stating structure in the use, each structural element is lamination in order, or is adhered together.The lamination of above-mentioned optically variable films need not particular determination in proper order, and can carry out lamination from either direction, can make to the left side from the left side to the right or from the right.

The light that optically variable films of the present invention preferably absorbs light source has more long wavelength's light to send, organic EL, LED (photodiode), cold-cathode tube, inorganic EL element, luminescent lamp or incandescent light can be used as above-mentioned light source, and it is particularly preferred launching the less organic EL and the LED element that can damage the UV ray of pigment.

To further describe in detail the present invention according to embodiment and comparative example below, but the present invention is not limited by these embodiment.

Various evaluations to optically variable films in the following example are carried out with following method:

(1) evaluation of discoloration

The particular instance that optically variable films is formed the color organic EL element with organic EL as shown in Figure 1.As shown in the same figure, the color organic EL element comprises, from emergent light one side, and substrate of glass 1, optically variable films 2, anode 3, organic EL fluorescent layer 4 and negative electrode 5.Organic EL fluorescent layer 4 is easy to damage under the condition of moisture and oxygen existence, and therefore the side from negative electrode 5 seals by the opposite substrate of glass, comprises that thus the whole componentry of optically variable films is capped.

In having the color organic EL element of said structure, the performance of individual component is a dispersive, and has the transformation period as organic EL emission trimmed book body of exciting light, therefore is difficult to estimate separately distinctively the fluorescence property and the wearing quality of optically variable films itself.

Then, as shown in Figure 2, make sample by on transparency glass plate, forming optically variable films, then, will be thereon overlapping according to the blue organic EL that the pigment that is used for optically variable films makes respectively with the peak wavelength that suitably is selected from the 440-470nm scope, and shine to measure the spectrum of the transmitted light that obtains by optically variable films and spectral filter within sweep of the eye by spectral brightness (CS-1000, by Minolta Co., Ltd. produces) at two degree with blue light.

Compare with the luminescent spectrum of blue organic EL, determine the relative intensity of fluorescence of optically variable films by the following method:

Variable color efficient=(brightness of the transmitted light that obtains by optically variable films and spectral filter)/(brightness of EL element)

In addition, determine chromaticity coordinates by the spectrum of measuring.

The performance of optically variable films can compare by using identical EL element by aforesaid method mutually.

(2) the exciting light Continuous irradiation is to the test (estimating pigment-sustainment rate) of optically variable films

Because the transformation period that EL element has luminous intensity, the blue organic EL that will have peak wavelength and be 470nm is as the excitation light source with constant intensity, and as shown in Figure 3, with excitation light source and optically variable films (sample of preparation in (1)) but be arranged in the nitrogen alternate chamber, it contacts with light source thus, and they are placed under the dry nitrogen atmosphere with constantly following some sapphirine organic EL of 400 nits (nit) 1000 hours.

By relatively calculating pigment-sustainment rate with the pigment light absorption ratio (light absorption ratio of coumarin 6 among the comparative example) in the sample of before the blue light illumination and irradiation back.

Synthesizing of synthetic embodiment 1 compound (I-a)

With 1 of 1.0g (3.8mmol), the CuCl2 of 2-naphthoquinones-4-sodium sulfonate and 0.26g (1.92mmol) packs in the mortar, and is dissolved in the small amount of acetic acid aqueous solution.Then, to wherein add 0.85g (3.84mmol) be dissolved in the small amount of acetic acid aqueous solution between (dibutylamino) phenol, in mortar, mix.At this mixture placing response after a couple of days, to wherein adding entry, filter deposition thing, and drying under reduced pressure.

With the above-mentioned settling of dichloromethane extraction, the methylene dichloride in the concentrated extract then.Residual solution is handled to separate and to purify with silicagel column (developping agent: dichloromethane/ethyl acetate, volume ratio are 6/1), obtains the Powdered crystal 5 86mg of purple (productive rate 40.9%), promptly obtains target compound (I-a).

The analytical results of above-claimed cpd is as follows.

(1) fusing point: 149-153 ℃

(2) ¹H-NMR(CDCl ₃)：δ(ppm)1.00(6H，t)，1.37-1.50(4H，m)，1.62-1.74(4H，m)，3.34(4H，t)，6.65(1H，s)，6.80(1H，dd)，7.43(1H，dt)，7.65(1H，dt)，7.88(1H，d)，7.93(1H，d)，8.11(1H，d)。

(3) infrared absorption spectrum (IR, KBr): 1618cm ^-1

(4) ultimate analysis value

C H N

Observed value (%) 76.91 6.83 3.76

Calculated value (%) 76.77 6.71 3.73

(5) photoabsorption and fluorescent characteristics

(the measurement solvent: 1, the 4-dioxane)

Light absorption characteristics; λ _Max(ε _Max/ dm ³Mol ^-1Cm ^-1): 410nm (7800), 533nm (10800)

Fluorescent characteristics: no fluorescence

Synthetic embodiment 2 compounds (V-a) and synthesizing (VI-a)

With the compound (I-a) of 0.8g (2.13mmol) and 0.42g (3.16mmol) cyanobenzaldehyde is dissolved in the acetate of 60ml, to the ammonium acetate that wherein adds 2.63g (34.1mmol), in 90 ℃ of reactions 2 hours.After finishing reaction,, further add methylene dichloride with extraction product to wherein adding entry.The separate dichloromethane layer, and after washing with water, concentrate, residual solution is handled to separate and to purify with silicagel column (developping agent: dimethylbenzene/acetate, volume ratio are 20/1).

Obtain 521mg (productive rate 50.2%) orange powder shape crystalline compounds (V-a) and 266mg (productive rate 25.7%) yellow powder shape crystalline compounds (VI-a).

The analytical results of compound (V-a) and compound (VI-a) is as follows.

＜compound (V-a) 〉

(1) fusing point: 203-204 ℃

(2) ¹H-NMR(CDCl ₃)：δ(ppm)1.00(6H，t)，1.37-1.50(4H，m)，1.62-1.74(4H，m)，3.34(4H，t)，6.85(1H，dd)，6.95(1H，ds)，7.66(2H，m)，7.81(2H，d)，8.15(1H，d)，8.41(2H，d)，8.60(1H，d)，8.64(1H，d)。

(3) infrared absorption spectrum (IR; KBr): 1507,1632,2226cm ^-1

(4) ultimate analysis

C H N

Observed value (%) 78.58 5.75 8.70

Calculated value (%) 78.83 6.00 8.62

(5) photoabsorption and fluorescent characteristics

(the measurement solvent: 1, the 4-dioxane)

Light absorption characteristics; λ _Max(ε _Max/ dm ³Mol ^-1Cm ^-1): 362nm (14000), 420nm (28900)

Fluorescent characteristics: λ _Em: 526nm

＜compound (VI-a) 〉

(1) fusing point: 227-229 ℃

(2) ¹H-NMR(CDCl ₃)：δ(ppm)1.01(6H，t)，1.39-1.49(4H，m)，1.62-1.72(4H，m)，3.42(4H，t)，6.85(1H，d)，7.00(1H，ds)，7.65(1H，t)，7.71(1H，t)，7.85(2H，d)，8.13(1H，d)，8.40(1H，d)，8.48(2H，d)，8.65(1H，d)。

(3) infrared absorption spectrum (IR; KBr): 1505,1633,2228cm ^-1

(4) ultimate analysis value

C H N

Observed value (%) 78.83 5.90 8.63

Calculated value (%) 78.83 6.00 8.62

(5) photoabsorption and fluorescent characteristics

(the measurement solvent: 1, the 4-dioxane)

Light absorption characteristics; λ _Max(ε _Max/ dm ³Mol ^-1Cm ^-1): 366nm (26800), 418nm (4500)

Fluorescent characteristics: λ _Em: 553nm

Synthetic embodiment 3 compounds (V-b) and synthesizing (VI-b)

The compound (I-a) of 0.8g (2.13mmol) and the 9-anthracene aldehyde of 1.10g (5.33mmol) are dissolved in the 150ml acetate, to the ammonium acetate that wherein adds 8.21g (0.107mol), in 80 ℃ of reactions 2 hours.After finishing reaction,, further add methylene dichloride with extraction product to wherein adding entry.The separate dichloromethane layer and wash with water after concentrate, residual solution is handled to separate and to purify with silicagel column (developping agent: dimethylbenzene/acetate, volume ratio are 20/1).

Obtain red crystals compound (V-b) and 585mg (productive rate 21.7%) the orange crystalline compounds (VI-b) of 823mg (productive rate 30.6%).

Compound (V-b) and analytical results (VI-b) are as follows.

＜compound (V-b) 〉

(1) fusing point: 112-114 ℃

(2) ¹H-NMR (acetone-d ⁶): δ (ppm) 1.00 (6H, t), 1.42-1.51 (4H, m), 1.67-1.75 (4H, m), 3.51 (4H, q), 7.03 (1H, dd), 7.09 (1H, d), 7.63-7.67 (4H, m), 7.78-7.87 (2H, m), 8.27-8.30 (4H, m), 8.40 (1H, d), 8.76 (1H, d), 8.86 (1H, d), 8.95 (1H, s).

(3) infrared absorption spectrum (IR; KBr): 1506,1632cm ^-1

(4) ultimate analysis

C H N

Observed value (%) 83.36 6.14 5.02

Calculated value (%) 83.24 6.09 4.98

(5) photoabsorption and fluorescent characteristics

(the measurement solvent: 1, the 4-dioxane)

Light absorption characteristics; λ _Max(ε _Max/ dm ³Mol ^-1Cm ^-1): 373nm (26800), 420nm (14400)

Fluorescent characteristics: λ _Em: 569nm

＜compound (VI-b) 〉

(1) fusing point: 175-176 ℃

(2) ¹H-NMR (acetone-d ⁶): δ (ppm) 1.02 (6H, t), 1.43-1.55 (4H, m), 1.69-1.77 (4H, m), 352 (4H, q), 7.02 (1H, dd), 7.14 (1H, d), 7.63-7.67 (4H, m), 7.72-7.76 (1H, m), and 7.83-7.87 (1H, m), 8.25-8.30 (4H, m), 8.38 (1H, d), 8.44 (1H, d), 8.87 (1H, d), 8.96 (1H, s).

(3) infrared absorption spectrum (IR; KBr): 1507,1634cm ^-1

(4) ultimate analysis

C H N

Observed value (%) 83.48 6.23 5.16

Calculated value (%) 83.24 6.09 4.98

(5) photoabsorption and fluorescent characteristics

(the measurement solvent: 1, the 4-dioxane)

Light absorption characteristics; λ _Max(ε _Max/ dm ³Mol ^-1Cm ^-1): 373nm (26400)

Fluorescent characteristics: λ _Em: 570nm

Synthetic embodiment 4 compounds (V-c) and synthesizing (VI-c)

The compound (I-a) of 0.8g (2.13mmol) and the pyrene formaldehyde of 0.98g (4.26mmol) are dissolved in the 150ml acetate, to the ammonium acetate that wherein adds 6.57g (85mmol), in 80 ℃ of reactions 1.5 hours.After finishing reaction,, further add methylene dichloride with extraction product to wherein adding entry.The separate dichloromethane layer and wash with water after concentrate, residual solution is handled to separate and to purify with silicagel column (developping agent: dimethylbenzene/acetate, volume ratio are 20/1).

Obtain orange crystalline compounds (V-c) and 0.82g (productive rate 36.2%) the yellow crystals compound (VI-c) of 1.117g (productive rate 49.4%).

Compound (V-c) and analytical results (VI-c) are as follows.

＜compound (V-c) 〉

(1) fusing point: 222-224 ℃

(2) ¹H-NMR (acetone-d ⁶): δ (ppm) 1.04 (6H, t), 1.45-1.54 (4H, m), 1.70-1.78 (4H, m), 3.53 (4H, q), 7.02 (1H, dd), 7.12 (1H, d), 7.82-7.84 (2H, m), 8.19 (1H, t), and 8.29-8.38 (3H, m), 8.42-8.47 (2H, m), 8.51-8.55 (2H, m), 8.80-8.82 (1H, m), 8.84-8.87 (1H, m), 9.11 (1H, d), 10.15 (1H, d).

(3) infrared absorption spectrum (IR; KBr): 1506,1635cm ^-1

(4) ultimate analysis

C H N

Observed value (%) 83.88 5.86 4.72

Calculated value (%) 83.93 5.84 4.77

(5) photoabsorption and fluorescent characteristics

(the measurement solvent: 1, the 4-dioxane)

Light absorption characteristics; λ _Max(ε _Max/ dm ³Mol ^-1Cm ^-1): 362nm (24800), 397nm (28800), 436nm (33600)

Fluorescent characteristics: λ _Em: 538nm

＜compound (VI-c) 〉

(1) fusing point: 225-227 ℃

(2) ¹H-NMR (acetone-d ⁶): δ (ppm) 1.04 (6H, t), 1.48-1.53 (4H, m), 1.71-1.79 (4H, m), 3.53 (4H, q), 7.01 (1H, dd), 7.18 (1H, d), 7.78-7.87 (2H, m), 8.20 (1H, t), and 8.31-8.39 (3H, m), 8.43-8.49 (2H, m), 8.53-8.57 (2H, m), 8.64-8.67 (1H, m), 8.83 (1H, d), 9.21 (1H, d), 10.18 (1H, d).

(3) infrared absorption spectrum (IR; KBr): 1500,1635cm ^-1

(4) ultimate analysis

C H N

Observed value (%) 83.76 5.99 4.65

Calculated value (%) 83.93 5.84 4.77

(5) photoabsorption and fluorescent characteristics

(the measurement solvent: 1, the 4-dioxane)

Light absorption characteristics; λ _Max(ε _Max/ dm ³Mol ^-1Cm ^-1): 377nm (48800), 395nm (36400)

Fluorescent characteristics: λ _Em: 551nm

Synthetic embodiment 5 compounds (III-a) and synthesizing (IV-a)

4-[4-(dibutylamino) phenyl with 2.00g (5.54mmol)]-1, the ammonium acetate of 2-naphthoquinones, 0.83g (5.54mmol) p-ethoxybenzaldehyde and 6.82g (88.4mmol) is dissolved in the 59ml acetate, and in 80 ℃ of stirrings 110 minutes that reflux.After reaction was finished, solution neutralized with aqueous sodium carbonate, added the dichloromethane extraction organism.Wash methylene dichloride with water, and drying under reduced pressure, resistates is handled to separate and to purify with silicagel column (developping agent: dichloromethane/ethyl acetate, volume ratio are 10/1).

Obtain compound (III-a) and 0.75g (productive rate 27.5%) compound (IV-a) of 1.15g (productive rate 42.3%).

＜compound (III-a) 〉

(1) fusing point :-

(2) ¹H-NMR (acetone-d ⁶): δ (ppm) 1.00 (6H, t), 1.40 (4H, m), 1.47 (3H, t), 1.66 (4H, m), 3.35 (4H, t), 4.12 (2H, q), 6.79 (2H, d), 7.03 (2H, d), 7.39 (2H, d), 7.46 (1H, t), 7.64 (1H, t), 7.65 (1H, s), 8.13 (1H, d), 8.27 (2H, d), 8.62 (1H, d).

(3) infrared absorption spectrum (IR; KBr) :-

(4) ultimate analysis

C H N

Observed value (%) 80.67 7.16 6.57

Calculated value (%) 80.45 7.37 6.50

(5) photoabsorption and fluorescent characteristics

(the measurement solvent: 1, the 4-dioxane)

Light absorption characteristics; λ _Max(ε _Max/ dm ³Mol ^-1Cm ^-1): 377nm, 446nm

Fluorescent characteristics: λ _Em: 512nm

＜compound (IV-a) 〉

(1) fusing point :-

(2) ¹H-NMR (acetone-d ⁶): δ (ppm) 1.00 (6H, t), 1.40 (4H, m), 1.46 (3H, m), 1.66 (4H, m), 3.35 (4H, t), 4.14 (2H, q), 6.77 (2H, d), 7.05 (2H, d), 7.38 (2H, d), 7.45 (1H, t), 7.64 (1H, t), 7.77 (1H, s), 8.13 (1H, d), 8.28 (2H, d), 8.33 (1H, d).

(3) infrared absorption spectrum (IR; KBr) :-

(4) ultimate analysis

C H N

Observed value (%) 80.63 7.02 6.72

Calculated value (%) 80.45 7.37 6.50

(5) photoabsorption and fluorescent characteristics

(the measurement solvent: 1, the 4-dioxane)

Light absorption characteristics; λ _Max(ε _Max/ dm ³Mol ^-1m ^-1): 351nm, 437nm

Fluorescent characteristics: λ _Em: 540nm

Synthetic embodiment 6 compounds (III-b) and synthesizing (IV-b)

4-[4-(dibutylamino) phenyl with 2.00g (5.54mmol)]-1,3 of 2-naphthoquinones, 0.78g (5.54mmol), the ammonium acetate of 4-difluorobenzaldehyde and 6.82g (88.4mmol) is dissolved in the 59ml acetate, and in 80 ℃ of stirrings 2.5 hours that reflux.After reaction was finished, solution neutralized with aqueous sodium carbonate, added the dichloromethane extraction organism.Wash dichloromethane layer with water, and drying under reduced pressure, resistates is handled to separate and to purify with silicagel column (developping agent: dichloromethane/ethyl acetate, volume ratio are 10/1).

Obtain compound (III-b) and 0.19g (productive rate 7.2%) compound (IV-b) of 0.29g (productive rate 10.8%).

＜compound (III-b) 〉

(1) fusing point :-

(2) ¹H-NMR (acetone-d ⁶): δ (ppm) 1.00 (6H, t), 1.43 (4H, m), 1.66 (4H, m), 3.36 (4H, t), 6.77 (2H, d), 7.32 (1H, m), 7.37 (2H, d), 7.49 (1H, t), 7.65 (1H, s), 7.67 (1H, t), 8.08 (1H, m), 8.16 (2H, m), 8.60 (1H, d).

(3) infrared absorption spectrum (IR; KBr) :-

(4) ultimate analysis

C H N

Observed value (%) 76.89 6.37 5.91

Calculated value (%) 76.67 6.43 5.77

(5) photoabsorption and fluorescent characteristics

(the measurement solvent: 1, the 4-dioxane)

Light absorption characteristics; λ _Max(ε _Max/ dm ³Mol ^-1m ^-1): 303nm, 353nm

Fluorescent characteristics: λ _Em: 454nm

＜compound (IV-b) 〉

(1) fusing point :-

(2) ¹H-NMR (acetone-d ⁶): δ (ppm) 1.00 (6H, t), 1.42 (4H, m), 1.66 (4H, m), 3.36 (4H, m), 6.78 (2H, d), 7.36 (3H, d), 7.49 (1H, t), 7.65 (1H, t), 7.77 (1H, s), 8.17 (3H, m), 8.39 (1H, d).

(3) infrared absorption spectrum (IR; KBr) :-

(4) ultimate analysis

C H N

Observed value (%) 77.01 6.24 5.83

Calculated value (%) 76.67 6.43 5.77

(5) photoabsorption and fluorescent characteristics

(the measurement solvent: 1, the 4-dioxane)

Light absorption characteristics; λ _Max(ε _Max/ dm ³Mol ^-1Cm ^-1): 345nm (16000) ,-

Fluorescent characteristics: λ _Em: 466nm

Synthetic embodiment 7 compounds (III-c) and synthesizing (IV-c)

4-[4-(dibutylamino) phenyl with 3.00g (9.82mmol)]-1, the 1-pyrene formaldehyde of 2-naphthoquinones, 2.26g (9.82mmol) is dissolved in the 150ml acetate, to wherein adding 15.14g (0.196mol) ammonium acetate, in 80 ℃ of heating and back flow reaction 1.5 hours.After reaction is finished,, further add the dichloromethane extraction product to wherein adding entry.The separate dichloromethane layer and wash with water after concentrate, residual solution is handled to separate and to purify with silicagel column (developping agent: dimethylbenzene/acetate, volume ratio are 20/1).

Obtain orange crystalline compounds (III-c) and 0.977g (productive rate 19.2%) the yellow crystals compound (IV-c) of 0.253g (productive rate 4.9%).

Compound (III-c) and analytical results (IV-c) are as follows.

＜compound (III-c) 〉

(1) fusing point: 187-189 ℃

(2) ¹H-NMR(CDCl ₃)：δ(ppm)1.27(6H，t)，3.48(4H，q)，6.85(2H，d)，7.46(2H，d)，7.52-7.55(1H，m)，7.72-7.76(1H，m)，7.80(1H，s)，8.09(1H，t)，8.13-8.20(3H，m)，8.26-8.39(4H，m)，8.84(1H，d)，8.98(1H，d)，10.00(1H，d)。

(3) infrared absorption spectrum (IR; KBr): 1522,1609cm ^-1

(4) ultimate analysis

C H N

Observed value (%) 86.13 5.26 5.45

Calculated value (%) 86.02 5.46 5.42

(5) photoabsorption and fluorescent characteristics

(the measurement solvent: 1, the 4-dioxane)

Light absorption characteristics; λ _Max(ε _Max/ dm ³Mol ^-1Cm ^-1): 278nm (36700), 404nm (41500)

Fluorescent characteristics: λ _Em: 518nm

＜compound (IV-c) 〉

(1) fusing point: 211-223 ℃

(2) ¹H-NMR(CDCl ₃)：δ(ppm)1.27(6H，t)，3.47(4H，q)，6.68(2H，d)，745(2H，d)，7.49-7.54(1H，m)，7.67-7.71(1H，m)，7.95(1H，s)，8.08(1H，t)，8.13-8.21(3H，m)，8.26-8.37(4H，m)，8.48(1H，d)，9.02(1H，d)，9.87(1H，d)。

(3) infrared absorption spectrum (IR; KBr): 1521,1609cm ^-1

(4) ultimate analysis

C H N

Observed value (%) 86.59 5.37 5.52

Calculated value (%) 86.02 5.46 5.42

(5) photoabsorption and fluorescent characteristics

(the measurement solvent: 1, the 4-dioxane)

Light absorption characteristics; λ _Max(ε _Max/ dm ³Mol ^-1Cm ^-1): 273nm (39200), 395nm (33300)

Fluorescent characteristics: λ _Em: 520nm

Synthesizing of synthetic embodiment 8 compounds (IV-d)

Except replace the 1-pyrene formaldehyde among the synthetic embodiment 7 with 9-anthracene aldehyde, carry out obtaining compound (IV-d) as synthetic embodiment 7 identical operations.

The analytical results of compound (IV-d) is as follows.

(1) fusing point: 178-180 ℃

(2) ¹H-NMR (acetone-d ⁶): δ (ppm) 1.23 (6H, t), 3.50 (4H), 6.90 (2H, d), 7.42 (2H, d), 7.57-7.64 (5H, m), 7.69-7.73 (1H, m), 7.89 (1H, s), 8.13-8.18 (3H, m), 8.22-8.26 (2H, m), 8.32-8.34 (1H, m), 8.91 (1H, s).

(3) infrared absorption spectrum (IR; KBr): 1521,1609cm ^-1

(4) ultimate analysis

C H N

Observed value (%) 85.34 5.73 5.69

Calculated value (%) 85.60 5.77 5.85

(5) photoabsorption and fluorescent characteristics

(the measurement solvent: 1, the 4-dioxane)

Light absorption characteristics; λ _Max(ε _Max/ dm ³Mol ^-1Cm ^-1): 333nm (12800), 350nm (12900), 371nm (12800), 386nm (12800),

Fluorescent characteristics: λ _Em: 547nm

The photoabsorption of following formula (III-e) compound and fluorescent characteristics (the measurement solvent: 1, the 4-dioxane) be:

＜compound (III-e) 〉

Light absorption characteristics;

λ _max(ε _max/dm ³mol ^-1cm ^-1)：385nm(21800)

Fluorescent characteristics; λ _Em: 513nm

Synthesizing of synthetic embodiment 9 compounds (I-d)

Following formula: compound (I-d) (9-(cyclohexyl methyl-hexyl-amino) benzo [b] naphtho-[1,2-d] furans-5,6-diketone) is synthetic with following method.

With 1,2-naphthoquinones-4-sodium sulfonate (1.0g, 3.84 * 10 ^-3Mol), 3-(cyclohexyl methyl-hexyl-amino) phenol (1.11g, 3.84 * 10 ^-3Mol) and CuCl ₃(0.52g, 3.84 * 10 ^-3Mol) be dissolved in the 15ml acetate, this solution heats and refluxed 3 hours in 40 ℃.After reaction is finished,, further add the dichloromethane extraction product to wherein adding entry.The separate dichloromethane layer and wash with water after concentrate, residual solution is with silicagel column (developping agent: dichloromethane/ethyl acetate=20/1) handle to separate and to purify, obtain the green flour powder crystalline compounds (I-d) of 0.135g (productive rate 8%).

Compound (I-d) analytical results (Mw=433.25) is as follows.

(1) fusing point :-

(2) ¹H-NMR (acetone-d ⁶): δ (ppm) 0.89-0.94 (5H, m), 1.34-1.40 (11H, m), 1.66-1.83 (6H, m), 3.34 (2H, d), 3.57 (2H, t), 6.84 (1H, d), 7.07 (1H, dd), 7.55 (1H, td), 7.78 (1H, td), 8.04 (1H, dd), 8.14 (1H, d), 8.23 (1H, d).

Synthesizing of synthetic embodiment 10 compounds (V-d)

Following formula: compound [in formula V, R ¹=hexyl, R ²Substituting group=CN of=cyclohexyl methyl, X=O, Y=O, Ar=phenyl ring and Ar] synthesize with following method.

Aforesaid compound (I-d) (9-(cyclohexyl methyl-hexyl-amino) benzo [b] naphtho-[1,2-d] furans-5,6-diketone) (0.135g, 3.04 * 10 ^-4Mol) with to cyanobenzaldehyde (0.048g, 3.66 * 10 ^-4Mol) be dissolved in the acetate of 20ml, to wherein adding ammonium acetate (0.375g, 4.86 * 10 ^-3Mol), in 90 ℃ of reactions 10 hours.After reaction is finished,, further add the dichloromethane extraction product to wherein adding entry.The separate dichloromethane layer and wash with water after concentrate, residual solution is with silicagel column (developping agent: methylene dichloride) handle to separate and to purify, obtain the yellow crystals compound (V-d) of 0.04g (productive rate 23.5%).

Compound (V-d) analytical results (Mw=533.31) is as follows.

(1) fusing point :-

(2) ¹H-NMR (acetone-d ⁶): δ (ppm) 0.89-0.96 (5H, m), 1.29-1.48 (11H, m), 1.61-1.89 (6H, m), 3.36 (2H, d), 3.54 (2H, t), 7.01 (1H, dd), 7.07 (1H, d), 7.65-7.68 (1H, m), and 7.74-7.81 (1H, m), 8.06-8.08 (2H, m), 8.32 (1H, d), 8.52-8.54 (2H, m), 8.65 (1H, d), 8.76 (1H, d).

Synthesizing of synthetic embodiment 11 Ben Ji naphthoxazole fluorochromes

[compound 1; In formula (III), R ¹=R ²Substituting group=CN of=ethyl, Y=O, Ar=phenyl ring and Ar],

[compound 2; In formula (IV), R ¹=R ²Substituting group=CN of=ethyl, Y=O, Ar=phenyl ring and Ar],

Compound 1 compound 2

4-[4-(diethylamino) phenyl]-1, the 2-naphthoquinones (2.00g, 5.54mmol), to cyanobenzaldehyde (0.73g, 5.54mmol) and ammonium acetate (6.82g, 88.4mmol are dissolved in the 59ml acetate, and reflux to stir 110 minutes in 80 ℃.After reaction was finished, solution neutralized with aqueous sodium carbonate, added the dichloromethane extraction organism.Wash dichloromethane layer with water, and drying under reduced pressure, (developping agent: methylene dichloride: ethyl acetate=10: 1) processing is to separate and to purify with silicagel column for resistates.Obtain the Powdered crystal of compound 1 (0.82g, productive rate 35.7%) and compound 2 (0.59g, productive rate 25.4%).

Synthetic embodiment 12

(1) 4-[4-(dibutylamino)-2-hydroxyphenyl]-1,2-naphthoquinones (intermediate 1) synthetic

With 1, and 2-naphthoquinones-4-sodium sulfonate (1.0g, 3.84mmol), N, N-dibutyl-3-amino-phenol (1.28g, 4.01mmol) and NiCl ₂(0.5g 3.84mmol) is dissolved in the 45ml dimethyl formamide (DMF), heats and stirs 3 hours at 50 ℃.After reaction finishes, will pour in the liquid in the ion exchanged water of 300ml with filtering precipitate.With methylene dichloride extraction product from filtrate, decompression concentrates this liquid down, and (developping agent: dichloromethane/ethyl acetate=20/1) processing is to separate and to purify with silicagel column for residual liquid.Obtain 4-[4-(dibutylamino)-2-hydroxyphenyl of blue powder shape crystal 0.77g (productive rate 53.1%)]-1,2-naphthoquinones (intermediate 1).

(2) compound 6 and 7 synthetic

(2.07g, 5.49mmol) (995mg, 5.49mmol are dissolved in the 60ml methyl-sulphoxide (DMSO), heat and stir 11 hours in 100 ℃ with Glacial acetic acid copper with intermediate 1.After reaction finishes, reaction product is poured in the distilled water of 400ml, and (developping agent: dichloromethane/ethyl acetate=10/1) processing is to separate and to purify with silicagel column with filtering precipitate.Obtain the compound 6 of the Powdered crystal 0.22g of purple (productive rate 10.4%) and the compound 7 of blue powder shape crystal 1.27g (productive rate 61.7%).

Intermediate 1 compound 6 compounds 7

Synthesize embodiment 13 compound 8[in formula (VII), R ¹=R ²=normal-butyl, X=O, Y=O, and Ar=anthracene nucleus] synthetic

(1.5g, 4.00mmol) (0.98g 4.79mmol) is dissolved in the acetate of 120ml, and (4.93g 64.0mmol), reacted 15 hours in 105 ℃ to wherein adding ammonium acetate with 9-anthracene aldehyde with compound 7.Reaction to wherein adding entry, further adds methylene dichloride with extraction product after finishing.The separate dichloromethane layer washes the back with water and concentrates, and (developping agent: methylene dichloride) processing is to separate and to purify with silicagel column for residual solution.Obtain the compound 8 of red crystals 0.91g (productive rate 46.7%) thus.

Compound 8

Synthesize embodiment 14 compound 9[in formula (VII), R ¹=R ²=normal-butyl, X=O, Y=O, and Ar=pyrene ring] and compound 10[in formula (VIII), R1=R2=normal-butyl, X=O, Y=O, and Ar=pyrene ring] synthetic

(1.5g, 4.00mmol) (1.10g 4.79mmol) is dissolved among the acetcompound 8ml, and (4.93g 63.9mmol), reacted 15 hours in 100 ℃ to wherein adding ammonium acetate with the 1-pyrene formaldehyde with compound 7.Reaction to wherein adding entry, further adds methylene dichloride with extraction product after finishing.The separate dichloromethane layer washes the back concentrating under reduced pressure with water, and (developping agent: dimethylbenzene/acetate=20/1) processing is to separate and to purify with silicagel column for residual solution.Obtain the compound 9 (naphthoxazole derivatives of orange crystal 1.12g (productive rate 49.4%) thus) and the compound 10 of yellow crystals 0.82g (productive rate 36.2%).

Compound 9 compounds 10

Synthesize embodiment 15 compound 11[in formula (VII), R ¹=R ²Substituting group=CN of=normal-butyl, X=O, Y=O, Ar=phenyl ring and Ar], compound 12[in formula (VIII), R ¹=R ²Substituting group=CN of=normal-butyl, X=O, Y=O, Ar=phenyl ring and Ar] and compound 13[in formula (VII), R ¹=R ²Substituting group=CN of=normal-butyl, X=O, Y=NH, Ar=phenyl ring and Ar] synthetic

(0.176g, 0.47mmol) and to cyanobenzaldehyde (0.61g 0.47mmol) is dissolved in the acetate of 8ml, and (0.578g 7.5mmol), reacted 7 hours in 80 ℃ to wherein adding ammonium acetate with compound 7.After reaction finished, reaction product concentrating under reduced pressure and with the aqueous sodium carbonate neutralization was used the dichloromethane extraction product.The separate dichloromethane layer washes the back concentrating under reduced pressure with water, and (developping agent: methylene dichloride) processing separates residual solution with silicagel column.Obtain the compound 13 of orange crystal 0.074g (productive rate 32%) thus, and the mixture of compound 11 and 12.Compound 11 and 12 mixture are with silicagel column (developping agent: dimethylbenzene/acetate=30/1) handle to separate and to purify.Obtain the compound 11 of orange crystal 0.02g (productive rate 9%) and the compound 12 of yellow crystals 0.019g (productive rate 8%) thus.

Compound 11 compounds 12 compounds 13

Synthesize embodiment 16 compound 14[in formula (VII), R ¹=R ²Substituting group=OC of=normal-butyl, X=O, Y=O, Ar=phenyl ring and Ar ₂H ₅] synthetic

With compound 7 (2.0g, 5.3mmol) and p-ethoxybenzaldehyde (0.96g 6.39mmol) is dissolved in the acetate of 60ml, to wherein add ammonium acetate (6.56g, 84.3mmol), in 100 ℃ the reaction 24 hours.After reaction finished, reaction product concentrating under reduced pressure and with the aqueous sodium carbonate neutralization further added methylene dichloride with extraction product.The separate dichloromethane layer washes the back concentrating under reduced pressure with water, and (developping agent: methylene dichloride) processing is to separate and to purify with silicagel column for resistates.Obtain the compound 14 of yellow crystals 0.978g (productive rate 36.5%) thus.

Compound 14

Synthesize embodiment 17 compound 15[in formula (VIII), R ¹=R ²Substituting group=F of=normal-butyl, X=O, Y=O, Ar=phenyl ring and Ar] synthetic

(1.50g, 4.00mmol) (0.56g 4.51mmol) is dissolved in the acetate of 70ml, and (4.93g 63.9mmol), reacted 3 hours in 90 ℃ to wherein adding ammonium acetate with the 4-fluorobenzaldehyde with compound 7.After reaction finishes, reaction product concentrating under reduced pressure and with aqueous sodium carbonate neutralization, product dichloromethane extraction.The separate dichloromethane layer washes the back concentrating under reduced pressure with water, and (developping agent: dimethylbenzene/acetate=20/1) processing is to separate and to purify with silicagel column for resistates.Obtain the compound 15 of 0.22g (productive rate 11.8%) thus.

Compound 15

Embodiment 1-3

(A) fluorochrome as shown in table 1 below respectively, (B) adhesive material, (C) adhesive resin, (D) have the monomer and/or the oligopolymer of the ethylenic unsaturated group of optical polymerism, compound and other component (comprising solvent) of (E) having epoxide group are used to prepare the off-color material composition.

Table 1

	Embodiment 1	Embodiment 2	Embodiment 3
	Embodiment 1	Embodiment 2	Embodiment 3	Fluorochrome (A component)	Compound 1 0.072g	Compound (V-a) 0.034g	Compound (V-a) 0.034g rhodamine 6G 0.017g rhodamine B 0.017g
Adhesive resin (C component)	Benzyl methacrylate-Sipacril 2739OF (Mw=27,000, q=0.80) 1.9g	Methyl methacrylate-Sipacril 2739OF (Mw=25,000, q=0.85) 1.9g	With embodiment 2	Fluorochrome (A component)	Compound 1 0.072g	Compound (V-a) 0.034g
Adhesive resin (C component)			With embodiment 2	Monomer/oligomer (D component)	Six vinylformic acid dipentaerythritol ester (Aronix M-400 is produced by Toa Gosei) 1.5g	Trimethyol propane triacrylate (Aronix M-309 is produced by Toa Gosei) 1.4g	With embodiment 2
Epoxy compounds (E component)	Cresol phenolic resin varnish type epoxy resin (ECN 1299, produced by Asahi Kasei) 0.20g	Do not have	Do not have	Monomer/oligomer (D component)			With embodiment 2
Epoxy compounds (E component)		Do not have	Do not have	Other component	The 2-acetoxyl group-(Irgacure 907 for 1-ethyl propyl ether (solvent) 2.5g pimelinketone (solvent) 3.0g Photoepolymerizationinitiater initiater, produce by Ciba Specialty Chemicals), 0.035g	The 2-acetoxyl group-(Irgacure 907 for 1-ethyl propyl ether (solvent) 2.4g pimelinketone (solvent) 3.0g Photoepolymerizationinitiater initiater, produce by Ciba Specialty Chemicals), 0.034g	With embodiment 2

The off-color material composition that obtains thus is used for the substrate of glass at 2.5cm * 5cm, uses the spin coating thin films.This film is produced under the rotational time condition of the spin coating revolution of 1000rpm and 10 seconds, and in 120 ℃ of drying treatment 2 minutes.Afterwards, use 300mJ/cm ²The UV radiation exposure, again in 200 ℃ of following thermal treatments 60 minutes, obtaining film thickness is 10 μ m or thinner optically variable films.

The optically variable films that obtains thus is used for (1) and estimates discoloration, and (2) use the blue EL element with 440nm wavelength peak to determine initial variable color efficient and tristimulus coordinates according to the exciting light prolonged exposure testing method on optically variable films (estimating the pigment sustainment rate).In addition, the blue EL element is measured its colourity and pigment sustainment rate then in 400 nits (nit) irradiation 1000 hours.It the results are shown in table 3.

Comparative example 1 and 2

The compound and other component (comprising solvent) that use fluorochrome as shown in table 2 below, adhesive material (adhesive resin and have the monomer and/or the oligopolymer of the ethylenic unsaturated group of optical polymerism), have an epoxide group prepare the off-color material composition.

Table 2

	The comparative example 1	The comparative example 2
	The comparative example 1	The comparative example 2	Fluorochrome (A component)	Coumarin 6 0.034g	Coumarin 6 0.034g rhodamine 6G 0.017g rhodamine B 0.017g
Adhesive resin (C component)	With embodiment 2	With embodiment 2	Fluorochrome (A component)	Coumarin 6 0.034g	Coumarin 6 0.034g rhodamine 6G 0.017g rhodamine B 0.017g
Adhesive resin (C component)	With embodiment 2	With embodiment 2	Monomer and/or oligopolymer (D component)	With embodiment 2	With embodiment 2
Epoxy compounds (E component)	Do not have	Do not have	Monomer and/or oligopolymer (D component)	With embodiment 2	With embodiment 2
Epoxy compounds (E component)	Do not have	Do not have	Other component	With embodiment 2	With embodiment 2

Use the off-color material composition that so obtains, obtain optically variable films, and determine its initial variable color efficient and tristimulus coordinates with the method identical with embodiment 1-3.In addition, measure its postradiation colourity and pigment sustainment rate.It the results are shown in table 3.

Table 3

	Initial variable color efficient (%)	Colourity (initially)	Colourity (after rayed)	Pigment sustainment rate (%)
	Initial variable color efficient (%)	Colourity (initially)	Colourity (after rayed)	Pigment sustainment rate (%)	Embodiment 1	49.6	0.23，0.63	0.22，0.62	72.7
Embodiment 2	50.3	0.25，0.65	0.23，0.63	78.3	Embodiment 1	49.6	0.23，0.63	0.22，0.62	72.7
Embodiment 2	50.3	0.25，0.65	0.23，0.63	78.3	Embodiment 3	19.2	0.64，0.35	0.63，0.36	79.1
The comparative example 1	52.0	0.23，0.63	0.20，0.60	49.3	Embodiment 3	19.2	0.64，0.35	0.63，0.36	79.1
The comparative example 1	52.0	0.23，0.63	0.20，0.60	49.3	The comparative example 2	19.0	0.64，0.35	0.61，0.37	62.1

As shown in table 3, in comparative example 1 and 2, initial variable color efficient is compared with embodiment 1-3 and is remained unchanged, but the pigment sustainment rate significantly is lower than embodiment 1-3, and the color change behind the pre-irradiation is very big.

In addition, in comparative example's off-color material composition, the crystal of coumarin 6 produces deposition (5 ℃ of refrigerators) in storage.

Embodiment 4-13

With (A) fluorochrome as shown in table 4 below, (B) adhesive material, (C) adhesive resin (D) has the monomer and/or the oligopolymer of the ethylenic unsaturated group of optical polymerism, and compound and other component (comprising solvent) of (E) having epoxide group are used for preparing the off-color material composition.

Table 4

	Embodiment 4	Embodiment 5	Embodiment 6
	Embodiment 4	Embodiment 5	Embodiment 6	Pigment (A component)	Compound 11 0.0018g compounds 12 0.0018g	Compound 10 0.0035g	Compound 9 0.0035g
Adhesive resin (C component)	Methyl methacrylate-Sipacril 2739OF (Mw=25,000, q=0.85) 0.40g	Benzyl methacrylate-Sipacril 2739OF (Mw=27,000, q=0.80) 0.40g	With embodiment 4	Pigment (A component)	Compound 11 0.0018g compounds 12 0.0018g	Compound 10 0.0035g	Compound 9 0.0035g
Adhesive resin (C component)			With embodiment 4	Monomer/oligomer (D component)	Pentaerythritol triacrylate (Aronix M-305 is produced by Toa Gosei) 0.29g	Trimethyol propane triacrylate (Aronix M-309 is produced by Toa Gosei) 0.29g	With embodiment 4
Epoxy compounds (E component)	Do not have	Do not have	Do not have	Monomer/oligomer (D component)			With embodiment 4
Epoxy compounds (E component)	Do not have	Do not have	Do not have	Other component	The 2-acetoxyl group-(Irgacure 907 for 1-ethoxy propane (solvent) 0.75g cyclohexanone (solvent) 0.56g Photoepolymerizationinitiater initiater; Produced by Ciba Specialty Chemicals), 0.0063g	With embodiment 4	With embodiment 4

Table 5

Embodiment	Embodiment 7	Embodiment 9
Embodiment	Embodiment 7	Embodiment 9	Pigment (A component)	Compound 13 0.0035g	Compound 9 0.0060g
Adhesive resin (C component	With embodiment 4	Methyl methacrylate-Sipacril 2739OF (Mw=25,000, q=0.87)) 0.40g	Pigment (A component)	Compound 13 0.0035g	Compound 9 0.0060g
Adhesive resin (C component	With embodiment 4		Monomer/oligomer (D component	With embodiment 4	With embodiment 4
Epoxy compounds (E component)	Do not have	Cresol phenolic resin varnish type epoxy resin (ECN 1299, produced by Asahi Kasei) 0.15g	Monomer/oligomer (D component	With embodiment 4	With embodiment 4
Epoxy compounds (E component)	Do not have		Other component	With embodiment 4	With embodiment 4

Table 6

	Embodiment 9	Embodiment 10	Embodiment 11
	Embodiment 9	Embodiment 10	Embodiment 11	Pigment (A component)	Compound (V-d) 0.0035g	Compound (V-c) 0.0021g	Compound (III-c) 0.0026g
Adhesive resin (C component)	Methyl methacrylate-Sipacril 2739OF (Mw=25,000, q=0.87) 0.40g	With embodiment 9	Benzyl methacrylate-Sipacril 2739OF (Mw=27,000, q=0.80) 0.40g	Pigment (A component)	Compound (V-d) 0.0035g	Compound (V-c) 0.0021g	Compound (III-c) 0.0026g
Adhesive resin (C component)		With embodiment 9		Monomer oligopolymer (D component)	Pentaerythritol triacrylate (AronixM-305 is produced by Toa Gosei) 0.29g	With embodiment 9	Six vinylformic acid dipentaerythritol ester (Aronix M-400 is produced by Toa Gosei) 0.39g
Epoxy compounds (E component)	Do not have	Do not have	Cresol phenolic resin varnish type epoxy resin (ECN 1299, produced by Asahi Kasei) 0.023g	Monomer oligopolymer (D component)		With embodiment 9
Epoxy compounds (E component)	Do not have	Do not have		Other component	The 2-acetoxyl group-(Irgacure 907 for 1-ethyl propyl ether (solvent) 0.75g tetrachloroethane (solvent) 0.56g Photoepolymerizationinitiater initiater, produce by Ciba Specialty Chemicals), 0.0063g	With embodiment 9	The 2-acetoxyl group-(Irgacure 907 for 1-ethoxy propane (solvent) 0.86g tetrachloroethanes (solvent) 0.28g Photoepolymerizationinitiater initiater; Produced by Ciba Specialty Chemicals), 0.0044g

Table 7

Embodiment	Embodiment 12	Embodiment 13
Embodiment	Embodiment 12	Embodiment 13	Pigment (A component)	Compound 8 0.010g	With embodiment 9
Adhesive resin (C component)	Polycarbonate (Mw=20,000) 1.99g		Pigment (A component)	Compound 8 0.010g
Adhesive resin (C component)	Polycarbonate (Mw=20,000) 1.99g	Monomer/oligomer (D component)	Do not have
Epoxy compounds (E component)	Do not have	Monomer/oligomer (D component)	Do not have
Epoxy compounds (E component)	Do not have	Other component	Toluene (solvent) 8.0g

The off-color material composition that use obtains in embodiment 4-13, on 2.5cm * 5cm substrate of glass by the spin coating thin films.This film is produced under the rotational time condition of the spin coating revolution of 1000rpm and 10 seconds, and in 120 ℃ of drying treatment 2 minutes.

Afterwards, the film 300mJ/cm that in embodiment 4-11, produces ²The UV radiation exposure, again in 200 ℃ of following thermal treatments 60 minutes, obtaining thickness is 10 μ m or thinner optically variable films.The film that makes among the embodiment 12 is only in 200 ℃ of following thermal treatments 60 minutes.In addition, the off-color material composition for preparing among the embodiment 13 is coated on the commercially available blue-led element, and in 70 ℃ of dryings.

Use the optically variable films that so obtains to be used for (1) and estimate discoloration, and (2) use the blue EL element with 470nm wavelength peak to determine initial variable color efficient and tristimulus coordinates according to the exciting light prolonged exposure survey method on optically variable films (estimating the pigment sustainment rate).In addition, the blue EL element is measured its colourity and pigment sustainment rate then in 400 nits (nit) irradiation 1000 hours.It the results are shown in table 8.

Table 8

	Initial variable color efficient (%)	Colourity (initially)	Colourity (after rayed)	Pigment sustainment rate (%)
	Initial variable color efficient (%)	Colourity (initially)	Colourity (after rayed)	Pigment sustainment rate (%)	Embodiment 4	51.0	0.23，0.63	0.21，0.61	57.9
Embodiment 5	48.5	0.23，0.64	0.21，0.62	57.5	Embodiment 4	51.0	0.23，0.63	0.21，0.61	57.9
Embodiment 5	48.5	0.23，0.64	0.21，0.62	57.5	Embodiment 6	48.7	0.24，0.63	0.21，0.61	58.8
Embodiment 7	49.9	0.22，0.63	0.21，0.62	65.8	Embodiment 6	48.7	0.24，0.63	0.21，0.61	58.8
Embodiment 7	49.9	0.22，0.63	0.21，0.62	65.8	Embodiment 8	51.1	0.24，0.62	0.22，0.61	58.2
Embodiment 9	51.5	0.22，0.62	0.20，0.60	75.8	Embodiment 8	51.1	0.24，0.62	0.22，0.61	58.2
Embodiment 9	51.5	0.22，0.62	0.20，0.60	75.8	Embodiment 10	51.9	0.23，0.63	0.21，0.61	78.3
Embodiment 11	47.9	0.20，0.60	0.20，0.60	79.8	Embodiment 10	51.9	0.23，0.63	0.21，0.61	78.3
Embodiment 11	47.9	0.20，0.60	0.20，0.60	79.8	Embodiment 12	47.6	0.22，0.62	0.21，0.61	73.9

The off-color material composition that obtains by embodiment 4-12 can be in 5 ℃ refrigerator stable storage.In addition, in embodiment 13, can be visually observed and send green glow.

Industrial applicibility

According to the present invention, a kind of novel assorted polynuclear compound that can be used as fluorescent material can be provided, it is used for dispersed dye, the pigment of spray ink Printing and organic electroluminescent device or as the organic fluorescence pigment, this pigment has the ability that forms Runge-Kutta integration, fluorescence property and can wherein contain the Solid character (color harmony fluorescence property) of various organic low molecular compounds (organic guest molecule) by making to change pigment to a great extent, and be suitable for multiple application, and the pigment that comprises above-mentioned assorted polynuclear compound can be used for various uses with the pigment or the dyestuff that contain above-mentioned assorted polynuclear compound, is particularly suitable for the material as the off-color material composition.

Even the optically variable films that is obtained by off-color material composition of the present invention is after long-time the use, discoloration can not damage yet, and can prevent because pigment deposition causes in storing can't use.

Therefore, optically variable films of the present invention is suitable for the optically variable films as full color organic electroluminescent device, LED element etc. most.

Claims

1, the represented assorted polynuclear compound of following formula (I):

Wherein, R ¹And R ²Representative independently of one another can have the heteroaryl that the alkyl of the substituent 1-10 of a having carbon atom, the aralkyl that can have the substituent 7-30 of a having carbon atom, the aryl that can have the substituent 6-20 of a having carbon atom maybe can have the substituent 5-20 of a having carbon atom, and they can be connected to each other with the formation ring texture or can be with bonding the phenyl ring of nitrogen-atoms form ring texture; And

X represention oxygen atom, sulphur atom ,-NH-or-NR ³-(R ³Representative can have the heteroaryl that the alkyl of the substituent 1-10 of a having carbon atom, the aryl that can have the substituent 6-20 of a having carbon atom maybe can have the substituent 5-20 of a having carbon atom).

2, the represented assorted polynuclear compound of following formula (II):

3, the represented assorted polynuclear compound of following formula (III):

Wherein, R ¹And R ²Representative independently of one another can have the heteroaryl that the alkyl of the substituent 1-10 of a having carbon atom, the aralkyl that can have the substituent 7-30 of a having carbon atom, the aryl that can have the substituent 6-20 of a having carbon atom maybe can have the substituent 5-20 of a having carbon atom, and they can be connected to each other with the formation ring texture or can be with bonding the phenyl ring of nitrogen-atoms form ring texture;

Y represention oxygen atom, sulphur atom or-NR ⁴-(R ⁴Representative can have the heteroaryl that the alkyl of the substituent 1-10 of a having carbon atom, the aryl that can have the substituent 6-20 of a having carbon atom maybe can have the substituent 5-20 of a having carbon atom); And on behalf of the aryl that can have the substituent 6-20 of a having carbon atom, Ar maybe can have the heteroaryl of the substituent 5-20 of a having carbon atom.

4, the represented assorted polynuclear compound of following formula (IV):

5, the following represented assorted polynuclear compound of formula V:

Y represention oxygen atom, sulphur atom ,-NH-or-NR ⁴-(R ⁴Representative can have the heteroaryl that the alkyl of the substituent 1-10 of a having carbon atom, the aryl that can have the substituent 6-20 of a having carbon atom maybe can have the substituent 5-20 of a having carbon atom); And on behalf of the aryl that can have the substituent 6-20 of a having carbon atom, Ar maybe can have the heteroaryl of the substituent 5-20 of a having carbon atom.

6, the represented assorted polynuclear compound of following formula (VI):

X represention oxygen atom, sulphur atom ,-NH-or-NR ³-(R ³Table can have the heteroaryl that the alkyl of the substituent 1-10 of a having carbon atom, the aryl that can have the substituent 6-20 of a having carbon atom maybe can have the substituent 5-20 of a having carbon atom);

7, the represented assorted polynuclear compound of following formula (VII):

8, the represented assorted polynuclear compound of following formula (VIII):

9, a kind of off-color material composition, it comprise (A comprises the fluorochrome of at least a assorted polynuclear compound by following formula (III)-(VIII) representative, and (B) adhesive material:

Y represention oxygen atom, sulphur atom ,-NH-or-NR ⁴-(R ⁴Representative can have the heteroaryl that the alkyl of the substituent 1-10 of a having carbon atom, the aryl that can have the substituent 6-20 of a having carbon atom maybe can have the substituent 5-20 of a having carbon atom); Condition is in formula (III) with (IV), Y represention oxygen atom, sulphur atom or-NR ⁴-; And

10, off-color material composition as claimed in claim 9, wherein above-mentioned (B) adhesive material is the light reaction resin.

11, off-color material composition as claimed in claim 9, wherein above-mentioned (B) adhesive material is a thermosetting resin.

12, off-color material composition as claimed in claim 9, wherein above-mentioned (B) adhesive material is a thermoplastic resin.

13, off-color material composition as claimed in claim 9, wherein above-mentioned (B) adhesive material comprise (C) methacrylic ester-Sipacril 2739OF and (D) have the monomer and/or the oligopolymer of the ethylenic unsaturated group of optical polymerism.

14, off-color material composition as claimed in claim 13, wherein above-mentioned (B) adhesive material is with respect to (C) methacrylic ester-Sipacril 2739OF of per 100 weight parts, and (D) that contain the 10-200 weight part has the monomer and/or the oligopolymer of the ethylenic unsaturated group of optical polymerism.

15, off-color material composition as claimed in claim 9, it comprises that further (E) has the compound of epoxide group.

16, off-color material composition as claimed in claim 15, based on the total amount of the solid matter of above-mentioned off-color material composition, it comprises that 0.5-15 weight % (E) has the compound of epoxide group.

17, off-color material composition as claimed in claim 9, based on the total amount of the solid matter of above-mentioned off-color material composition, it comprises above-mentioned (A) component of 0.1-10 weight %.

18, off-color material composition as claimed in claim 9, it further comprises fluorochrome, this fluorochrome comprises at least a fluorochrome that is selected from rhodamine base fluorochrome.

19, comprise optically variable films as each described off-color material composition of claim 9-18.

20, use as claim 9,10 and the optically variable films of each described off-color material composition of 13-18 by photolithography formation.

21, optically variable films as claimed in claim 19, its light that absorbs light source has more long wavelength's light to send.

22, optically variable films as claimed in claim 21, wherein above-mentioned light source are organic electroluminescent device or LED element.

23, comprise pigment as each described assorted polynuclear compound of claim 1-8.

24, comprise pigment or dyestuff as each described assorted polynuclear compound of claim 1-8.