WO2008001693A1

WO2008001693A1 - Fluorescent composition and fluorescence conversion substrate using the same

Info

Publication number: WO2008001693A1
Application number: PCT/JP2007/062605
Authority: WO
Inventors: Satoshi Hachiya; Mitsuru Eida
Original assignee: Idemitsu Kosan Co., Ltd.
Priority date: 2006-06-29
Filing date: 2007-06-22
Publication date: 2008-01-03

Abstract

Disclosed is a composition containing the following components (A)-(C). (A) a fluorescent inorganic nanocrystal (B) a polyfunctional crosslinkable compound (C) a polymerizable compound having a group selected from substituted or unsubstituted alkyl groups having 4-20 carbon atoms, substituted or unsubstituted alkylene groups having 4-20 carbon atoms, substituted or unsubstituted aryl groups having 6-20 carbon atoms, and substituted or unsubstituted arylene groups having 6-20 carbon atoms

Description

Specification

Fluorescent composition and fluorescent conversion substrate using the same

Technical field

[0001] The present invention relates to a composition containing a fluorescent inorganic nanocrystal, and more particularly to a fluorescent ink composition suitable for forming a fluorescent layer (fluorescent conversion film) on a substrate by an ink jet method or a nonoresid method.

Background art

[0002] Light from light-emitting elements such as organic EL (electric-mouth luminescence) elements is converted into light of other wavelengths in the fluorescence conversion layer, resulting in full-color light of blue, green, and red. Techniques for obtaining display play are known.

[0003] The fluorescence conversion layer is usually formed on the substrate by a general-purpose photolithography method, a printing method, or the like. On the other hand, the use of fluorescent inorganic nanocrystals as fluorescent conversion materials has been studied.

[0004] However, a technique for manufacturing a fluorescence conversion film or a fluorescence conversion substrate by an ink jet method using an ink containing a fluorescent inorganic nanocrystal as a fluorescence conversion material has not been completed.

That is, the composition containing fluorescent inorganic nanocrystals has various reported forces. When this composition is used to form a fluorescent layer, it contains a large amount of solvent, so the difference between the wet film thickness and the dry film thickness. It was difficult to obtain a fluorescent layer (fluorescence conversion film) having a desired film thickness. In particular, when used as an ink for ink jet or nozure jet, in order to obtain a fluorescent film having a desired film thickness, it was necessary to apply several times or more, and the productivity was remarkably deteriorated. It was difficult to obtain a fluorescent layer (fluorescence conversion film) dispersed at a high concentration.

[0005] Patent Document 1 discloses a technique of forming a phosphor conversion film by an ink jet method using a composition containing an organic fluorescent dye.

However, the organic fluorescent dye has insufficient durability against light irradiation. In addition, when fluorescent inorganic nanocrystals are used in place of organic fluorescent dyes, it is necessary to disperse fluorescent inorganic nanocrystals at a higher concentration than organic fluorescent dyes in order to exhibit sufficient fluorescence conversion performance. However, it was difficult to stably disperse the fluorescent inorganic nanocrystals.

[0006] Patent Document 2 discloses a photopolymerizable resin composition for use in the production of a non-linear optical material optoelectronic device, comprising a fluorescent inorganic nanocrystal, a solvent, and a polymerizable monomer. It is disclosed.

If an ink-jet method is used to form a thick fluorescent conversion film on a substrate using this composition, the ink contains a large amount of solvent. In order to obtain a desired film thickness, it was necessary to repeat the coating, and the productivity was extremely poor.

[0007] Patent Documents 3 and 4 disclose an inkjet ink containing a fluorescent inorganic nanocrystal using an aqueous medium for use in printing on paper or an OHP film by an inkjet method.

Since an aqueous medium is used, in applications where the film thickness is on the order of / m, such as a fluorescence conversion film, moisture remains, making it difficult to combine with an electronic device. Patent Document 1: Japanese Unexamined Patent Publication No. 2003-229260

Patent Document 2: Japanese Patent Laid-Open No. 10-186426

Patent Document 3: Japanese Unexamined Patent Publication No. 2000-119575

Patent Document 4: Japanese Unexamined Patent Application Publication No. 2004-149765

[0008] An object of the present invention is to provide a composition that can be used when a fluorescent conversion film containing a fluorescent inorganic nanocrystal at a concentration capable of exhibiting sufficient fluorescent conversion performance is produced by a printing method, particularly, an inkjet ink. When used as, it is to provide a highly productive composition.

Another object of the present invention is to provide a method for producing a fluorescence conversion substrate using the composition.

Another object of the present invention is to provide a fluorescence conversion substrate and a light emitting device manufactured using the composition. Disclosure of the invention

According to the present invention, the following compositions and the like are provided.

1. A composition comprising the following components (A) to (C).

(A) Fluorescent inorganic nanocrystal

(B) Polyfunctional crosslinkable compound

(C) a substituted or unsubstituted alkyl group having 4 to 20 carbon atoms, a substituted or unsubstituted alkylene group having 4 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, and the number of carbon atoms A polymerizable compound having a group selected from 6 to 20 substituted or unsubstituted arylene groups

2. The composition according to 1, wherein the ratio of the total of components (A) to (C) to the composition is 40% by weight or more.

3.Ingredient (A) is:! ~ 45wt%,

Ingredient (B) is:! ~ 40% by weight,

3. The composition according to 1 or 2, comprising 1 to 40% by weight of component (C).

4. The composition according to any one of 1 to 3, wherein the polyfunctional crosslinking compound (B) comprises at least one of a polyfunctional (meth) acrylate and a polyfunctional epoxy compound.

5. Furthermore, the composition in any one of 1-4 containing the following component (D).

(D) Surface treatment agent for fluorescent inorganic nanocrystals

6. The composition according to 5, wherein part or all of the surface treatment agent (D) for the fluorescent inorganic nanocrystal has a force S, and has a polymerizable or crosslinkable substituent.

7. The composition according to 5 or 6, comprising 20% by weight or less of component (D).

8. Surface treatment agent (D) of fluorescent inorganic nanocrystal is selected from amino group, thiol group, phosphate ester group, phosphonic acid group, carboxyl group, olefin group, phosphine group, phosphine oxide group, epoxy group The composition according to any one of 5 to 7, which has at least one substituent.

9. The composition according to any one of 1 to 8, further comprising a polymerization initiator.

10. The composition according to any one of 1 to 9, wherein the content of a component having a boiling point of 200 ° C or lower is 0 to 60% by weight. 11. 25. Rice occupancy power in C S, in the range of 0.001 to 0.020 Pa's:!

12 :! A cured product obtained by curing the composition according to 11-11.

13. the substrate,

A fluorescence conversion substrate comprising a fluorescence conversion film comprising the cured product according to 12 on the substrate.

14. The fluorescence conversion substrate according to 13, wherein a partition wall is provided on the substrate, and the fluorescence conversion film has a strength in an area partitioned by the partition wall.

15. A method for producing a fluorescence conversion substrate, wherein a fluorescence conversion film is formed by curing the composition according to any one of 11 to 11 on a substrate.

16. The method for producing a fluorescence conversion substrate according to 15, wherein a fluorescence conversion film is formed by applying the composition according to any one of 1 to 11 on a substrate by a printing method.

17. The method for producing a fluorescence conversion substrate according to 16, wherein the printing method is an ink-jet method or a nozzo resist method.

18. The method for producing a fluorescence conversion substrate according to any one of 15 to 17: wherein a fluorescence conversion film is formed by applying a composition to an area on a substrate separated by a partition wall.

19. Light emitting element,

A light emitting device comprising the fluorescence conversion substrate according to 13 or 14.

[0010] According to the present invention, a composition that can be used when producing a fluorescent conversion film containing a fluorescent inorganic nanocrystal at a concentration capable of exhibiting sufficient fluorescence conversion performance by a printing method, in particular, an inkjet ink. When used as a composition, a highly productive composition can be provided. ADVANTAGE OF THE INVENTION According to this invention, the manufacturing method of the fluorescence conversion board | substrate using the composition can be provided. According to the present invention, a fluorescence conversion substrate and a light-emitting device manufactured using the composition can be provided.

Brief Description of Drawings

FIG. 1 is a view showing a light emitting device created in Example 3.

BEST MODE FOR CARRYING OUT THE INVENTION

[0012] The composition of the present invention includes the following components (A) to (C).

(A) Fluorescent inorganic nanocrystal (B) Polyfunctional crosslinkable compound

(C) A substituted or unsubstituted alkyl group having 4 to 20 carbon atoms, a substituted or unsubstituted alkylene group, a substituted or unsubstituted arylene group having 6 to 20 carbon atoms, and a substituted or unsubstituted arylene group Polymerizable compound having a group

[0013] Examples of the fluorescent inorganic nanocrystal (component (A)) include the following substances.

(i) Semiconductor nanocrystal phosphor

Se-VI compound semiconductor nanocrystals such as ZnSe, ZnTe, CdSe, ΠΙ-V compound semiconductor nanocrystals such as InP, chalcopyrite type semiconductor nanotalis such as CuInS, CuInSe

twenty two

Stanole.

The semiconductor nanocrystal is a semiconductor crystal made into ultrafine particles of nanometer order, and preferably has a particle size of 20 nm or less, more preferably lOnm or less.

(ii) Nanocrystal phosphors doped with transition metal ions in metal chalcogenides

A metal canorecogenide such as ZnS, ZnSe, CdS, or CdSe doped with transition metal ions such as Eu ²⁺ , Eu ³⁺ , Ce ³⁺ , T b ³⁺ , or Cu ²⁺ .

(iii) Nanocrystal phosphors doped with transition metal ions in metal oxides

YO, Gd O, ZnO, Y Al O, a metal oxide such as Zn ^{^{Si_〇, Eu 2+, Eu 3+, Ce}} 3

2 3 2 3 3 5 12 2 4

Dopes doped with transition metal ions that absorb visible light, such as ⁺ and Tb ³⁺ .

[0014] The nanocrystal phosphor of (i) and (ii) above may be oxidized on the surface of the nanocrystal.

In order to prevent the extraction of S, Se, etc., the surface may be modified with a metal oxide such as silica or an organic substance such as a long chain alkyl group or phosphoric acid.

Furthermore, nanoparticles in which the surface of the nanoparticles is covered with another semiconductor called a shell are more preferable in terms of stability and fluorescence. The surface of the shell may be further coated with a metal oxide such as silica or titania.

[0015] The fluorescent inorganic nanocrystals may be used alone or in combination of two or more.

[0016] As the polyfunctional curable compound (polyfunctional crosslinkable compound, component (B)), a compound in which the cured product is translucent can be used. Functional epoxy compounds, polyfunctional (meth) acrylate compounds, trialkoxysilanes are preferred Poxy compounds are more preferred.

Specific polyfunctional (meth) atalylate compounds include pentaerythritol triatalylate, pentaerythritol tetraatalylate, trimethylolpropane tritalylate, dipentaerythritol pentaatalylate, neopentylglycol dimetatalylate, 2-methacryloyl An example is ruoxymethyloctyl methacrylate.

Specific polyfunctional epoxy compounds include 1,7-octagen diepoxide, diglycidinol 1,2-cyclohexanecarboxylate, neopentyl glycol diglycidyl ether, triglycidyl isocyanurate, commercially available Examples include epoxy resins (for example, Dainippon Ink and Chemicals: trade name ECN, EPICL * N, Japan epoxy resin: trade name EP * N).

Specific examples of trialkoxysilane include hexyltrimethoxysilane, etyltriethoxysilane, dodecinoletriethoxysilane, and benzyltriethoxysilane.

The above polyfunctional curable compounds may be used alone or in combination of two or more.

As the polymerizable compound (component (C)), a compound in which the polymer is translucent can be used. Various known polymerizable compounds can be used, but it is preferably a polymerizable group copolymerizable with the polyfunctional curable compound (component B).

That is, (meth) atalylate compounds containing an addition polymerizable double bond in the molecule, styrene derivatives, butyl ester compounds, epoxy compounds containing a ring-opening polymerizable cyclic group in the molecule, oxetane compounds, oxazole compounds, condensation polymerization A dialkoxy silane compound containing a functional group in the molecule is preferred.

Of these, (meth) attalei toy compounds, styrene derivatives, butyl ester compounds, epoxy compounds, dialkoxysilane compounds are particularly preferred.

One addition polymerizable double bond, ring-opening polymerizable cyclic group and dialkoxysilyl group are preferably contained in the molecule.

In order to improve the dispersibility of the fluorescent inorganic nanocrystal, an alkyl group having 4 to 20 carbon atoms, an alkylene group having 4 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, It preferably has a substituent selected from a len group. [0018] Specific examples of the (meth) atalyte toy compound include 2-ethylhexyl acrylate, dodecyl acrylate, and benzyl methacrylate.

Specific examples of the styrene derivative include styrene, 4-methylstyrene, 4-vinylbiphenol, and methyl 4-burbenzoate.

Specific examples of the epoxy compound include benzyl glycidyl ether, styrene oxide, 1,2_epoxydecane, and glycidyl 4_tertiary butyl benzoate.

Specific examples of dialkoxysilane compounds include dimethoxyhexylmethylsilane, and examples of specific burester compounds include burhexanoate and burbenzoate.

The above polymerizable compounds may be used alone or in combination of two or more.

In the composition of the present invention, the sum of components (A) to (C) accounts for 40% by weight or more, preferably 60% by weight or more, more preferably 70% by weight or more of the composition.

Suitable blending amounts of components (A) to (C) are as follows.

Ingredient (A) ::! ~ 45 wt%, more preferably 10-45 wt%

Ingredient (B) ::!-40% by weight, more preferably 20-40% by weight

Ingredient (C) ::!-40% by weight, more preferably 10-30% by weight

[0020] Furthermore, the composition of the present invention preferably contains a surface treatment agent (component (D)). By adding a surface treating agent, the dispersion of the fluorescent inorganic nanocrystal in the composition can be further stabilized. Force capable of using a known surface treating agent as the surface treating agent Preferably, the surface treating agent is selected so that the polyfunctional curable compound is not cured during storage of the composition.

When the polyfunctional curable compound is a polyfunctional (meth) atalyl H compound, the surface treatment agent is an amino group, a thiol group, a phosphate ester group, a phosphonic acid group, a phosphine group, a phosphine oxide group, a carboxyl group, It preferably contains an olefin group. More preferably, thiol group, phosphate group, phosphonic acid group, carboxyl group, olefin group, Preferably, it contains a thiol group, a phosphate ester group, and an olefin group. When the polyfunctional curable compound is a polyfunctional epoxy compound, the surface treatment agent preferably contains a phosphine group, a phosphine oxide group, an olefin group, and an epoxy group.

[0021] Specific examples of the compound containing an amino group include an amino-terminated PEG, octylamine, decinoreamin, and glycine tert butyl ester.

Specific compounds containing a thiol group include octanethiol, octylthiodarylate, 2_ethylhexyl 3_mercaptopropionate, thiol-terminated PEG, 3_menole.

Specific examples of the compound containing a phosphoric acid ester group include dibutyl phosphate, di_n_decyl phosphate, di (polyethylene glycol 4-noylphenyl) phosphate, and tributyl phosphate.

[0022] Specific examples of the compound containing a carboxyl group include decanoic acid, 2-ethylhexanoic acid, 4-monohexylbenzoic acid, and 4-bulubenzoic acid.

Specific examples of the compound containing a phosphonic acid group include octylphosphonic acid, tetradecanophosphonic acid, and jetylbenzyl phosphonate.

Specific examples of the compound containing a phosphine group include tributylphosphine and trioctylphosphine.

Specific examples of the compound containing a phosphine oxide group include tributylphosphine oxide and trioctylphosphine oxide.

Specific examples of the compound containing an olephine group include dodecene, methylundecenoate, burundecenoate, and 1,2-epoxy-9-decene.

Specific examples of compounds containing an epoxy group include 1,2-epoxy-dodecane, 1,2-epoxy-9-decene, styrene oxide, hypopinene oxide, and 3-glycidyl oxide.

[0023] Part or all of the surface treatment agent (D) preferably has a polymerizable or crosslinkable substituent. By having such a substituent, the nanocrystal is firmly fixed in the cured product, and the dispersion stability of the nanocrystal in the film can be improved. It is preferable that the polymerizable or crosslinkable substituent is a polymerizable group or a crosslinkable group copolymerizable with the polyfunctional curable compound (component B). A (meth) acrylate group, a styryl group, or a vinyl ester group is preferable. And epoxy group, dialkoxysilyl group, trialkoxysilyl group.

[0024] The preferred amount of component (D) is as follows.

Component (D): 20% by weight or less, more preferably 2 to: 10% by weight

[0025] The composition of the present invention preferably contains a polymerization initiator in order to increase the curing rate and improve the productivity.

For example, when the polyfunctional curable compound (B) is a polyfunctional (meth) acrylate, a photopolymerization initiator or a thermal polymerization initiator can be added. A specific example of the photopolymerization initiator is Inoregacure 907 (manufactured by Ciba Specialty Chemicals).

When the polyfunctional curable compound (B) is a polyfunctional epoxy compound, a compound that generates an acid or an alkali by heating or light irradiation can be used as a polymerization initiator.

[0026] Since the composition of the present invention preferably has a small decrease in film thickness when cured, that is, a small amount of volatile components, the content of components having a boiling point of 200 ° C or less is 0 to 60 wt%. % Is preferable.

[0027] When the composition of the present invention is used as an inkjet ink, the viscosity at 25 ° C is preferably in the range of 0.001-0.020 Pa's. The method for measuring the viscosity is as described in the examples.

In the present invention, a polyfunctional curable compound (component (B)) is blended in order to maintain the strength of the fluorescence conversion film.

In general, polyfunctional curable compounds contain many polar groups such as acrylic groups and epoxy groups, and therefore, there are many highly viscous substances. Therefore, in order to adjust the solution viscosity to a suitable range, it is necessary to add a medium for adjusting the viscosity.

In ordinary inkjet inks, it is common to adjust the solution viscosity by adding a solvent.

However, when a solvent is added, the film thickness that can be formed by a single coating is reduced, and it is attempted to incorporate fluorescent inorganic nanocrystals that can exhibit sufficient fluorescence conversion performance into it. As a result, the concentration becomes too high, and the fluorescence conversion film may not have sufficient strength, and the fluorescent inorganic nanocrystals may aggregate and separate.

In order to maintain the strength of the fluorescent conversion film, the concentration of the fluorescent inorganic nanocrystal is low, and it becomes necessary to apply the composition many times, resulting in a decrease in productivity.

[0029] In order to increase the dispersibility of the fluorescent inorganic nanocrystals for polyfunctional curable compounds containing a large number of polar groups such as acrylic groups and epoxy groups, the surface of the fluorescent inorganic nanocrystals is made polar. It is preferable to treat with a high substance.

However, in this case, the polarity of the fluorescent conversion film is increased, and as a result, the water absorption is increased, which is not preferable for combining a current-carrying device such as an organic EL element or LED as a light source. In addition, the fluorescent inorganic nanocrystal itself may be altered by moisture.

[0030] Therefore, in the present invention, the fluorescent inorganic nanocrystals are highly non-volatile (a sufficient film thickness can be obtained by one application) and are too polar (low water absorption). (B) Component (C) is selected as the viscosity adjusting medium.

[0031] Component (C) used in the present invention includes an alkyl group having 4 to 20 carbon atoms, an alkylene group having 4 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, and an arylene group having 6 to 20 carbon atoms. A group selected from: a hydrocarbon group.

Since component (C) is polymerizable, it is easy to prevent separation from the fluorescence conversion membrane and surface stickiness.

In terms of non-volatility, the boiling point of component (C) is preferably 200 ° C or higher.

[0032] In the composition of the present invention, a resin or a solvent may be added in order to adjust the viscosity of the composition within a range not impairing the strength and productivity of the film. For example, a resin such as polybenzyl metatalylate, polymethyl metatalylate, polystyrene, and silicone modified polycarbonate, and a solvent such as xylene, diglyme, and cyclohexanone can be used.

[0033] The composition of the present invention can be dried and Z or cured to obtain a cured product. For example, when the composition contains a photopolymerization initiator, it is irradiated with actinic rays, and when it contains a thermal polymerization initiator, it is cured by heating.

[0034] A fluorescence conversion film made of a cured product of the composition of the present invention is formed on a substrate to form a fluorescence conversion group. A board can be created. The thickness of the fluorescent conversion film is not limited, but is usually 1 to 100 μm. As the substrate, a glass plate, a polymer plate or the like can be used. At this time, if a partition wall is provided on the substrate and the composition (ink) is allowed to flow into an area partitioned by the partition wall to form a fluorescence conversion film, it is easy to separately apply a plurality of types of ink.

[0035] The composition of the present invention is applied to a substrate and cured after being applied. However, when applied to a substrate by a printing method, a fluorescent conversion film can be formed only on a necessary portion, and the use efficiency of the material is preferably improved. . As a printing method, an inkjet method or a nozure jet method can be used.

When forming a fluorescence conversion film in the area delimited by the barrier ribs, apply the composition to the corresponding area to form the fluorescence conversion film.

[0036] The fluorescence conversion film produced using the composition of the present invention has a high concentration of fluorescent inorganic nanocrystals, and therefore can exhibit sufficient fluorescence conversion performance. In addition, since the composition of the present invention can be used as an ink jet ink, the productivity of the fluorescence conversion film and the fluorescence conversion substrate is increased.

Furthermore, a light emitting device can be manufactured by combining the light emitting element and the fluorescence conversion substrate. As the light-emitting element, one that emits visible light can be used. For example, an organic EL element, an inorganic EL element, a semiconductor light-emitting diode, and a fluorescent display tube can be used. Of these, organic EL elements and inorganic EL elements are preferred, and organic EL elements are particularly preferred because light-emitting elements with low voltage and high luminance can be obtained.

[Example]

[0038] Synthesis Example 1

[Synthesis of InP / ZnS nanoparticles]

The indicated nanoparticles were synthesized with reference to J. Am. Chem. So, 2005, 127, 11364. The following is an overview.

(1) Synthesis of ΙηΡ core

In a 200 ml four-necked flask, 0.29 g of indium acetate, 0.69 g of myristic acid and 4 Oml of octadecene 4 were weighed. The flask was set on a mantle heater. A mechanical stirrer equipped with a glass stirring shaft and a Teflon (registered trademark) stirring blade was set on the main tube of the flask. A three-way cock was attached to one of the branch pipes and connected to a nitrogen line and a vacuum line. another A rubber septum cap was attached to the branch pipe. A thermocouple was set in the remaining branch pipe. The inside of the flask was evacuated to a vacuum and stirred at 120 ° C for 2 hours. The pressure was returned to atmospheric pressure with nitrogen gas, and the temperature was increased to 2 80 ° C.

In a nitrogen-substituted glove box, 1.4 g of a 10% hexane solution of tristrimethylsilylphosphine and lml of octadecene were weighed into a sample bottle and sucked with a gas tight syringe.

A solution of the phosphine compound was injected all at once from the septum cap portion of the four-necked flask. After 5 seconds, 40 ml of octadecene was added, and the reaction temperature was rapidly lowered to 180 ° C. 1 Stirring was continued at 80 ° C for 2 hours.

The temperature was lowered to 50 ° C., and the pressure was reduced by a vacuum pump for 1 hour.

The reaction solution was taken out by returning to atmospheric pressure with nitrogen gas and lowering the temperature to room temperature, and the precipitate was removed by centrifugation (3000 rpm, 10 minutes). The supernatant was once stored in the glove box.

[0039] (2) Synthesis of InP / ZnS core-shell nanoparticles

In a 200 ml four-necked flask, 1 · 48 g of zinc laurate, 0 · l lg of sulfur, and 10 ml of octadecene were weighed. The same apparatus as (1) was attached to the flask.

The inside of the flask was evacuated to a vacuum and stirred at 80 ° C for 30 minutes. The solution was returned to atmospheric pressure with nitrogen gas, and a solution of InP nanoparticles stored in the glove box was added. Stirring was continued under reduced pressure at 80 ° C for 1.5 hours.

The pressure was returned to atmospheric pressure with nitrogen gas, and the temperature was increased to 140 ° C. 1. Stirring was continued for 5 hours. The temperature was lowered to room temperature, the reaction solution was taken out, and coarse particles and unreacted raw materials were removed by centrifugation (3000 rpm, 15 minutes).

The obtained nanoparticles had a fluorescence peak wavelength of 634 nm and a fluorescence quantum yield of 17%. These were measured using a quantum yield measuring apparatus (C9920-02 type) manufactured by Hamamatsu Photonicus.

[0040] Synthesis Example 2

[Synthesis of Cu-doped ZnSe nanoparticles]

J. Am. Chem. So, 2005, 127, 17586 It was. The following is an overview.

In a 200 ml four-necked flask, 0 · 20 g of zinc laurate and 50 ml of octadecene were weighed. The same instrument as in Synthesis Example 1 was set.

The inside of the flask was evacuated to a vacuum and stirred at 120 ° C for 2 hours. The pressure was returned to atmospheric pressure with nitrogen gas, and the temperature was increased to 300 ° C.

In a nitrogen-substituted glove box, 0.02 g of selenium, 0.5 g of hexadenoleamine and 7 g of tributylphosphine were weighed in a sample bottle to dissolve selenium.

The selenium solution was injected all at once from the septum cap portion of the four-necked flask. Stirring was continued for 1.5 hours at 290 ° C. The reaction temperature was then lowered to 180 ° C.

In a nitrogen-substituted glove box, 0.031 g of copper acetate and 10 ml of tributyl phosphate were weighed into a sample bottle to dissolve the copper acetate. Of this, 0.1 ml was sucked into a syringe and injected into the reaction solution.

After 10 minutes, a solution containing 0.1 lg zinc acetate and 5 ml tributylphosphine was added dropwise to the reaction solution. The dripping took 30 minutes.

After completion of the dropwise addition, the reaction temperature was raised to 230 ° C and stirring was continued for 1.5 hours.

The temperature was lowered to room temperature, the reaction solution was taken out, and the sediment was removed by centrifugation (3000 rpm, 10 minutes). The supernatant was stored in a glove box.

The obtained nanoparticles had a fluorescence peak wavelength of 528 nm and a fluorescence quantum yield of 13%.

Example 1

The Octadecane solution of InP / ZnS nanoparticles obtained in Synthesis Example 1 was poured into ethanol to reprecipitate the nanoparticles. The solvent was removed by decantation, followed by vacuum drying to obtain nanoparticles (component A) (140 mg).

In a nitrogen atmosphere, dibutyl phosphate (component D) (34 mg) and 2-ethyl hexyl acrylate (component C) (70 mg) were added to disperse the nanoparticles. Trimethylolpropane triacrylate (component B) (104 mg) and polybenzylmethacrylate (weight average molecular weight 15, 000) (14 mg) were added and ultrasonically dispersed. Finally, Irgacure 907 (manufactured by Ciba Specialty Chemicals) (2 mg) was dissolved at a certain place to obtain an ink composition.

The viscosity of the ink composition at 25 ° C is measured using an automatic micro viscometer (AM manufactured by Anton Paar) As a result of measurement using a Vn type), it had a viscosity of 0.012 Pa's.

A black matrix (V259 BK (manufactured by Nippon Steel Chemical Co., Ltd.)) having a width of 20 / im and a thickness of 1 · 5 μΐη was produced at intervals of 90 μm by a photolithography method. We also prepared a glass substrate on which a partition wall (VPA100ZP54-2 (manufactured by Nippon Steel Chemical Co., Ltd.)) with a width of 15 μm and a height of 10 μm was formed on a black matrix.

The ink composition was applied once to the area of the glass substrate separated by the partition walls, and cured by irradiating 300 mJ of ultraviolet light having a wavelength of 365 nm to produce a fluorescence conversion substrate.

When a blue light emitting organic EL device was attached to emit light, the blue light of the organic EL device was converted to red with a peak wavelength of 634 nm.

[0042] Example 2

The octadecane solution of Cu-doped ZnSe nanoparticles obtained in Synthesis Example 2 was poured into ethanol to reprecipitate the nanoparticles. The solvent was removed by decantation, followed by vacuum drying to obtain Cu-doped ZnSe nanoparticles (component A) (103 mg).

Under a nitrogen atmosphere, xylene (20 mg) and trioctylphosphine oxide (component D) (25 mg) were added to disperse the nanoparticles. Add an epoxy resin (EPON825, Japan Epoxy Resin Co., Ltd.) (component B) (80 mg), benzylglycidyl ether (component C) (60 mg), trimellitic acid tris (1 propoxychetyl ester) (2 mg) and ultrasonically disperse. It was.

When measured in the same manner as in Example 1, the ink composition had a viscosity of 0. OlPa's at 25 ° C.

In the same manner as in Example 1, the ink composition was applied once and xylene was evaporated, followed by heating to 160 ° C. to react and cure the epoxy compound, thereby producing a fluorescence conversion substrate.

When a blue light-emitting organic EL device was laminated on the glass substrate to emit light, the blue light of the organic EL device was converted to green with a peak wavelength of 528 nm.

[0043] Example 3

The light emitting device 1 shown in FIG. 1 was produced as follows.

In the same manner as in Example 1, a black matrix 12 was formed on a glass substrate 11, and a partition wall 13 was formed on the black matrix 12. The composition used in Example 1 was applied once every 3 lines in the area separated by the partition wall 13. It is cured by irradiating 300mJ with 365nm wavelength ultraviolet rays. Then, a red fluorescence conversion film 15 was formed.

In the next step, the composition used in Example 2 was applied once next to one of the red fluorescence conversion films 15. After evaporating xylene, the epoxy compound was reacted and cured by heating to 160 ° C. to form a green fluorescent conversion film 17.

Finally, methyl methacrylate 'methacrylic acid copolymer (Mw = 13, 000) (27 wt%), pentaerythritol tri Atari rate (19 wt ^_0/0), Irugakyua 907 (0.4 wt ^_0/0), Photo-curable ink 19 composed of 2-acetoxy 1-methoxypropane (53.6% by weight) was applied to the entire surface of the substrate by a spin coating method. After drying the solvent at 120 ° C., it was cured by irradiation with 300 mJ of ultraviolet light having a wavelength of 365 ηm.

Thereby, the fluorescence conversion substrate 10 was completed.

On the substrate 21, an electrode (not shown) processed in a matrix in accordance with the pitch of the partition walls 13 of the fluorescence conversion substrate 10 and a blue light-emitting organic EL element 23 were formed to produce an organic EL panel 20. .

The light emitting device 1 was manufactured by laminating the fluorescence conversion substrate 10 and the organic EL panel 20. When an image was displayed on the light emitting device 1, a full color image could be displayed.

Industrial applicability

The color display device using the color conversion substrate of the present invention is a consumer or industrial display, for example, a display for a portable display terminal, an in-vehicle display such as a car navigation system or an instrument panel, a personal computer for office automation (OA), Used for TV (TV receiver) or FA (factory automation) display devices. In particular, it is used for thin, flat monocolor, multicolor or full color displays.

Claims

The scope of the claims

[I] A composition comprising the following components (A) to (C).

(A) Fluorescent inorganic nanocrystal

(B) Polyfunctional crosslinkable compound

[2] The composition according to claim 1, wherein the total proportion of components (A) to (C) is 40% by weight or more.

[3] Ingredient (A) :: ~ 45% by weight,

Ingredient (B) is:! ~ 40% by weight,

The composition according to claim 1 or 2, wherein the component (C) is contained: from 40 to 40% by weight.

[4] The yarn according to any one of claims 1 to 3, wherein the polyfunctional crosslinkable compound (B) comprises at least one of a polyfunctional (meth) acrylate and a polyfunctional epoxy compound.

[5] The composition according to any one of claims 1 to 4, further comprising the following component (D):

(D) Surface treatment agent for fluorescent inorganic nanocrystals

[6] The composition according to claim 5, wherein the surface treatment agent (D) of the fluorescent inorganic nanocrystal has a partially polymerizable or crosslinkable substituent.

7. The composition according to claim 5 or 6, wherein component (D) is contained in an amount of 20% by weight or less.

[8] Surface treatment agent for fluorescent inorganic nanocrystals (D) force Selected from amino group, thiol group, phosphate ester group, phosphonic acid group, carboxyl group, olefin group, phosphine group, phosphine oxide group, epoxy group The composition according to any one of claims 5 to 7, which has at least one substituent.

[9] The composition according to any one of claims 8 to 8, further comprising a polymerization initiator.

10. The composition according to any one of claims 1 to 9, wherein the content of a component having a boiling point of 200 ° C or lower is 0 to 60% by weight.

[II] Viscosity at 25 ° C Any of claims 1 to 10 in the range of 0.001 to 0.020 Pa's A composition according to any of the above.

[12] Claims: A cured product obtained by curing the composition according to any one of! To 11.

[13] a substrate;

13. A fluorescence conversion substrate comprising a fluorescence conversion film comprising the cured product according to claim 12 on the substrate.

14. The fluorescence conversion substrate according to claim 13, wherein a partition wall is provided on the substrate, and the fluorescence conversion film is in an area partitioned by the partition wall.

[15] A method for producing a fluorescence conversion substrate, wherein a fluorescence conversion film is formed by curing the composition according to any one of claims 1 to 11 on a substrate.

16. The method for producing a fluorescence conversion substrate according to claim 15, wherein the fluorescence conversion film is formed by applying the composition according to any one of claims 1 to 11 on a substrate by a printing method.

17. The method for producing a phosphor conversion substrate according to claim 16, wherein the printing method is an inkjet method or a nozure jet method.

[18] The method for producing a fluorescence conversion substrate according to any one of [15] to [17], wherein the fluorescence conversion film is formed by applying the composition to the area on the substrate delimited by the partition walls.

[19] a light emitting device;

A light-emitting device comprising the fluorescence conversion substrate according to claim 13 or 14.