CN1893140B - A film manufacturing method - Google Patents
A film manufacturing method Download PDFInfo
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- CN1893140B CN1893140B CN 200610075547 CN200610075547A CN1893140B CN 1893140 B CN1893140 B CN 1893140B CN 200610075547 CN200610075547 CN 200610075547 CN 200610075547 A CN200610075547 A CN 200610075547A CN 1893140 B CN1893140 B CN 1893140B
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Abstract
A film manufacturing method characterized in that the method comprises providing and coating a composition composed of at least one solvent of benzene derivative having at least one substituent which has 3 or more carbon atoms in total and organic EL material on the substrate, and heats treatment of the substrate thereafter.
Description
The application is application number the dividing an application for the PCT application in entering country's stage of " manufacturing approach of composition and film and function element and manufacturing approach thereof " that be CN00800987.2 (international filing date is on March 29th, 2000), denomination of invention.
Technical field
The present invention relates to a kind of composition that can stablize ejection (ejection composition) that is used to adopt blowoff to form the functional material graphic films, and adopt said composition to form the film manufacturing method of uniform films (functional membrane), and possess the function element that adopts the formed luminous material layer of foregoing, particularly be applicable to the function element such as organic EL (display element) and the manufacturing approach thereof of luminous demonstration purposes.
Background technology
In the past, functional material graphically carried out through photoetching process.Cost is high because this method exists, the shortcoming of complex procedures, makes functional material carry out composition so studying the blowoff that passes through easy and that might reduce cost recently.Particularly studying the method that adopts ink-jet printing apparatus.
For example, as the example of the fine composition that adopts ink-jet printing apparatus, can enumerate the example of the colour filter manufacturing of liquid crystal display body and function.This is a printing equipment of getting red, green, blue three color ink nozzles through having, gets red, green, blue dyestuff or pigment ink etc. aptly respectively, makes the example of colour filter.The normally water miscible polarity printing ink of the printing ink that this manufacturing approach adopted.Such water-based ink because drying causes spray nozzle clogging, in most cases adds the glycerine equal solvent for preventing.
Again for example; Employing is with luminescent material printing inkization such as organic fluorescence materials; Through ink-jet method this printing ink (composition) ejection is supplied with on the base material; Carry out the method for the moulding of luminescent material, developing and have the colour display device of this luminous material layer being seized on both sides by the arms the structure between anode and negative electrode, particularly adopt organic EL (electroluminescence) display unit of luminous organic material as luminescent material.
The making of this colour display device (organic EL display) can for example be made by following.
At first, fluorescent material is dissolved in makes printing ink in the appropriate solvent.With this printing ink (composition) ejection, to cover as this transparency electrode on the subsidiary transparency electrode base material of organic EL display anode.At this, electrode forms at single face, or has rectangle, inlays the graphics shape of shape etc., has that connect with the mains just can driven structure.Then, drying is removed printing ink solvent and is formed luminous material layer, makes the little metal of work function through methods such as vapor deposition, spraying platings afterwards, and for example, being deposited on this luminous material layer that metals such as silver, lithium, calcium, aluminium are suitable forms negative electrode.Like this, obtain having the display unit of this luminous material layer being seized on both sides by the arms structure between anode and negative electrode.
Have no making sheet, resource-saving, very excellent characteristic such as laborsaving by the formation method of the figure of in the past this ink jet printing method, its shortcoming is to be limited by the material that adopts in the composition (ejection composition) on the contrary.
For ink-jet method, as the solvent composition of ejection composition, for example use, ethanol, water equal solvent, but for functional material a little less than nonpolar or the polarity or polymer-function material (luminescent material etc.), be not dissolved in these solvents.And, also existence and water and alcohol reaction or because pure the decomposition, functional material such as can not use at shortcoming.
Also have,, using benzene,toluene,xylene etc. to dissolve well under the situation of solvent of non-polar material,, have the shortcoming that causes the spray orifice plug-hole easily owing to boiling point low (vapour pressure is high), be prone to dryly as the solvent of dissolving functional material.And when ejection or in the ejection caudacoria forming process,, reduce the temperature of ejection composition sometimes because the volatile zone of solvent is walked heat of gasification, promote functional material to separate out.In addition, be under the situation of multicomponent system at functional material, also exist to be separated, cause inhomogeneous, down to the shortcoming that can not accomplish the original effect of functional membrane.
Further, force to use, under the situation that the concentration of ejection composition is thickened, produce and separate out with plug-hole etc. at the little material of solubility that rigidly can not so simple use.For stoping under the plug-hole situation that concentration is thinning, for showing the characteristic of functional material, must repeatedly spray, existence needs to increase shortcomings such as process number.
The object of the present invention is to provide a kind ofly to substitute in the past that the photoetching process of functional material patterning process can adopt ink jet printing method, can use the material a little less than nonpolar or the polarity and be prone to the composition of the reactive explosive of reaction with the water capacity as functional material.
And another object of the present invention is to provide a kind of composition, and plug-hole when said composition can prevent to spray reaches stable ejection, being separated during the film in preventing to spray after the separating out and further prevent to spray of content forms.In addition, another purpose of the present invention is to provide function element (display element) and manufacturing approaches thereof such as the manufacturing approach of a kind of uniform films (functional membrane), a kind of organic EL.
Summary of the invention
The present invention achieves the above object through a kind of composition is provided; Said composition is characterised in that it is a kind ofly to have more than one substituting group by containing at least, and the composition that constitutes of the solvent that adds up to the benzene derivative more than 3 of this substituent carbon number and functional material.
And the present invention also provides a kind of manufacturing approach of film, is characterised in that to adopt foregoing to form.In addition, the present invention also provides a kind of function element and manufacturing approach thereof that adopts the formed luminous material layer of foregoing that between first and second electrode, possess.
Description of drawings
First figure is the oblique view of pattern ground expression as the manufacturing process of the organic EL of functional film that adopts the present composition and function element.Second figure is a part (substrate form operation～positive hole injection/transfer layer form operation) the simple sectional drawing of pattern ground expression as the manufacturing process of the organic EL of the function element that adopts the present composition.The 3rd figure is a part (luminescent layer form operation～sealing process) the simple sectional drawing of pattern ground expression as the manufacturing process of the organic EL of the function element that adopts the present composition.
Embodiment
Specify manufacturing approach and the function element and the manufacturing approach thereof of composition of the present invention and film below.
Composition of the present invention is characterised in that it is a kind ofly to have more than one substituting group by containing at least, and the composition that constitutes of the solvent that adds up to the benzene derivative more than 3 of this substituent carbon number and functional material.
In addition, this so-called " this substituent the total number of carbon atoms is more than 3 " be meant the whole the total number of carbon atoms of substituted substituting group on the benzene derivative (with) more than 3.Therefore, be 1 or 2 methyl or ethyl even for example have a substituent carbon number, the carbon number of substituting group addition with other becomes more than 3 so, all is included in the aforementioned benzene derivative of the present invention.
The aforementioned benzene derivative that composition of the present invention adopted is to have as aforementioned substituent more than 1.As this single substituting group; If whole substituent the total number of carbon atoms are more than 3; Do not have special limitation, for example can enumerate, the aliphatic alkyl of straight or branched, ester ring type alkyl and aromatic hydrocarbyl etc.; Further, also can contain hetero-atoms such as oxygen atom, nitrogen-atoms and sulphur atom in these alkyl.And the ring structures such as forming the cycloalkane ring that also can mutually combine between each substituting group.
And its total number of carbon atoms of aforementioned benzene derivative is as aforementioned more than 3, but considers from the dissolubility aspect that can further improve the functional material a little less than nonpolar or the polarity, preferably 3～12, more preferably 3～6.
Aforementioned benzene derivative is used for composition of the present invention as the solvent that contains it at least.As such solvent, can also be mixture promptly by a kind of single solvent of forming of aforementioned illustrative benzene derivative or by the mixed solvent of forming more than two kinds of this benzene derivative by the solvent beyond aforementioned benzene derivative and the aforementioned benzene derivative.
At this; As the solvent beyond the aforementioned benzene derivative; Has 1 above substituting group at xylenes, toluene etc.; This substituent the total number of carbon atoms is the benzene derivative of (less than 3) below 2, or outside the benzene compound of unsubstituted, can enumerate with the substituted benzene derivative of substituting group of carbon atoms not etc.
As the used functional material of composition of the present invention, there is not special limitation, even the reactive explosive of the material a little less than nonpolar or the polarity, Yi Yushui reaction also can use.As such functional material; Can adopt the material that adapts to purposes of the present invention; For example; That can enumerate has, and the precursor of luminescent materials such as organic EL Material, silica glass, colour filter are with conductive materials such as material, organo-metallic compound, dielectric or semi-conducting material etc., and preferred especially organic EL Material, the precursor of silica glass, colour filter are used material.
Composition of the present invention can be used for various uses, but is suitable for ink-jet method especially.
If use when the composition of above-mentioned benzene derivative of the present invention must be arranged, especially, it is wide that the soluble material selectivity becomes, and can prevent the drying in the ejection process at least, so that can stablize ejection, can obtain evenly, homogeneous and fine film (functional membrane).For making the film of this excellence, can be through aforementioned composition ejection of the present invention being supplied with and is beaten respectively after on the base material, again with this base material heat treatment (heating) etc.Particularly, can enumerate through blowoff composition of the present invention ejection is beaten respectively after on the substrate, again with the method for handling under the substrate temperature that temperature is high when extruding etc.General ejection temperature is a room temperature, ejection back heated substrates.Through such processing, spray the content quilt dissolving again of separating out owing to the solvent evaporates temperature reduces the back, nothing is separated, and can obtain film even, homogeneous.
The temperature of heat treated is not seen any effect near room temperature, effect occurring more than 40 ℃.If heating surpasses 200 ℃, the solvent evaporation effect becomes not to be had.Therefore, as the heat treated temperature, preferred 40 ℃～200 ℃.More preferably, therefore can obtain functional membrane more even, homogeneous 50 ℃～200 ℃ heating.Through the setting of such heat treated temperature, can obtain following effect.Particularly under the situation through ink-jet method ejection composition (printing ink), it is generally acknowledged the solvent vaporization, the temperature of droplets of ink descends, and content is separated out.The content of printing ink is under the situation that composition constitutes more than 2 kinds, changes to inhomogeneous mixed system from homogeneous mixture system sometimes.At this moment, in luminescent material, be separated, so that can not get available colourity, luminous efficiency etc. in homogeneous system.Therefore, handle through heat hot in the said temperature scope, the content of the composition that is sprayed is had the effect of further homogenizing by dissolving again.
And when the manufacturing of film, not only heat treatment (heating) also can be reduced pressure as required, pressurize or they is carried out with the heating combination.
For example, as the combination of decompression and heating, preferred removal of solvent under reduced pressure at once intactly after heat treated.Pressure when the decompression is more even from obtaining, the aspect of the functional membrane of homogeneous is considered, preferably 20 * 10
-3Below the mmHg (Torr).Through such operation, can prevent being separated of content when composition concentrates.That is, when in a single day the content of dissolving was concentrated again, a gas removed and desolvates; Immobilized substance thing equably before the uneven homogenize; The uneven homogenize (being separated) of content can be prevented thus,, the luminous intensity and the colourity of desirable purpose originally can be obtained at formed luminous material layer.
And about begin the time when beginning to reduce pressure from heat treated, set according to spray volume and properties of materials.
Make employed blowoff when the above-mentioned film (functional membrane) as composition of the present invention being used for ink-jet method, can enumerate ink-jet printing apparatus, distributor etc., preferred ink-jet printing apparatus.
And when using composition of the present invention, can obtain the particularly function element of useful excellences such as organic EL in luminous demonstration purposes.Particularly; Can obtain in the display unit (preferably between aforementioned first electrode and aforementioned luminous material layer, injection/transfer layer formed device in positive hole being set further) that possesses the luminous material layer that adopts aforementioned composition formation of the present invention between first and second electrode.
At this, so-called positive hole injection/transfer layer is meant to have from holes such as positive holes injects inner function, also has simultaneously with the layer of holes such as positive hole in the function of delivered inside.Through so positive hole injection/transfer layer is set, particularly because the raising of element characteristics such as the luminous efficiency of organic EL, life-span is preferred.
In addition, as function element, can enumerate thin, light, the low power consumption of adopting luminous organic material, the so-called multicoloured display element of high angle of visibility; For example; Except that above-mentioned organic EL, have a plurality of pixels, display of switch elements such as thin-film transistor etc. is set on each pixel.
When the display unit of making as this excellent function element, preferably wait according to the following steps and carry out.Promptly; On base material with first electrode, optionally supply with aforementioned composition of the present invention, and preferred heating or decompression, pressurization or they and heating combination handled; Form the luminescent material layer pattern; Then on this luminescent material layer pattern, forming second electrode (is preferably having on the aforementioned substrates of first electrode, is adopting the solution that contains polar solvent, form positive hole injection/transfer layer with ink-jet method after; On this positive hole injection/transfer layer, preferred especially the employing uses the solution of non-polar solven to form aforementioned luminescent material layer pattern).Like this, can obtain excellent organic EL etc.
As the luminous material layer that adopts the functional membrane of the present composition in the function element, preferably the manufacturing approach by aforementioned films (functional membrane) forms.
Also have; As the solution that contains polar solvent (composition) that when forming positive hole injection/transfer layer, is adopted; For example can enumerate; Ethylene hydroxyl thiophene polythiophene class derivatives such as (Port リ ユ チ レ Application ジ オ キ シ チ オ Off エ Application) be will gather and, α-butyrolactone, N-methyl pyrrolidone, 1 will be engaged in, the solution in the gylcol ether isopolarity solvents such as 3-dimethyl-2-imidazolidinone and derivative thereof, carbitol acetate ester, butyl carbitol acetate ester etc. compositions such as polyvinyl sulfonic acids.Through adopting such polar solvent, can stop up and stable ejection by unlikely spray orifice, film forming is excellent, so be preferred.
Below, composition of the present invention is detailed by its embodiment preferred.
First embodiment
First embodiment of the present composition is the composition that is adopted when adopting blowoff to form the functional material graphic films, and it is by containing the composition that solvent that to have 1 above substituting group and this substituent carbon number sum be the benzene derivative more than 3 and functional material constitute at least.
Through this embodiment, can dissolve functional material nonpolar or that polarity is weak well, expanded functionality material chosen property; Simultaneously under the situation of using the low relatively solvent of vapour pressure; Consider that from slow dryness viewpoint the plug-hole in the time of can preventing the solvent ejection makes stable ejection become possibility; Particularly handle and the heating combination, can make when preventing to spray the back film forming content separate out and be separated and prove effective through back heating or pressurization or the decompression at once of heating back etc.
As be fit to first embodiment, contain the solvent that to have 1 above substituting group and this substituent carbon number sum be the benzene derivative more than 3 at least, can consider the mixed solvent of single solvent such as isopropylbenzene, cymol, cyclohexyl benzene, detergent alkylate, diethylbenzene, amylbenzene, diamyl benzene, butyl benzene, tetrahydronaphthalene and durol or these solvents.Perhaps also can in these single solvents or mixed solvent, suitably add xylenes, toluene and benzene etc.Through being employed in this illustrative single solvent of institute or mixed solvent, make dissolving the composition nonpolar or functional material that polarity is weak become possibility.That is, the change of material chosen property is big.Further, through adopting such single solvent or mixed solvent, can prevent plug-hole.
The boiling point of the benzene derivative that composition adopted of first embodiment is preferably more than 200 ℃.As such solvent, detergent alkylate, cyclohexyl benzene, tetrahydronaphthalene, diamyl benzene and amylbenzene etc. are arranged.Through adopting these solvents, can further prevent solvent evaporates, still preferred.
The benzene derivative of being adopted in the composition as first embodiment, preferred detergent alkylate.As detergent alkylate, both can be single dodecyl benzene, can also be mixture of isomers.
This solvent has boiling point more than 300 ℃, viscosity characteristic of (20 ℃) more than 6mPas, this single solvent can certainly, and, can prevent composition dries through adding other solvent, be preferred.And in above-mentioned solvent except that detergent alkylate ratio of viscosities less, therefore also can adjust viscosity through adding this solvent, so be very preferred.
As the functional material that is suitable for first embodiment, can consider organic EL Material.The organic EL Material that especially preferably constitutes by the material a little less than nonpolarity or the polarity.Also for example can consider, by (gathering) to penylene ethenylidene ((Port リ) パ ラ Off エ ニ レ Application PVC ニ レ Application) type, polyphenylene (Port リ Off エ ニ レ Application) type, gather EL material, other low molecular organic EL material that dissolves in benzene derivative and macromolecule organic EL Material etc. that fluorenes class, polyvinylcarbazole analog derivative are formed.Also for example might use rubrene 、 perylene, 9,10-diphenylanthrancene, tetraphenylbutadiene, naphthyridines ketone, (Na イ Le レ Star De), coumarin 6, quinoline a word used for translation ketone, polythiofuran derivative etc.And also might use for the electron transport property that shows the material around of body as organic EL, hole conveying property material.
Also have,, outside aforementioned organic EL Material, also can consider to be used for the polysilazane (for example, goods are fired in east), organic SOG material etc. of precursor substance of silex glass of the interlayer dielectric of semiconductor etc. more as the functional material that is suitable for first embodiment.
Further, as the functional material that forms the first embodiment composition, also preferred colour filter is used material.Use material as this colour filter; Can select Su Mika fast red dyestuff B (trade name; The Sumitomo Chemical system dye), card Yanaon Orange N GL (trade name, Japanese chemical drug system dye), the big sharp strong light blue-B various sublimation dye such as (names of an article, Mitsubishi changes into system dye) of liking to loose.
Further, also can adopt organo-metallic compound as functional material.So long as be dissolved in aforementioned solvents, be that what kind of functional material all possibly use as composition perhaps.
Through using the composition of first state, can make the functional membrane of the patterned film etc. of the functional material that adopts blowoff.The manufacture method of this functional membrane can be undertaken by the manufacturing approach of aforementioned films.That is, the ejection of the composition of first embodiment is supplied with and is beaten respectively after on the base material, again with this base material preferably 40 ℃～200 ℃ heat treated, can obtain functional membrane thus.In particular for first embodiment,, can obtain functional membrane more even, homogeneous, so more preferably through this heating-up temperature is set in 50～200 ℃.And for first embodiment, preferably when high-temperature process, heat while pressurize.Through such operation, the volatilization of solvent in the time of can postponing to heat, content dissolves and more becomes perfect.Its result can obtain functional membrane more even, homogeneous.Pressure when the pressurization, functional membrane aspect more even from obtaining, homogeneous is considered, preferably at 1520～76000mmHg (2～100 atmospheric pressure).
And for the heat treated of the composition of first embodiment, preferably before the composition bone dry through as aforesaid decompression etc. remove and desolvate.
Blowoff as the composition that is applicable to first state; Can adopt ink-jet printing apparatus and distributor etc.; And ink-jet printing apparatus is because its trickle property and correctness and more preferably, can make trickle functional membrane easy and at low cost through adopting this ink-jet printing apparatus.
Through using the composition of first embodiment; Can obtain display unit (preferably between aforementioned first electrode and aforementioned luminous material layer, injection/transfer layer formed display unit in positive hole being set) aptly as useful organic EL of aforementioned functional element etc.
Second embodiment
Second embodiment of the present composition is to contain the solvent that comprises detergent alkylate at least and the composition of at least a fluorenes family macromolecule derivative in the following compound 1 to 5.Promptly; Second embodiment is in composition of the present invention; As be fit to second embodiment of the invention, comprise the solvent that to have 1 above substituting group and this substituent carbon number sum be the benzene derivative more than 3 at least; Adopt the solvent that comprises detergent alkylate at least,, adopt at least a fluorenes family macromolecule derivative in the compound 1 to 5 as the functional material that is fit to second embodiment.
This embodiment is the preferred scheme of more aforementioned first embodiment, and the solvent that uses detergent alkylate and so on steam to force down is considered following result is proved effective from the viewpoint of slow dryness.That is, prevent the solvent plug-hole in when ejection, will stablize ejection and become possibility, particularly preferably be through after heating and pressurization or the decompression at once of heating back stated, can obtain not having and be separated and uniform film.
Embodiment of the present invention such as above-mentioned is than the preferred state of first embodiment, so the place about under this programme, not detailing, aforementioned first embodiment of suitable employing is detailed.
Compound 1
Compound 3
Compound 4
Compound 5
Second embodiment is detailed.The composition of this embodiment; Be through using detergent alkylate as its solvent; Under the situation of the ink composite when said composition is formed figure as ink-jet method, owing to show the slow dryness effect of this detergent alkylate, therefore; Can prevent over-drying when spraying from particularly can prevent the plug-hole in ink-spraying-head by ink-spraying-head.And, even also remaining in liquid state, ejection back ejecta is ejected on the material, reprocessing such as might heat.Further, the fluorenes family macromolecule derivative (compound 1～5) of above-mentioned ad hoc structure is used as luminescent material; Luminous intensity is high; And because a little less than the polarity, so to the detergent alkylate favorable solubility, through the combination of this luminescent material and solvent; Particularly, possibly carry out composition well as the organic EL display member of formation.
For the composition of second embodiment,, can in detergent alkylate, mix and use various second solvents that can dissolve luminescent material as solvent.The preferred mixing used the solvent of boiling point more than 140 ℃.As second solvent of this boiling point more than 140 ℃, can use cymol, tetrahydronaphthalene, isopropylbenzene, decahydronaphthalene, durene, cyclohexyl benzene, dihexyl benzene, durol and dibutyl benzene etc.Preferred especially the employing contained the solvent that has the substituent compound of carbon number more than 3 on the phenyl ring.And preferably adopt tetrahydronaphthalene, 1,2,3,4-durol, 1,2,3, the solvents of boiling point more than 180 ℃ such as 5-durol, cyclohexyl benzene, decahydronaphthalene and dibutyl benzene.Through adding these solvents, can regulate the concentration and the rate of drying of ink composite.And has an effect of the high viscosity that reduces detergent alkylate.Further, adopted the composition of tetrahydronaphthalene, had the advantage that can its concentration be concentrated as solvent with above-mentioned 180 ℃ of boiling points.In addition, can adopt toluene, xylenes, chloroform and carbon tetrachloride etc. as solvent.
Luminescent material as the functional material that is fit to second embodiment; Outside above-mentioned specific fluorenes family macromolecule derivative; Materials a little less than also should selecting for use (gathering) to penylene ethenylidene derivative, polyphenylene derivative, polyvinylcarbazole analog derivative, polythiofuran derivative 、 perylene class pigment, Coumarins pigment, rhodamine class pigment and nonpolar or polarity etc. also can use other low molecular organic EL material that dissolves in benzene derivative and macromolecule organic EL Material etc.Also for example might use rubrene 、 perylene, 9,10-diphenylanthrancene, tetraphenylbutadiene, naphthyridines ketone (Na イ Le レ Star De), coumarin 6, quinoline a word used for translation ketone etc.And carry material and electron transport materials etc. also might suit to use for the hole that constitutes organic EL display.
And, also can add compound (6) with following structure as luminescent material.
Compound 6
Through using the composition of second embodiment; Same with aforementioned first embodiment; Can obtain display unit (preferably between aforementioned first electrode and aforementioned luminous material layer, injection/transfer layer formed display unit in positive hole being set) aptly as useful organic EL of aforementioned functional element etc.
When using the second embodiment composition to make aforementioned luminous material layer; For example; As previously mentioned, through blowoff said composition ejection is beaten respectively after on the substrate, again with heat treated under the temperature of this substrate temperature high (preferred 40～200 ℃) when spraying.It is good more that heating treatment step is handled under high-temperature more, and under the situation of using low boiling point solvent, the ejection back stops dry at once, and the advantage that probably can not fully obtain this operation is arranged.By this embodiment, owing to adopt the high boiling solvent detergent alkylate, therefore, through heat treatment, the content of the composition that is sprayed is by dissolving again, homogenizing further, and so aforementioned effect becomes very big.
The heat treated of above-mentioned composition preferably with the same temperature of the aforementioned first embodiment situation under carry out.And the heat treated of above-mentioned composition and aforementioned first embodiment are same, preferably carry out adding to depress, and further, in the heat treatment of above-mentioned composition, preferably before the composition bone dry, wait to remove through decompression and desolvate.
The 3rd embodiment
The 3rd embodiment of the present composition be a kind ofly have 1 above substituting group by containing at least, this substituent carbon number sum is more than 3 and vapour pressure (room temperature; Below identical) be the composition that solvent and the functional material of the benzene derivative of 0.10～10mmHg constitutes.Promptly; The 3rd embodiment is in composition of the present invention; As be fit to third embodiment of the invention, at least contain have 1 above substituting group, solvent that this substituent carbon number sum is the benzene derivative more than 3, be to adopt to contain the solvent that vapour pressure is the benzene derivative of 0.10～10mmHg at least.
Through this embodiment, in the functional material excellent dissolution a little less than nonpolar or the polarity, following result is proved effective; Promptly; Prevent solvent when ejection plug-hole, make stable ejection become possibility, and being separated can reach content in preventing to spray and separate out, spray the back film forming time.Especially,, be difficult to drying to a certain degree, under the degree that material is not separated, can obtaining having the characteristic of accelerating drying and so on balance, film forming under the no phase-separated state under natural drying at room temperature if use the solvent of the vapour pressure in the above-mentioned scope.
The aforementioned vapour pressure that is adopted as the 3rd embodiment composition is that the benzene derivative of 0.10～10mmHg contains a kind of solvent at least, can enumerate 1,2; 3,4-durol, 1,2; 3,5-durol, cyclohexyl benzene, amylbenzene, mesitylene, isopropylbenzene, cymol, diethylbenzene, tetrahydronaphthalene, decahydronaphthalene etc. are in them preferred especially 1; 2,3, the 5-durol.
And as aforementioned benzene derivative, at least a and vapour pressure that also preferred vapour pressure is the benzene derivative of 0.10～0.50mmHg is at least a mixture of the benzene derivative of 0.50～10mmHg.
At this, as preferred durol of the benzene derivative of aforementioned vapour pressure 0.10～0.50mmHg or cyclohexyl benzene.
And as the benzene derivative of aforementioned vapour pressure 0.50～10mmHg, preferred diethylbenzene and/or mesitylene.
As the functional material that is fit to the 3rd embodiment composition; There is not special limitation; For example; Can the precursor substance of aforementioned organic EL Material, silex glass etc. be applicable to this embodiment, preferred especially fluorenes family macromolecule derivative at least a, the aforesaid compound 1～5 that is adopted in the especially preferred aforementioned second embodiment composition.Therefore, as the functional material that this embodiment adopted, the suitable luminescent material of explaining in aforementioned second embodiment that adopts as functional material.
In addition, the 3rd embodiment composition, the combination through heating after the film forming or heating and decompression removes desolvates, and can obtain specific excellent element.At this moment, preferred 40 ℃～200 ℃ of heating-up temperature, preferred especially 50～100 ℃.And below the preferred 20 * 10-3mmHg of pressure in when decompression.And ejection back (on substrate ejection back) comprehensively even drop is remaining, also can be under heating or heating and decompression combination film forming.
Through using the composition of the 3rd embodiment; Same with aforementioned first and second embodiment; Can obtain display unit (preferably between aforementioned first electrode and aforementioned luminous material layer, injection/transfer layer formed display unit in positive hole being set) aptly as useful organic EL of aforementioned functional element etc.
Below, lift embodiment the present invention more specifically is described.But the present invention does not receive any restriction of these embodiment.
The embodiment of first embodiment
Embodiment 1-1
In the side with electrode of subsidiary ITO (tin indium oxide) transparency electrode glass substrate, apply the tetrahydrofuran solution of PVK, form 0.1 micron polyvinylcarbazole film through spraying process.On this film, adopt ink-jet printing apparatus, the 0.1wt% mixed solution (xylenes/tetrahydronaphthalene=1/4, volume ratio) that will gather the xylenes/tetrahydronaphthalene of hexyl hydroxyl phenylene vinylidene press fixed shape ejection.Further, AM aluminum metallization above that.
Drawing lead by ITO and aluminium, is anode with ITO, and aluminium is negative electrode, adds 10 volts of voltages, presses orange luminescence with the shape of regulation really.In ejection in the past is that rate of drying is fast under the situation of solvent ink with xylenes only, and plug-hole takes place, so that just can not use, in contrast, through this method, unlikely generation plug-hole. at once
Embodiment 1-2
In the mixed solution (cymol/tetrahydronaphthalene=1/1) of cymol/tetrahydronaphthalene, the 20wt% xylene solution of polysilazane (east combustion system) is deployed into 20% (volume ratio) with respect to mixed solvent.The polysilazane solution that obtains like this is ejected on the plastics system liquid crystal panel face with ink discharge device reaches wetting entirely, dry then.Reverse side also carries out same treatment, makes two-sided polysilazanes film.This panel is put into 85 ℃, 90% constant temperature and humidity cabinet and placed 20 minutes, make the silica glass film.After taking out this panel drying, bonding from both sides two pieces of polarizers are met at right angles.
By this method, the consumption that gathers silazane is compared with metallikon and is die-offed, at the lossless silica glass film that forms down almost.And the gas permeation rate of liquid crystal panel is enhanced and the life-span of liquid crystal panel also is enhanced.
Embodiment 1-3
In the mixed solution of cymol/tetrahydronaphthalene (cymol/tetrahydronaphthalene=1/1), the 20wt% xylene solution of polysilazane (east combustion system) is deployed into 20% (volume ratio) with respect to mixed solvent.The polysilazane solution that obtains like this is ejected in the formation semiconductor element and has implemented on the silicon substrate of aluminum wiring whole coating with ink discharge device.Apply the back 150 ℃ of dryings 20 minutes, then under steam atmosphere 350 ℃ of roastings 2 hours.
Its result compares with the situation of spraying process, can obtain the planar film that forms owing to the silica glass effect of identical characteristics slightly.But consumption reduces about two.
Embodiment 1-4
Further explain embodiment of the present invention.As shown in Figure 1; On the electrode of the glass substrate that is divided into ITO (tin indium oxide) transparency electrode of inlaying shape and the subsidiary dykes and dams that surround transparency electrode; With the ejection composition that is described below of rubescent, green, the blue organic EL Material of dissolving, through as print respectively by the ink-jet printing apparatus that inlays shape that is arranged as of all kinds.Solids with respect to the ratio of solvent all in 0.4% (weight per volume).Among Fig. 1,1,2,3,4,5 represent nozzle, glass substrate, ito transparent electrode, dykes and dams (partition), composition (droplets of ink) respectively.
The ejection composition
Solvent detergent alkylate/tetrahydronaphthalene (1/1, volume ratio)
The red Wu/perylene dyestuff (98/2, weight ratio) that gathers
Green fluorenes/the coumarine dye (98.5/1.5, weight ratio) that gathers
Indigo plant is gathered fluorenes
To on this substrate, carry out proper metal except that the back of desolvating and shelter the aluminium of vapor deposition 2000 dusts by the substrate that sprays gained 100 ℃ of heating.
Drawing lead by ITO and aluminium, is anode with ITO, and aluminium is negative electrode, adds 15 volts of voltages, and it is luminous to press the red, green, blue look with the shape of regulation really.Spraying under the situation of the printing ink that with xylenes is solvent, rate of drying is fast, and plug-hole takes place in the past, so that just can not use, in contrast, through this method, unlikely generation plug-hole. at onceAnd, because ejection back heated substrates dissolves content again, therefore, can prevent that content from separating, to no any problems such as luminescent spectrums.Adopt under the situation of low boiling point solvents such as xylenes, the drying that will begin in a minute after the ejection owing to contents such as removing of heat of gasification are separated out, is separated, and causes the variation of luminescent spectrum, is undesirable.
If above-mentioned each ITO electrode connects with the TFT element, can make and the present general identical display of LCD through organic EL.
Embodiment 1-5
To, remove down in decompression (2mmHg) at once and desolvate after 1 minute 100 ℃ of dryings with the substrate of the same ejection of embodiment 1-4.With the substrate of operating gained like this, the method through same with embodiment 1-4 makes panel and lights, and can obtain the result same with embodiment 1-4.
Embodiment 1-6
To be arranged in the glass bell jar with the substrate of the same ejection of embodiment 1-4, enclose nitrogen interior pressure is become 2 atmospheric pressure, remove 100 ℃ of dryings and desolvate.With the substrate of operating gained like this, the method through same with embodiment 1-4 makes panel and lights, and can obtain the result same with embodiment 1-4.
The embodiment of second embodiment
Embodiment 2-1
Present embodiment is made colour display device.
Operation in the present embodiment is also same with the embodiment of aforesaid first embodiment, can pass through Fig. 1 explanation.That is, in structure shown in Figure 1, ito transparent electrode 3 forms with the point-like mode of composition, and is independent separately, and direct connection is gone up at TFT element (not shown) and formed pixel and can drive.Divide the such dykes and dams 4 that form of each pixel with the boundary member of each pixel (point of ito transparent electrode 3), the composition of getting from spray orifice (ink composite) 5 is supplied to and attached on the ito transparent electrode by 4 intervals of dykes and dams.As composition, owing to adopt the luminescent material of three looks, so can make multicolor luminous display.
At first, cooperate luminescent material modulation three kind compositions with prescription as shown in table 1 below corresponding to solvent as composition (ink composite).Select from the distinctive compound 1～5 of aforementioned the present invention as luminescent material, further, adopt compound 6 as required.
Secondly, adopt ink discharge device that said composition is ejected in to have the dykes and dams 4 that constitute by polyimides, by on the substrate that TFT is set on each pixel (TFT substrate).The size in the zone that is sprayed (zone of being divided with dykes and dams 4) is 30 μ m * 30 μ m, and spacing is 70 μ m, and composition (ink composite) ejection spacing makes 70 μ m.Ejection well under the situation of plug-hole does not take place in ink-spraying-head, can obtain three kinds of printing ink by inlaying the substrate that shape is arranged.
Table 1
| Luminescent material | Solvent | |
| R (red) printing ink | Compound 1 0.70 |
Detergent alkylate 100ml tetrahydronaphthalene 100ml |
| G (green) printing ink | Compound 1 0.76 |
Detergent alkylate 100ml tetrahydronaphthalene 100ml |
| B (indigo plant) printing ink | Compound 1 0.78 |
Detergent alkylate 100ml tetrahydronaphthalene 100ml |
With this substrate under the blanket of nitrogen on 100 ℃ electric hot plate heat treatment obtain luminescent layer.The thickness of the luminescent layer of gained is 0.08～0.1 μ m.In addition, vapor deposition lithium fluoride (100nm), calcium (100nm), aluminium (150nm) successively on luminescent layer, the laminated construction with the epoxy sealing gained obtains organic EL display.
Each ito transparent electrode (head) is gone up set TFT element with 10 volts of drivings, really, can show desirable color (color that is equivalent to luminescent layer set on this pixel) by pixel.And can show animation.Especially, the peakedness ratio (440nm/530nm) of the pixel of ejection G printing ink being measured emission wavelength spectrum 440nm and 530nm is 1.0, demonstrates visually good green.
Embodiment 2-2
Cooperate luminescent material with the corresponding solvent of composition as shown in table 2 below; Modulate three kinds of compositions (ink composite), operate equally, adopt ink discharge device with embodiment 2-1; As shown in Figure 1, be ejected on the substrate (TFT substrate) with the dykes and dams 4 that constitute by polyimides.The size in the zone that is sprayed (zone of being divided with dykes and dams 4) is 30 μ m * 30 μ m, and spacing is 70 μ m, and the ejection spacing makes 70 μ m.Ejection well under the situation of plug-hole does not take place in ink-spraying-head, can obtain three kinds of printing ink by inlaying the substrate that shape is arranged.
Table 2
| Luminescent material | Solvent | |
| R (red) printing ink | Compound 1 0.70 |
Detergent alkylate 100ml tetrahydronaphthalene 100ml |
| G (green) printing ink | Compound 1 0.76 |
Detergent alkylate 100ml tetrahydronaphthalene 100ml |
| B (indigo plant) printing ink | Compound 1 0.78 |
Detergent alkylate 100ml tetrahydronaphthalene 100ml |
With this substrate in blanket of nitrogen on 100 ℃ electric hot plate heat treatment obtain luminescent layer.The thickness of the luminescent layer of gained is 0.08～0.1 μ m.Vapor deposition lithium fluoride (100nm), calcium (100nm), aluminium (150nm) successively on above-mentioned luminescent layer again, the laminated construction with the epoxy sealing gained obtains organic EL display.
Each ito transparent electrode (head) is gone up set TFT element with 10 volts of drivings, can show desirable color (color that is equivalent to luminescent layer set on this pixel) by pixel.And can show animation.Especially, the peakedness ratio (440nm/530nm) of the pixel of ejection G printing ink being measured emission wavelength spectrum 440nm and 530nm is 1.0, demonstrates visually good green.
Embodiment 2-3
Operate equally with embodiment 2-1, at first modulate three kinds of compositions (ink composite) of composition as shown in table 1, adopt ink discharge device, as shown in Figure 1, this printing ink is ejected on the TFT substrate with dykes and dams 4 of being made up of polyimides.Ejection well under the situation of plug-hole does not take place in ink-spraying-head.
With the heat treatment 1 minute on 100 ℃ electric hot plate in blanket of nitrogen of this substrate, decompression (mercury 1mmHg) at once removes desolvates, and obtains luminescent layer.The thickness of the luminescent layer of gained is 0.08～0.1 μ m.Further, vapor deposition lithium fluoride (100nm), calcium (100nm), aluminium (150nm) successively on above-mentioned luminescent layer, the laminated construction with the epoxy sealing gained obtains organic EL display.
Each ito transparent electrode (head) is gone up set TFT element with 10 volts of drivings, can show desirable color (color that is equivalent to luminescent layer set on this pixel) by pixel.And can show animation.Especially, the peakedness ratio (440nm/530nm) of the pixel of ejection G printing ink being measured emission wavelength spectrum 440nm and 530nm is 1.8, demonstrates better green.
Embodiment 2-4
Operate equally with embodiment 1, at first modulate three kinds of compositions (ink composite) of composition as shown in table 1, adopt ink discharge device, as shown in Figure 1, this printing ink is ejected on the TFT substrate with the dykes and dams 4 that are made up of polyimides.Ejection well under the situation of plug-hole does not take place in ink-spraying-head.
With the heat treatment 1 minute on 100 ℃ electric hot plate in the blanket of nitrogen of 2 pressure of this substrate, decompression (mercury 1mmHg) at once removes desolvates, and obtains luminescent layer.The thickness of the luminescent layer of gained is 0.08～0.1 μ m.Further, vapor deposition lithium fluoride (100nm), calcium (100nm), aluminium (150nm) successively on above-mentioned luminescent layer, the laminated construction with the epoxy sealing gained obtains organic EL display.
Each ito transparent electrode (head) is gone up set TFT element with 10 volts of drivings, can show desirable color (color that is equivalent to luminescent layer set on this pixel) by pixel.And can show animation.Especially, the peakedness ratio (440nm/530nm) of the pixel of ejection G printing ink being measured emission wavelength spectrum 440nm and 530nm is 2.0, demonstrates better green.
Embodiment 2-5
In the composition shown in the above-mentioned table 2-2; Cooperate cyclohexyl benzene 100ml to substitute tetrahydronaphthalene, other is identical, and solvent cooperates luminescent material modulation three kinds of compositions (ink composite) relatively; Same with embodiment 2-1; Adopt ink discharge device, as shown in Figure 1, be ejected on the TFT substrate with dykes and dams 4 of forming by polyimides.Ejection is spaced apart 70 μ m, obtains three kinds of printing ink by the substrate that inlays the shape assortment.
With the heat treatment on 130 ℃ electric hot plate in blanket of nitrogen of this substrate.The thickness of the luminous material layer of gained is 0.08～0.1 μ m.Further, vapor deposition lithium fluoride (100nm), calcium (100nm), aluminium (150nm) successively on above-mentioned luminous material layer.
Each ito transparent electrode (head) is gone up set TFT element with 10 volts of drivings, can show desirable color (color that is equivalent to luminescent layer set on this pixel) by pixel.And can show animation.
Embodiment 2-6
Use the composition modulation three kind compositions (ink composite) same,, adopt ink discharge device with same with embodiment with embodiment 2-5, as shown in Figure 1, this printing ink is ejected on the TFT substrate with dykes and dams 4 of being made up of polyimides.
This substrate is reduced pressure (1mmHg) in heat treatment on 180 ℃ the electric hot plate after 1 minute at once obtain luminous material layer in 2 atmospheric blanket of nitrogen except that desolvating.The thickness of the luminescent layer of gained is 0.08～0.1 μ m.Further, vapor deposition lithium fluoride (100nm), calcium (100nm), aluminium (150nm) successively on above-mentioned luminescent layer.With sealing around the laminated construction of gained, obtain organic EL display with epoxy resin.
When going up set TFT element, can show desirable color (color that is equivalent to luminescent layer set on this pixel) by pixel with 10 volts of each ito transparent electrodes of driven (head).And can show animation.
Comparative example 2-1
Modulate the composition (R (red) uses ink composite) that corresponding solvent cooperates luminescent material with composition as shown in table 3 below; Operate equally with embodiment 2-1; Adopt ink discharge device, as shown in Figure 1, attempt to go up ejection at the substrate with dykes and dams 4 of forming by polyimides (TFT substrate).But, plug-hole takes place in ink-spraying-head, can not on substrate, carry out the formation of luminescent layer.
Table 3
| Luminescent material | Solvent | |
| R (red) printing ink | Compound 7 0.98g compounds 8 0.02g | Xylenes 200ml |
In addition, illuminant compound 7 that uses in this example and compound 8 are the compounds with following structure.
Compound 7
Compound 8
The embodiment of the 3rd embodiment
Embodiment 3-1
At first, as composition,, the macromolecular compound of functional material (luminescent material) cooperated with solvent be modulated into composition 1～6 (, dividing R (red), G (green), B (indigo plant) three kinds) by each composition with the prescription shown in the below table 4～9.As macromolecular compound, from being to be particularly suitable for selecting to use the compound 1～compound 5 of functional material of the 3rd embodiment.
Table 4 (composition 1)
Table 5 (composition 2)
Table 6 (composition 3)
Table 7 (composition 4)
Table 8 (composition 5)
Table 9 (composition 6)
The vapour pressure (room temperature) of the solvent that adopts in the composition 1～6 in addition, as follows.
Xylenes 13.80
Mesitylene 1.73
1,2,3,4-durol 0.23
Diethylbenzene 0.70
Cyclohexyl benzene 0.193
Detergent alkylate 0.0000125
For above-mentioned composition, the evaluation of carrying out stability of solution, ejection property respectively and being separated by following standard.Their evaluation result is as shown in table 10.
Stability of solution: place more than two days in room temperature during from modulation, see whether visible separating out (whether having turbidity to change), estimate thus.In addition, the turbidity of observing at 650nm for the composition of G, B changes, and the turbidity of observing at 700nm for the composition of R changes.
Zero: no turbidity changes (clear solution)
*: there is turbidity to change (separating out)
Ejection property: observation group's compound (printing ink) drop is from the flight of the ink-spraying-head (the system MJ-930C of エ プ ソ Application society) of Piezoelectric Driving.
Zero: good (more or less flight is crooked, but can composition).
*: cause flight bending and plug-hole.
Be separated: behind R, G, B composition of all kinds, estimate with the PL or the EL luminescent spectrum of air dry film.
Zero: can not observe short wavelength's spectrum from compound 1.
*: can observe short wavelength's spectrum from compound 1.
Table 10
But, same with the condition of embodiment 2-1～2-6 for composition 6, through heating or when adding the heat treated of depressing, being separated becomes " zero " after ejection.
Embodiment 3-2
Substrate forms
By following operation, form substrate with pixel shown in Fig. 2 (A).On the substrate 11 of subsidiary TFT, through photoetching process with ITO12, SiO
213 and polyimides 14 form figures.This SiO
2And polyimides is the part that constitutes embankment (dykes and dams).At this moment, at SiO
2On the circular opening portion of φ 28 μ m is set, further, the circular opening portion of φ 32 μ m is set on the polyimides above that, thus, form the circular pixel of forming by these two opening portions 15.This pixel pitch a is 70.5 μ m.Use SiO
2And polyimides institute above-mentioned circular pixel at interval is the component part of the ejection composition coating composition of the organic EL Material stated after will containing through ink-jetting style.
The plasma treatment of substrate
Then, on the aforesaid substrate that circular pixel is formed,, carry out O in the direction of arrow of Fig. 2 (B)
2And CF
4Continuous atmospheric plasma processes.This plasma treatment condition is following.That is, under atmospheric pressure, power is made as between 300W, electrode-substrate apart from being made as 1mm.And, for O
2Plasma is with O
2Gas flow is set at that 80ccm, helium gas flow are set at 10L/min, the belt transporting velocity is set at 10mm/s, for CF
4Plasma is with CF
4Gas flow is set at that 100cm, helium gas flow are set at 10L/min, the belt transporting velocity is set at 5mm/s.
The formation of the positive hole injection/transfer layer of carrying out with ink-jetting style
To be modulated into the ink composite that positive hole injection/transfer layer is used by the composition that form forming shown in the table 11.
Table 11
| Material | Content (wt%) |
| Gather ethylene hydroxyl thiophene/polyvinyl sulfonic acid mixed liquor | 11.08 |
| Polyvinyl sulfonic acid | 1.44 |
| Isopropyl alcohol | 10 |
| The N-methyl pyrrolidone | 27.48 |
| 1,3-dimethyl-2-imidazolidinone | 50 |
Shown in Fig. 2 (C), spray the ink composite 17 that above-mentioned positive hole injection/transfer layer is used from ink-spraying-head (エ プ ソ Application society system MJ-930C head) 16 with 20pl, on each pixel capacitors, apply composition.Apply the back and in vacuum (ltorr), under the room temperature, 20 minutes condition, remove and desolvate, afterwards, in atmosphere, 200 ℃ of (on the hot plate) heat treatment 10 minutes, form positive hole injection/transfer layer 18 (with reference to Fig. 2 (D)) thus.The thickness of the positive hole injection/transfer layer 18 of gained is 40nm.
The formation of the luminescent layer that is undertaken by ink-jetting style
Like Fig. 3 (E) and (F); From ink-spraying-head (the system MJ-930C of エ プ ソ Application society head) 16; To spray with 20pl as the composition 2 of the table 5 that adopts among illuminating composition 19, the previous embodiment 3-1; On each plain electrode, carry out composition by the order of B, R, G and apply, form luminescent layer of all kinds 20 (with reference to Fig. 3 (G)) thus.After forming luminescent layer 20, under the decompression below the 1Torr, 30 minutes, carry out substrate at 60 ℃ and bake.
The electrode sealing process
Form after the luminescent layer, form lithium fluoride (thickness: 2nm), calcium (thickness: 20nm) and aluminium (thickness: 20nm), make electrode (negative electrode) 21 with vapor deposition.At last, with the above-mentioned electrode of epoxy resin 22 sealings, make color organic EL panel 10 (with reference to Fig. 3 (H)).
Embodiment 3-3
Adopt the composition 3 of the table 6 of previous embodiment 3-1 employing to form luminescent layer of all kinds, in addition,, make the color organic EL panel through the operation same with previous embodiment 3-2.
Embodiment 3-4
Adopt the composition 4 of the table 7 of previous embodiment 3-1 employing to form luminescent layer of all kinds, in addition,, make the color organic EL panel through the operation same with previous embodiment 3-2.
Embodiment 3-5
Adopt the composition 5 of the table 8 of previous embodiment 3-1 employing to form luminescent layer of all kinds, in addition,, make the color organic EL panel through the operation same with previous embodiment 3-2.
Practicality in the industry
As stated; Composition of the present invention can substitute the photoetching process of functional material composition in the past and adopt ink jet printing method; As functional material, can use the weak material of nonpolar or polarity, have and the reactive material of water, plug-hole in the time of can preventing to spray; Reach stable ejection, separating out of the content in preventing to spray and being separated when spraying the back film forming.
In addition, functional membrane of the present invention is to adopt the film that foregoing forms, even, that homogeneous is fine.In addition, display unit of the present invention is provided with and adopts the formed luminous material layer of foregoing and form, and is the display unit that is specially adapted to the organic EL etc. of luminous demonstration purposes.
In addition, through the manufacturing approach of display unit of the present invention, can obtain having the arrangement of the film of difference in functionality simply.And owing to use the material of necessary amount in the part of necessity, so, even compare, also can reduce material with method such as spraying process.
Claims (11)
1. the manufacturing approach of a film is characterized in that, will use the ink-jet printing apparatus with nozzle through the composition that obtains of dissolving organic EL Material in solvent, supply with and beat with being scattered after on the base material from this nozzle, and again with this base material heat treatment,
Wherein said solvent comprises at least a benzene derivative; Said benzene derivative is from isopropylbenzene, cymol, cyclohexyl benzene, detergent alkylate, diethylbenzene, amylbenzene, diamyl benzene, butyl benzene, tetrahydronaphthalene, durol, decahydronaphthalene, dihexyl benzene, dibutyl benzene and mesitylene, select at least a, and
Said organic EL Material is from the compound of following compound 1 to 4, select at least a,
Compound 1
Compound 2
Compound 3
Compound 4.
2. by the manufacturing approach of the described film of claim 1, wherein, aforementioned solvents comprises the benzene derivative of boiling point more than 200 ℃, and said benzene derivative is from detergent alkylate, cyclohexyl benzene, tetrahydronaphthalene, diamyl benzene and amylbenzene, select at least a.
3. by the manufacturing approach of the described film of claim 2, wherein, the benzene derivative of aforementioned boiling point more than 200 ℃ is detergent alkylate.
4. press the manufacturing approach of claim 2 or 3 described films, wherein,
Aforementioned solvents comprises:
The benzene derivative of aforementioned boiling point more than 200 ℃; With
The benzene derivative of boiling point more than 140 ℃, and said benzene derivative is from cymol, tetrahydronaphthalene, isopropylbenzene, decahydronaphthalene, durene, cyclohexyl benzene, dihexyl benzene, durol and dibutyl benzene, select at least a.
5. press the manufacturing approach of claim 2 or 3 described films, wherein,
Aforementioned solvents comprises:
The benzene derivative of aforementioned boiling point more than 200 ℃; With
The benzene derivative of boiling point more than 180 ℃, and said benzene derivative is from tetrahydronaphthalene, 1,2,3,4-durol, 1,2,3, that selects in 5-durol, cyclohexyl benzene, decahydronaphthalene and the dibutyl benzene is at least a.
6. by the manufacturing approach of the described film of claim 1, wherein, aforementioned benzene derivative vapour pressure at room temperature is 0.10-10mmHg.
7. by the manufacturing approach of the described film of claim 6, wherein, aforementioned benzene derivative is 1,2,3, the 4-durol.
8. by the manufacturing approach of the described film of claim 6, wherein, aforementioned benzene derivative is that vapour pressure is that at least a and vapour pressure of the benzene derivative of 0.10-0.50mmHg is at least a mixture of the benzene derivative of 0.50-10mmHg.
9. by the manufacturing approach of the described film of claim 8, wherein, aforementioned vapour pressure is that the benzene derivative of 0.10-0.50mmHg is a durol.
10. by the manufacturing approach of the described film of claim 8, wherein, aforementioned vapour pressure is that the benzene derivative of 0.10-0.50mmHg is a cyclohexyl benzene.
11. by the manufacturing approach of each described film of claim 8-10, wherein, aforementioned vapour pressure is that the benzene derivative of 0.50-10mmHg is diethylbenzene and/or mesitylene.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP86944/1999 | 1999-03-29 | ||
| JP8694499 | 1999-03-29 | ||
| JP250486/1999 | 1999-09-03 | ||
| JP25048699 | 1999-09-03 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN00800987A Division CN1310930A (en) | 1999-03-29 | 2000-03-29 | Composition, method for preparing film, and functional element and method for preparing the same |
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| CN1893140B true CN1893140B (en) | 2012-03-07 |
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| CN 200610075547 Expired - Lifetime CN1893140B (en) | 1999-03-29 | 2000-03-29 | A film manufacturing method |
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| CN101510591B (en) * | 2009-01-21 | 2011-02-09 | 西安交通大学 | Group printing method and device for OLED unit three-dimensional microstructure based on formwork |
| CN107251259B (en) * | 2015-03-05 | 2020-06-30 | 住友化学株式会社 | Composition and light-emitting element using the same |
| CN115663597A (en) * | 2017-05-19 | 2023-01-31 | 中国科学院化学研究所 | Laser array device |
| EP3611234B1 (en) | 2017-05-19 | 2023-06-21 | Institute of Chemistry, Chinese Academy of Science | Ink for producing laser light sources |
| CN115145046A (en) * | 2017-05-19 | 2022-10-04 | 中国科学院化学研究所 | Laser panel |
| CN115047640A (en) * | 2017-05-19 | 2022-09-13 | 中国科学院化学研究所 | Voltage-driven laser display |
| CN108948862A (en) * | 2017-05-19 | 2018-12-07 | 中国科学院化学研究所 | It is a kind of for the ink of laser light source to be made |
| CN108948857A (en) * | 2017-05-19 | 2018-12-07 | 中国科学院化学研究所 | A method of printing laser light source |
| CN115079428A (en) * | 2017-05-19 | 2022-09-20 | 中国科学院化学研究所 | Laser display |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4713198A (en) * | 1984-04-27 | 1987-12-15 | Sangamo Weston, Inc. | High temperature plastic scintillators |
| US5091004A (en) * | 1987-09-22 | 1992-02-25 | Dainippon Ink And Chemicals, Inc. | Ink composition |
| CN1192223A (en) * | 1995-07-28 | 1998-09-02 | 陶氏化学公司 | 2,7-aryl-9-substituted fluorenes and 9-substituted fluorene oligomers and polymers |
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| US6207301B1 (en) * | 1996-08-21 | 2001-03-27 | Sumitomo Chemical Company, Limited | Polymer fluorescent substance and organic electroluminescence device |
| US5777070A (en) * | 1997-10-23 | 1998-07-07 | The Dow Chemical Company | Process for preparing conjugated polymers |
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2000
- 2000-03-29 CN CN2008101097047A patent/CN101353472B/en not_active Expired - Lifetime
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4713198A (en) * | 1984-04-27 | 1987-12-15 | Sangamo Weston, Inc. | High temperature plastic scintillators |
| US5091004A (en) * | 1987-09-22 | 1992-02-25 | Dainippon Ink And Chemicals, Inc. | Ink composition |
| CN1192223A (en) * | 1995-07-28 | 1998-09-02 | 陶氏化学公司 | 2,7-aryl-9-substituted fluorenes and 9-substituted fluorene oligomers and polymers |
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