CN104041181A

CN104041181A - Light-emitting element and resin composition for forming light-emitting element

Info

Publication number: CN104041181A
Application number: CN201380005156.2A
Authority: CN
Inventors: 杉山直树; 大月敏敬
Original assignee: JSR Corp
Current assignee: JSR Corp
Priority date: 2012-01-12
Filing date: 2013-01-11
Publication date: 2014-09-10
Also published as: KR20140110931A; JPWO2013105626A1; TW201336342A; WO2013105626A1

Abstract

A light-emitting element provided with a first electrode, a light-emitting layer, a second electrode, and a first resin layer. The light-emitting element is characterized in that the first electrode, the light-emitting layer, and the second electrode are stacked in that order, the first resin layer being formed on at least one of (a) the side of the first electrode opposite the side where the light-emitting layer is formed, and (b) the side of the second electrode opposite the side where the light-emitting layer is formed; and in comprising resin having a glass-transition temperature (Tg) of at least 170 DEG C as measured using differential scanning calorimetry (DSC, temperature-increase speed 20 DEG C/min), and a particle (A) with an average particle diameter of 0.1-5 [mu]m.

Description

Luminescence component and luminescence component formation resin combination

Technical field

The present invention relates to a kind ofly there is the luminescence component of specific resin bed and in order to form the luminescence component formation resin combination of this resin bed.

Background technology

Luminescence component has at the surface of the transparency carrier basic comprising that the transparent positive electrode layer of sequential lamination, luminous material layer and negative electrode layer form according to this.For example organic electroluminescence assembly is: by the electric hole from its positive electrode layer, inside from the electronic injection of its negative electrode layer to the luminous material layer that comprises organic material, in the inside of luminous material layer, be combined again in electric hole with electronics, thereby generate exciton (exciton), the release (fluorescence, phosphorescence) of the light during by this exciton inactivation and luminous luminescence component, the light self-induced transparency substrate-side outgoing being produced by this luminous material layer is to the outside of luminescence component.

In patent documentation 1, disclose the luminescence component of the high refractive index layer with high refractive index resins such as using polyethersulfone resin, polyetherimide resin.

Prior art document

Patent documentation

Patent documentation 1: Japanese Patent Laid-Open 2004-296438 communique

Summary of the invention

Invent problem to be solved

The luminescence component of recording according to patent documentation 1, can the self-induced transparency substrate-side light that outgoing is produced by luminous material layer efficiently to a certain degree.But, there is the light sending because of luminous material layer, and cause the deteriorated problem of the high refractive index resins such as polyethersulfone resin or polyetherimide resin.

Therefore, the object of this invention is to provide a kind of luminescence component of outgoing efficiency excellence of light.

The means of dealing with problems

Present inventor is research with keen determination in order to solve above-mentioned problem, found that, according to the luminescence component that comprises following resin bed, and can reach above-mentioned purpose, thereby complete the present invention: this resin bed comprises the polymer with specific glass transition temperature, and comprised the particle with specific particle diameter.

, the invention provides following [1]～[7].

[1] luminescence component, it comprises the 1st electrode, luminescent layer, the 2nd electrode and the 1st resin bed, it is characterized in that: described the 1st electrode, described luminescent layer, described the 2nd electrode according to this sequential lamination form, and described the 1st resin bed is formed at

(a) opposition side of the side that is formed with described luminescent layer of described the 1st electrode and

(b) at least one of the opposition side of the side that is formed with described luminescent layer of described the 2nd electrode,

And comprising the glass transition temperature (Tg) of measuring (DSC (differential scanning calorimetry), 20 DEG C/min of programming rates) by differential scanning calorimetry is that 170 DEG C of above resin and average grain diameters are the particle (A) of 0.1 μ m～5 μ m.

[2] luminescence component as described in [1], it is that 1nm is above and be less than metal oxide microparticle (B) of 100nm that wherein said the 1st resin bed also comprises average grain diameter.

[3] luminescence component as described in [1] or [2], it more comprises the 2nd resin bed, and described the 2nd resin bed is formed at

(c) opposition side of the side that is formed with described luminescent layer of described the 1st electrode and

(d) at least one of the opposition side of the side that is formed with described luminescent layer of described the 2nd electrode,

And comprising the glass transition temperature (Tg) of measuring (DSC, 20 DEG C/min of programming rates) by differential scanning calorimetry is 170 DEG C of above resins, and use the light of wavelength 632.8nm and the refractive index measured is more than 1.60.

[4] luminescence component as described in [3], wherein said the 2nd resin bed is formed at

(c) between described the 1st electrode and described the 1st resin bed and

(d) at least one between described the 2nd electrode and described the 1st resin bed.

[5] luminescence component as described in any one in [1] to [4], wherein said luminescence component is organic electroluminescence assembly.

[6] a luminescence component formation resin combination, it is in order to form the 1st resin bed of the luminescence component as described in any one in [1] to [5].

[7] a luminescence component formation resin combination, it is in order to form the 2nd resin bed of the luminescence component as described in any one in [3] to [5].

The effect of invention

The outgoing efficiency excellence of the light of luminescence component of the present invention.In addition, the durability of luminescence component of the present invention is also excellent, even if therefore under harsh service condition, also can not reduce performance for a long time and uses.

Brief description of the drawings

Fig. 1 is the profile of the example example 1 of conceptual expression luminescence component of the present invention.

Fig. 2 is the profile of the example example 2 of conceptual expression luminescence component of the present invention.

Fig. 3 is the profile of the example example 3 of conceptual expression luminescence component of the present invention.

Embodiment

" luminescence component "

Below, describe with reference to the graphic various example examples to luminescence component of the present invention, but as long as following luminescence component, there is no particular restriction, it is a kind of luminescence component, it comprises the 1st electrode, luminescent layer, the 2nd electrode, the 1st resin bed, and above-mentioned the 1st electrode, above-mentioned luminescent layer, above-mentioned the 2nd electrode according to this sequential lamination forms, above-mentioned the 1st resin bed comprises by differential scanning calorimetry measures (DSC, 20 DEG C/min of programming rates) glass transition temperature (Tg) be 170 DEG C of above resins (being also called below " polymer (I) "), and average grain diameter is the particle (A) of 0.1 μ m～5 μ m, and be formed at

(a) opposition side of the side that is formed with above-mentioned luminescent layer of above-mentioned the 1st electrode and

(b) at least one of the opposition side of the side that is formed with above-mentioned luminescent layer of above-mentioned the 2nd electrode.

Fig. 1 represents that the example example 1 of luminescence component of the present invention is luminescence component 10.Luminescence component 10 has the structure that sequential lamination substrate 11, the 1st electrode 13, luminescent layer 15, the 2nd electrode 17 and the 1st resin bed 18 form according to this., the 1st resin bed 18 is arranged on the face of opposition side of the side that is provided with luminescent layer 15 of the 2nd electrode 17.

The 2nd electrode 17 is preferably penetrating type electrode, and the light now being produced by luminescent layer 15 is by the 2nd electrode 17 and the 1st resin bed 18, and can outgoing to the outside of luminescence component 10.

Luminescence component of the present invention, owing to comprising the 1st resin bed 18, when the light therefore being produced by luminescent layer 15 enters in air by the 2nd electrode 17, can improve the efficiency of outgoing to luminescence component outside by the refraction of light.

Luminescence component 10 is preferably the refractive index of the 2nd electrode 17, the refractive index of the 1st resin bed 18, refractive index (approximately 1.0) luminescence component that order diminishes according to this of air.In addition, be preferably specific refractivity, the 1st resin bed 18 of the 2nd electrode 17 and the 1st resin bed 18 little with the specific refractivity of air.If there is this kind of relation in the refractive index of the 2nd electrode, the 1st resin bed and air, in the light outgoing being produced by luminescent layer 15 to the outside step of luminescence component 10, interface and the 1st resin bed 18 at the 2nd electrode 17 and the 1st resin bed 18 are difficult to occur total reflection with the interface of air, therefore think that the outgoing efficiency of light uprises.

In Fig. 1, to contact with a face of the 2nd electrode 17, former illustrates the 1st resin bed 18, but between the 1st resin bed 18 and the 2nd electrode 17, various layers also can be further set as required.

In addition, between opposition side, substrate 11 and the 1st electrode 13 of the side that is formed with the 1st electrode 13 of substrate 11, between the 1st electrode 13 and luminescent layer 15, between luminescent layer 15 and the 2nd electrode 17, the opposition side of the side that is formed with the 2nd electrode 17 of the 1st resin bed 18, various layers also can be set as required.

As this kind of various layer, with regard to obtaining the aspect of luminescence component that the outgoing efficiency of light is higher etc., for make refractive index along with luminescent module 15 through the 1st resin bed 18 to the outer row of luminescence component 10 and then diminish, and between the 2nd electrode 17 and the 1st resin bed 18 and/or the opposition side of the side that is formed with the 2nd electrode 17 of the 1st resin bed 18, the layer such as the 2nd resin bed or the 3rd resin bed can be set.

In addition, though not shown in Fig. 1, the known sealant in order to sealed light emitting assembly 10 also can be further set, and can realize various variation.

Fig. 2 represents that the example example 2 of luminescence component of the present invention is luminescence component 20.

Luminescence component 20 has the structure that sequential lamination substrate 21, the 1st resin bed the 28, the 1st electrode 23, luminescent layer 25 and the 2nd electrode 27 form according to this., the 1st resin bed 28 is arranged on the face of opposition side of the face that is provided with luminescent layer 25 of the 1st electrode 23.

The 1st electrode 23 is preferably penetrating type electrode, the light now being produced by luminescent layer 25, by the 1st electrode the 23, the 1st resin bed 28 and substrate 21, and can outgoing to the outside of luminescence component 20.

The variation of luminescence component 20 is same as described above.

Luminescence component 20 is preferably the refractive index of the 1st electrode 23, the refractive index of the 1st resin bed 28, the refractive index of substrate 21, refractive index (approximately 1.0) luminescence component that order diminishes according to this of air.

In addition, if consider the outgoing efficiency of the light of luminescence component 20, aforesaid substrate 21 is preferably glass substrate or the transparent plastic substrate that refractive index is less than the 1st resin bed 28.

Luminescence component 20 is owing to having the 1st resin bed 28, therefore can by the light being produced by luminescent layer 25 by the refraction of light effectively outgoing to outside, and become the high luminescence component of outgoing efficiency of light.

Fig. 3 represents that the example example 3 of luminescence component of the present invention is luminescence component 30.

Luminescence component 30 has the structure that sequential lamination substrate 31, the 1st or the 2nd resin bed the 38, the 1st electrode 33, luminescent layer 35, the 2nd electrode 37 and the 1st or the 2nd resin bed 39 form according to this.That is, resin bed 38 is arranged on the face of opposition side of the face that is provided with luminescent layer of the 1st electrode 33, and resin bed 39 is arranged on the face of opposition side of the face that is provided with luminescent layer of the 2nd electrode 37.But at least one of above-mentioned resin bed 38 and resin bed 39 is the 1st resin bed.In addition, but also both are the 1st resin bed for above-mentioned resin bed 38 and resin bed 39.

The 1st electrode 33 and the 2nd electrode 37 are preferably penetrating type electrode, the light now being produced by luminescent layer 35, after the 1st electrode 33 and the 2nd electrode 37, respectively by resin bed 38 and resin bed 39, and can outgoing to the outside of luminescence component 30.

The variation of luminescence component 30 is same as described above.

Luminescence component 30 is preferably: the refractive index (approximately 1.0) of the refractive index of the 2nd electrode 37, the refractive index of resin bed 39, air according to this order diminishes, and the refractive index of the refractive index of the 1st electrode 33, resin bed 38, the refractive index of substrate 31, refractive index (approximately 1.0) luminescence component that order diminishes according to this of air.

In addition, if consider the outgoing efficiency of the light of luminescence component 30, aforesaid substrate 31 is preferably glass substrate or the transparent plastic substrate that refractive index is less than resin bed 38.

Luminescence component 20 is owing to having resin bed 38 and resin bed 39, therefore can by the light being produced by luminescent layer 35 by the refraction of light effectively outgoing to outside, and become the high luminescence component of outgoing efficiency of light.

< substrate >

Aforesaid substrate can use the substrate using in common luminescence component, is preferably glass substrate or the transparent plastic substrate of mechanical strength, thermal stability, the transparency, surface smoothness, processing ease and water proofing property excellence.

< the 1st electrode >

Above-mentioned the 1st electrode can use the 1st electrode formation material, manufactures at upper surface of substrate etc. by vapour deposition method or sputtering method etc.In the time forming penetrating type electrode, the 1st electrode forms tin indium oxide (Indium Tin Oxide, ITO), indium zinc oxide (Indium Zinc Oxide, IZO), the tin oxide (SnO that can use transparent and electrically conductive excellence with material ₂), zinc oxide (ZnO) etc.

In addition, in the time forming reflective electrode, the 1st electrode formation can be used magnesium (Mg), aluminium (Al), aluminium-lithium (Al-Li), calcium (Ca), magnesium-indium (Mg-In), magnesium-Yin (Mg-Ag) etc. with material.The thickness of the 1st electrode is as long as carry out suitably selecting according to desired object.

< luminescent layer >

Above-mentioned luminescent layer is preferably and utilizes the material that shows luminescence phenomenon by applying electric field to carry out the luminescent layer of film forming.Electroluminescence (electroluminescence, the EL) material always having used since this kind of material can use previously: activation zinc sulphide ZnS:X (wherein X is the active elements such as Mn, Tb, Cu, Sm), CaS:Eu, SrS:Ce, SrGa ₂s ₄: Ce, CaGa ₂s ₄: Ce, CaS:Pb, BaAl ₂s ₄: the inorganic ELs such as Eu (EL) material; The low molecule pigments such as the aluminium misfit thing of oxine, aromatic amine, anthracene single crystal are organic EL material; Poly-(to phenylacetylene), poly-[2-methoxyl group-5-(2-ethyl hexyl oxy)-Isosorbide-5-Nitrae-phenylacetylene], poly-(3-alkylthrophene), the organic EL material of polyvinylcarbazole equiconjugate macromolecular etc.

In these, because the 1st resin bed comprises polymer (I), therefore luminescent layer is preferably the layer that uses organic EL material and form.So, be when layer that uses organic EL material to form at luminescent layer, can obtain organic el element.The thickness of luminescent layer is generally 10nm～1000nm, is preferably 30nm～500nm, and You Jia is 50nm～200nm.Luminescent layer can or form chloroform etc. by evaporation or sputter equal vacuum film forming processing procedure as the coating process of solvent.

< the 2nd electrode >

Above-mentioned the 2nd electrode can use the 2nd electrode formation material, manufactures by vapour deposition method or sputtering method etc.The 2nd electrode formation can be enumerated with material: lithium (Li), magnesium (Mg), aluminium (Al), aluminium-lithium (Al-Li), calcium (Ca), magnesium-indium (Mg-In), magnesium-Yin (Mg-Ag) etc.

Form film and can obtain penetrating type electrode by these materials.In addition, also can be and comprise the penetrating type electrode that ITO, IZO form.The thickness of the 2nd electrode is as long as carry out suitably selecting according to desired object.

It is negative electrode that above-mentioned the 2nd electrode is preferably electron injection electrode.

< the 1st resin bed >

It is that the particle (A) of 0.1 μ m～5 μ m and the luminescence component of organic solvent (being also called below " specific solvent ") form the layer forming with resin combination that above-mentioned the 1st resin bed is preferably by least comprising polymer (I), average grain diameter.

Luminescence component of the present invention, owing to containing above-mentioned the 1st resin bed, therefore becomes the luminescence component of the outgoing efficiency excellence of light.

This kind the 1st resin bed can comprise more than 2 layers in luminescence component of the present invention.Now, the 1st resin bed that comprises same composition can comprise more than 2 layers in luminescence component of the present invention, and the 1st resin bed of different compositions also can comprise more than 2 layers in luminescence component of the present invention.

[glass transition temperature (Tg) is 170 DEG C of above resins (polymer (I))]

Above-mentioned polymer (I) can preferably use: the thermoplastic resins such as aromatic polyether based polymer (being also called below " polymer (II) ") and polyimides based polymer and silicone-based, epoxy system, acrylic acid series, cyanoacrylate system, epoxy are the thermosetting resins such as acrylate.Particularly by being used as the aftermentioned polymer (III) of thermoplastic resin, and the resin combination of film forming excellence can be obtained, and outgoing efficiency and the fully excellent luminescence component of thermal endurance isoequilibrium of light can be obtained.

Polymer (I) can be used alone a kind, also two or more can be used in combination.

[polymer (I)]

Above-mentioned polymer (I) is measured (DSC by differential scanning calorimetry, 20 DEG C/min of programming rates) glass transition temperature (Tg) be the polymer of 170 DEG C～350 DEG C, be preferably 240 DEG C～330 DEG C, be more preferred from 250 DEG C～300 DEG C.

8230 types (trade name) the DSC determinator (20 DEG C/min of programming rates) that the glass transition temperature of above-mentioned polymer (I) for example uses Neo-Confucianism (Rigaku) company to manufacture is measured.

The resin bed that comprises this kind of polymer (I), its thermal endurance, mechanical strength and electrical characteristic isoequilibrium are fully excellent.

Above-mentioned polymer (II) is the polymer that the reaction by form ehter bond on main chain obtains, and is preferably the polymer (being also called below " polymer (III) ") with at least one construction unit (i) in the choosing cohort that freely construction unit (being also called below " construction unit (1) ") shown in following formula (1) and the construction unit (being also called below " construction unit (2) ") shown in following formula (2) form.There is construction unit (i) by polymer, and become the aromatic polyether based polymer that glass transition temperature is above-mentioned scope.The resin bed that comprises this kind of polymer (III), its thermal endurance, electrical characteristic and the transparency are excellent, and have high refractive index.In addition,, if resin bed comprises polymer (III), can obtain the outgoing efficiency of light and the luminescence component of excellent in te pins of durability.

In addition, above-mentioned polymer (II), particularly polymer (III) are compared with polyethersulfone resin or polyetherimide resin etc., and the absorption of the light of visible-range is few, are therefore difficult to cause that because of visible ray resin is deteriorated.Therefore comprise the luminescence component, particularly excellent in te pins of durability of the resin bed that comprises above-mentioned polymer (II), particularly polymer (III), therefore better.

[changing 1]

In above-mentioned formula (1), R ¹～R ⁴the independent 1 valency organic group that represents carbon number 1～12 respectively.A～d is independent 0～4 the integer that represents respectively, is preferably 0 or 1.

1 valency organic group of carbon number 1～12 can be enumerated: 1 valency alkyl of carbon number 1～12 and comprising selects 1 valency organic group of the carbon number 1～12 of at least a kind of atom in the cohort that free oxygen atom and nitrogen-atoms form etc.

1 valency alkyl of carbon number 1～12 can be enumerated: the aromatic hydrocarbyl of the straight or branched alkyl of carbon number 1～12, the ester ring type alkyl of carbon number 3～12 and carbon number 6～12 etc.

The straight or branched alkyl of above-mentioned carbon number 1～12 is preferably the straight or branched alkyl of carbon number 1～8, is more preferred from the straight or branched alkyl of carbon number 1～5.

The preferably concrete example of above-mentioned straight or branched alkyl can be enumerated: methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl, the second butyl, tributyl, n-pentyl, n-hexyl and n-heptyl.

The ester ring type alkyl of above-mentioned carbon number 3～12 is preferably the ester ring type alkyl of carbon number 3～8, is more preferred from the ester ring type alkyl of carbon number 3 or carbon number 4.

The preferably concrete example of the ester ring type alkyl of carbon number 3～12 can be enumerated: the cycloalkyl such as cyclopropyl, cyclobutyl, cyclopenta and cyclohexyl; The cycloalkenyl groups such as cyclobutane base, cyclopentenyl and cyclohexenyl group.The bonding position of this ester ring type alkyl can be any carbon on alicyclic ring.

The aromatic hydrocarbyl of above-mentioned carbon number 6～12 can be enumerated: phenyl, xenyl and naphthyl etc.The bonding position of this aromatic hydrocarbyl can be any carbon on aromatic ring.

The organic group of the carbon number 1～12 that comprises oxygen atom can be enumerated: the organic group that comprises hydrogen atom, carbon atom and oxygen atom, is wherein preferably and can enumerates: the organic group of the total carbon number 1～12 that comprises ehter bond, carbonyl or ester bond and alkyl etc.

The organic group with total carbon number 1～12 of ehter bond can be enumerated: alkynyloxy group, the aryloxy group of carbon number 6～12 and the alkoxyalkyl of carbon number 1～12 etc. of the alkoxyl of carbon number 1～12, the alkene oxygen base of carbon number 2～12, carbon number 2～12.Specifically can enumerate: methoxyl group, ethyoxyl, propoxyl group, isopropoxy, butoxy, phenoxy group, propenyloxy group, cyclohexyloxy and methoxy etc.

In addition, the organic group that has total carbon number 1～12 of carbonyl can be enumerated: the acyl group of carbon number 2～12 etc.Specifically can enumerate: acetyl group, propiono, isopropyl acyl group and benzoyl etc.

The organic group with total carbon number 1～12 of ester bond can be enumerated: the acyloxy of carbon number 2～12 etc.Specifically can enumerate: acetoxyl group, propionyloxy, isopropyl acyloxy and benzoyloxy etc.

The organic group of the carbon number 1～12 that comprises nitrogen-atoms can be enumerated: the organic group that comprises hydrogen atom, carbon atom and nitrogen-atoms, specifically can enumerate: cyano group, imidazole radicals, triazolyl, benzimidazolyl and BTA base etc.

The organic group of the carbon number 1～12 that comprises oxygen atom and nitrogen-atoms can be enumerated: the organic group that comprises hydrogen atom, carbon atom, oxygen atom and nitrogen-atoms, specifically can enumerate: oxazolyl, oxadiazoles base, benzoxazolyl and benzo oxadiazoles base etc.

R in above-mentioned formula (1) ¹～R ⁴be preferably 1 valency alkyl of carbon number 1～12, be more preferred from the aromatic hydrocarbyl of carbon number 6～12, You Jia is phenyl.

[changing 2]

In above-mentioned formula (2), R ¹～R ⁴and a～d R independently and in above-mentioned formula (1) respectively ¹～R ⁴and a～d synonym, Y represents singly-bound ,-SO ₂-or > C=O, R ⁷and R ⁸independent 1 valency organic group or the nitro that represents halogen atom, carbon number 1～12 respectively, m represents 0 or 1.Wherein m is 0 o'clock, R ⁷be not cyano group.G and h be independent 0～4 the integer that represents respectively, is preferably 0.

1 valency organic group of carbon number 1～12 can be enumerated: the organic group identical with 1 valency organic group of the carbon number 1～12 in above-mentioned formula (1) etc.

In above-mentioned polymer (III), the mol ratio of said structure unit (1) and said structure unit (2) (wherein both (construction unit (1)+construction units (2)) add up to 100), just become optical characteristics, the aspect of the polymer of the excellence such as thermal endurance and mechanical characteristic etc., be preferably construction unit (1): construction unit (2)=50: 50～100: 0, be more preferred from construction unit (1): construction unit (2)=70: 30～100: 0, You Jia is construction unit (1): construction unit (2)=80: 20～100: 0.

Herein, mechanical characteristic refers to the character such as hot strength, elongation at break and the modulus of elasticity in direct stress of polymer.

In addition, above-mentioned polymer (III) can have more at least one construction unit (ii) in the choosing cohort that freely construction unit shown in following formula (3) and the construction unit shown in following formula (4) form.If above-mentioned polymer (III) has this kind of construction unit (ii), the mechanical characteristic of the resin bed being obtained by the constituent with this polymer (III) improves, therefore better.

[changing 3]

In above-mentioned formula (3), R ⁵and R ⁶the independent 1 valency organic group that represents carbon number 1～12 respectively, Z represents singly-bound ,-O-,-S-,-SO ₂-, the divalent organic group of > C=O ,-CONH-,-COO-or carbon number 1～12, n represents 0 or 1.E and f be independent 0～4 the integer that represents respectively, is preferably 0.

The divalent organic group of carbon number 1～12 can be enumerated: the divalent alkyl of carbon number 1～12, the divalent halogenation alkyl of carbon number 1～12, the divalent organic group that comprises the carbon number 1～12 that selects at least a kind of atom in the cohort that free oxygen atom and nitrogen-atoms form and comprising selects divalent halogenation organic group of the carbon number 1～12 of at least a kind of atom in the cohort that free oxygen atom and nitrogen-atoms form etc.

The divalent alkyl of carbon number 1～12 can be enumerated: straight or branched divalent alkyl, the divalent ester ring type alkyl of carbon number 3～12 and the divalent aromatic hydrocarbyl of carbon number 6～12 etc. of carbon number 1～12.

The straight or branched divalent alkyl of carbon number 1～12 can be enumerated: methylene, ethylidene, trimethylene, isopropylidene, pentamethylene, hexa-methylene and heptamethylene etc.

The divalent ester ring type alkyl of carbon number 3～12 can be enumerated: the cycloalkylidenes such as cyclopropylidene, sub-cyclobutyl, cyclopentylene and cyclohexylidene; The sub-cycloalkenyl groups such as sub-cyclobutane base, cyclopentenylidene and cyclohexadienylidene etc.

The divalent aromatic hydrocarbyl of carbon number 6～12 can be enumerated: phenylene, naphthylene and biphenylene etc.

The divalent halogenation alkyl of carbon number 1～12 can be enumerated: straight or branched divalent halogenation alkyl, the divalent halogenation ester ring type alkyl of carbon number 3～12 and the divalent halogenated aromatic alkyl of carbon number 6～12 etc. of carbon number 1～12.

The straight or branched divalent halogenation alkyl of carbon number 1～12 can be enumerated: difluoro methylene, dichloro methylene, tetrafluoro ethylidene, tetrachloro ethylidene, hexafluoro trimethylene, chlordene trimethylene, hexafluoroisopropyli,ene and chlordene isopropylidene etc.

The divalent halogenation ester ring type alkyl of carbon number 3～12 can be enumerated: in the divalent ester ring type alkyl of above-mentioned carbon number 3～12, at least a portion hydrogen atom of illustrated group is replaced group forming etc. by fluorine atom, chlorine atom, bromine atoms or iodine atom.

The divalent halogenated aromatic alkyl of carbon number 6～12 can be enumerated: in the divalent aromatic hydrocarbyl of above-mentioned carbon number 6～12, at least a portion hydrogen atom of illustrated group is replaced group forming etc. by fluorine atom, chlorine atom, bromine atoms or iodine atom.

The organic group that comprises the carbon number 1～12 that selects at least a kind of atom in the cohort that free oxygen atom and nitrogen-atoms form can be enumerated: comprise hydrogen atom and carbon atom, organic group with oxygen atom and/or nitrogen-atoms, and can enumerate: the divalent organic group of the total carbon number 1～12 that comprises ehter bond, carbonyl, ester bond or amido link and alkyl etc.

The divalent halogenation organic group that comprises the carbon number 1～12 that selects at least a kind of atom in the cohort that free oxygen atom and nitrogen-atoms form specifically can be enumerated: in the divalent organic group that comprises the carbon number 1～12 that selects at least a kind of atom in the cohort that free oxygen atom and nitrogen-atoms form, at least a portion hydrogen atom of illustrated group is replaced group forming etc. by fluorine atom, chlorine atom, bromine atoms or iodine atom.

Z in above-mentioned formula (3) is preferably singly-bound ,-O-,-SO ₂-, the divalent organic group of > C=O or carbon number 1～12, be more preferred from divalent alkyl, the divalent halogenation alkyl of carbon number 1～12 or the divalent ester ring type alkyl of carbon number 3～12 of carbon number 1～12.

[changing 4]

In above-mentioned formula (4), R ⁷, R ⁸, Y, m, g and the h R in independent and above-mentioned formula (2) respectively ⁷, R ⁸, Y, m, g and h synonym, R ⁵, R ⁶, Z, n, e and the f R in independent and above-mentioned formula (3) respectively ⁵, R ⁶, Z, n, e and f synonym.In addition, m is 0 o'clock, R ⁷be not cyano group.

In above-mentioned polymer (III), the mol ratio of said structure unit (i) and said structure unit (ii) (wherein both ((i)+(ii)) add up to 100), with regard to becoming the aspect of the excellent polymer such as optical characteristics, thermal endurance and mechanical characteristic etc., be preferably (i): (ii)=50: 50～100: 0, be more preferred from (i): (ii)=70: 30～100: 0, You Jiawei (i): (ii)=80: 20～100: 0.

Above-mentioned polymer (III) is with regard to becoming the aspect of the excellent polymer such as optical characteristics, thermal endurance and mechanical characteristic etc., be preferably said structure unit (i) and said structure unit (ii) contains more than 70 % by mole in entire infrastructure unit, be more preferred from entire infrastructure unit and contain more than 95 % by mole.

Above-mentioned polymer (III) for example can obtain in the following manner: make to comprise the composition (being also called below " (A) composition ") of at least one compound in the choosing cohort that freely compound (being also called below " compound (5) ") shown in following formula (5) and the compound (being also called below " compound (7) ") shown in following formula (7) form, react with the composition that comprises the compound shown in following formula (6) (being also called below " (B) composition ").

[changing 5]

In above-mentioned formula (5), X independently represents halogen atom, is preferably fluorine atom.

[changing 6]

In above-mentioned formula (7), R ⁷, R ⁸, Y, m, g and the h R in independent and above-mentioned formula (2) respectively ⁷, R ⁸, Y, m, g and h synonym, X independent with above-mentioned formula (5) in X synonym.Wherein m is 0 o'clock, R ⁷be not cyano group.

[changing 7]

In above-mentioned formula (6), R ^aindependent hydrogen atom, methyl, ethyl, acetyl group, mesyl or the trifyl of representing, is wherein preferably hydrogen atom respectively.In addition, in formula (6), R ¹～R ⁴and a～d R independently and in above-mentioned formula (1) respectively ¹～R ⁴and a～d synonym.

Above-claimed cpd (5) specifically can be enumerated: 2,6-difluorobenzonitrile (2,6-difluorobenzonitrile, DFBN), 2,5-difluorobenzonitrile, 2,4-difluorobenzonitrile, 2,6-dichlorobenzonitrile, 2,5-dichlorobenzonitrile, 2,4-dichlorobenzonitrile and these reactive derivatives etc.Particularly, with regard to the viewpoint of reactivity and economy etc., be preferably and use 2,6-difluorobenzonitrile and 2,6-dichlorobenzonitrile.These compounds also can be used in combination two or more.

Compound shown in above-mentioned formula (6) (being also called below " compound (6) ") specifically can be enumerated: 9, two (4-hydroxy phenyl) Fluorene (9 of 9-, 9-Bis (4-hydroxyphenyl) fluorene, BPFL), 9, two (3-phenyl-4-hydroxy phenyl) Fluorene of 9-, 9, 9-two (3, 5-diphenyl-4-hydroxy phenyl) Fluorene, 9, two (the 4-hydroxy-3-methyl phenyl) Fluorene of 9-, 9, two (4-hydroxyl-3 of 9-, 5-3,5-dimethylphenyl) Fluorene, 9, two (4-hydroxyl-3-cyclohexyl phenyl) Fluorene of 9-and these reactive derivatives etc.In above-claimed cpd, be preferably and use two (4-hydroxy phenyl) Fluorene of 9,9-and two (3-phenyl-4-hydroxy phenyl) Fluorene of 9,9-.These compounds also can be used in combination two or more.

Above-claimed cpd (7) specifically can be enumerated: 4, 4 '-difluoro benzophenone, 4, 4 '-difluorodiphenyl base sulfone (4, 4 '-difluorodiphenylsulfone, DFDS), 2, 4 '-difluoro benzophenone, 2, 4 '-difluorodiphenyl base sulfone, 2, 2 '-difluoro benzophenone, 2, 2 '-difluorodiphenyl base sulfone, 3, 3 '-dinitro-4, 4 '-difluoro benzophenone, 3, 3 '-dinitro-4, 4 '-difluorodiphenyl base sulfone, 4, 4 '-dichloro benzophenone, 4, 4 '-dichloro diphenylsulfone, 2, 4 '-dichloro benzophenone, 2, 4 '-dichloro diphenylsulfone, 2, 2 '-dichloro benzophenone, 2, 2 '-dichloro diphenylsulfone, 3, 3 '-dinitro-4, 4 '-dichloro benzophenone and 3, 3 '-dinitro-4, 4 '-dichloro diphenylsulfone etc.In these, be preferably 4,4 '-difluoro benzophenone, 4,4 '-difluorodiphenyl base sulfone.These compounds also can be used in combination two or more.

Select at least one compound in the cohort that free compound (5) and compound (7) form, in 100 % by mole of (A) compositions, be preferably and contain 80 % by mole～100 % by mole, be more preferred from and contain 90 % by mole～100 % by mole.

In addition, (B) composition is preferably and comprises as required the compound shown in following formula (8).Compound (6), in 100 % by mole of (B) compositions, is preferably and contains 50 % by mole～100 % by mole, is more preferred from and contains 80 % by mole～100 % by mole, and You Jiawei contains 90 % by mole～100 % by mole.

[changing 8]

In above-mentioned formula (8), R ⁵, R ⁶, Z, n, e and the f R in independent and above-mentioned formula (3) respectively ⁵, R ⁶, Z, n, e and f synonym, R ^ar independently and in above-mentioned formula (6) respectively ^asynonym.

Compound shown in above-mentioned formula (8) can be enumerated: hydroquinones, resorcinol, 2-phenyl hydroquinones, 4, 4 '-'-biphenyl diphenol, 3, 3 '-'-biphenyl diphenol, 4, 4 '-dihydroxy-diphenyl sulfone, 3, 3 '-dihydroxy-diphenyl sulfone, 4, 4 '-dihydroxy benaophenonel, 3, 3 '-dihydroxy benaophenonel, 1, 1 '-union-2-naphthol, 1, 1 '-Lian-4-naphthols, 2, two (4-hydroxy phenyl) propane of 2-, 1, 1-bis(4-hydroxyphenyl)cyclohexane, 2, two (the 4-hydroxy phenyls)-1 of 2-, 1, 1, 3, 3, 3-HFC-236fa and these reactive derivatives etc.In above-claimed cpd, be preferably resorcinol, 4,4 '-'-biphenyl diphenol, 2, two (4-hydroxy phenyl) propane, 1 of 2-, 1-bis(4-hydroxyphenyl)cyclohexane, 2, two (the 4-hydroxy phenyls)-1 of 2-, 1,1,3,3,3-HFC-236fa, with regard to the viewpoint of reactivity and mechanical characteristic, be preferably and use 4,4 '-'-biphenyl diphenol.These compounds also can be used in combination two or more.

Above-mentioned polymer (III) more specifically, can synthesize by method shown below (I ').

Method (I '):

(B) composition is reacted with alkali metal compound in organic solvent, and obtain after the alkali metal salt of (B) composition (compound (6) and/or compound (8) etc.), the alkali metal salt of gained is reacted with (A) composition.In addition, by carrying out reacting of (B) composition and alkali metal compound under the existence at (A) composition, and can make the alkali metal salt of (B) composition react with (A) composition.

The alkali metal compound that reaction is used can be enumerated: the alkali metal such as lithium, potassium and sodium; The hydrogenated alkali metals such as lithium hydride, hydrofining and sodium hydride; The alkali hydroxide metals such as lithium hydroxide, potassium hydroxide and NaOH; The alkali carbonates such as lithium carbonate, potash and sodium carbonate; The alkali metal hydrogencarbonates such as lithium bicarbonate, saleratus and sodium acid carbonate etc.These can use a kind or also two or more can be used in combination.

Alkali metal compound uses with following amount: with respect in above-mentioned (B) composition whole-O-R ^a, and the amount of metallic atom in alkali metal compound to be generally 1 times～3 times equivalents, to be preferably 1.1 times～2 times equivalents, You Jia be 1.2 times～1.5 times equivalents.

In addition, the organic solvent that reaction is used can use: N, N-dimethylacetylamide (DMAc), N, dinethylformamide, METHYLPYRROLIDONE, 1,3-dimethyl-2-imidazolidine ketone, γ-butyl lactone, sulfolane, dimethyl sulfoxide (DMSO), diethyl sulfoxide, dimethyl sulfone, diethyl sulfone, diisopropyl sulfone, diphenyl sulfone, diphenyl ether, benzophenone, dialkoxy benzene (carbon number 1～4 of alkoxyl) and tri-alkoxy benzene (carbon number 1～4 of alkoxyl) etc.In these solvents, special good for using the high polar organic solvents of dielectric constant such as METHYLPYRROLIDONE, DMA, sulfolane, diphenyl sulfone and dimethyl sulfoxide (DMSO).These can use a kind or also two or more can be used in combination.

Moreover, when above-mentioned reaction, also can further use the solvent of benzene,toluene,xylene, hexane, cyclohexane, octane, chlorobenzene, dioxanes, oxolane, methyl phenyl ethers anisole and phenetole etc. and water azeotropic.These can use a kind or also two or more can be used in combination.

(A) composition and (B) usage ratio of composition, by (A) composition when (B) total of composition is made as 100 % by mole, (A) composition is preferably 45 % by mole above below 55 % by mole, be more preferred from 50 % by mole above below 52 % by mole, You Jiawei exceedes below 50 % by mole and 52 % by mole, (B) composition is preferably 45 % by mole above below 55 % by mole, be more preferred from 48 % by mole above below 50 % by mole, You Jia be 48 % by mole above and be less than 50 % by mole.

In addition, reaction temperature is preferably 60 DEG C～250 DEG C, is more preferred from the scope of 80 DEG C～200 DEG C.Reaction time is preferably 15 minutes～and 100 hours, be more preferred from 1 hour～scope of 24 hours.

The weight average molecular weight (Mw) of the polystyrene conversion that HLC-8220 type (trade name) GPC (gel permeation chromatography) device (tubing string: TSKgel α-M (trade name), developing solvent: oxolane (being also called below " THF ")) that above-mentioned polymer (II) is manufactured by eastern Cao (TOSOH) is measured, be preferably 5,000～500,000, be more preferred from 15,000～400,000, You Jia is 30,000～300,000.

The heat decomposition temperature that above-mentioned polymer (II) is measured by thermogravimetry (Thermo Gravimetric Analysis, TGA), is preferably more than 450 DEG C, is more preferred from more than 475 DEG C, and You Jia is more than 490 DEG C.

Above-mentioned luminescence component formation can directly be used the polymer (III) of gained and the mixture of organic solvent in said method (I ') with resin combination.Now, the organic solvent that above-mentioned reaction is used is specific solvent.

In addition, above-mentioned constituent also can be prepared in the following manner: the mixture from the polymer (III) obtaining by said method with organic solvent,, after (purifying) polymer (III), be again dissolved in specific solvent with the form list of solid constituent.

Form list with solid constituent for example can carry out in the following manner from the method for (purifying) above-mentioned polymer (III): in the poor solvent of the polymer such as methyl alcohol, make polymer again precipitate, then filter, then by screening drying under reduced pressure etc.

Make the specific solvent that above-mentioned polymer (III) dissolves again be preferably selection: easily to dissolve above-mentioned polymer (III) person.For example be preferably use: carrene, oxolane, cyclohexanone, N, dinethylformamide, N, N-dimethylacetylamide, METHYLPYRROLIDONE and gamma-butyrolacton, with regard to the viewpoint of screening characteristics, economy, be preferably suitable use carrene, cyclohexanone, DMA and METHYLPYRROLIDONE.These solvents can be used alone a kind or can and use two or more.

In addition, in order to realize the raising of drying property or uniformity, surface smoothness etc. in when coating, can be that organic solvent, ester are that organic solvent, ketone are that organic solvent, hydrocarbon system organic solvent, alcohol are that a kind of organic solvent or solvent of more than two kinds carry out appropriately combined and use by being selected from other specific solvents, for example ether.Now, under atmospheric pressure, the boiling point of (1,013hPa) is preferably 40 DEG C～250 DEG C, is more preferred from the organic solvent in the scope of 50 DEG C～150 DEG C, is preferably in the scope that can make polymer (III) dissolve equably, disperse and uses.

The better example of these other specific solvents can be enumerated: the glycol ethers such as ethylene glycol monoethyl ether, propylene glycol monomethyl ether; The ethylene glycol alkane ether acetic acid ester classes such as acetic acid ethyl cellosolve, propylene glycol methyl ether acetate, propylene-glycol ethyl ether acetic acid esters; The ester classes such as ethyl lactate, 2 hydroxy propanoic acid ethyl ester; The diethylene glycol classes such as diethylene glycol monomethyl ether, diethylene glycol dimethyl ether, diethylene glycol ethyl methyl ether; The ketones such as methyl ethyl ketone, methyl iso-butyl ketone (MIBK), 2-HEPTANONE, cyclohexanone, methyl amyl ketone.These can use a kind or also two or more can be used in combination.

In addition, above-mentioned specific solvent also can be preferably for comprising the luminescence component formation resin combination of polymer (III) polymer (I) in addition.

[epoxy is resin]

Comprise the resin bed that above-mentioned epoxy is resin, its thermal endurance, mechanical strength and gluing isoequilibrium are fully excellent.Comprise the resin bed that this kind of epoxy is resin, can comprise epoxy compounds and can make the luminescence component formation resin combination of the compound (being also called below " curing agent ") of this epoxy compounds sclerosis form by use.

Epoxy compounds specifically can be enumerated: the bisphenol type epoxy compoundss such as bisphenol A diglycidyl ether, Bisphenol F diglycidyl ether, bisphenol-S diglycidyl ether, the phenolic varnish type epoxy compoundss such as phenol phenolic varnish type epoxy compounds, cresols phenolic varnish type epoxy compounds, 3 ', 4 '-7-oxa-bicyclo[4.1.0 formic acid 3, 4-epoxycyclohexyl methyl esters, 2-(3, 4-epoxycyclohexyl-5, 5-spiral shell-3, 4-epoxy) a cyclohexane-dioxanes, two (3, 4-epoxycyclohexyl methyl) adipate ester, vinyl epoxy cyclohexane, 4 vinyl epoxy cyclohexane, two (3, 4-epoxy-6-methyl cyclohexane ylmethyl) adipate ester, 3 ', 4 '-epoxy-6 '-hexahydrotoluene formic acid 3, 4-epoxy-6-methyl cyclohexyl, di-2-ethylhexylphosphine oxide (3, 4-7-oxa-bicyclo[4.1.0), bicyclopentadiene diepoxide, second two (3, 4-7-oxa-bicyclo[4.1.0 formic acid esters), epoxidation four benzylalcohols, lactone upgrading 3 ', 4 '-7-oxa-bicyclo[4.1.0 formic acid 3, 4-epoxycyclohexyl methyl esters, lactone upgrading epoxidation tetrahydrochysene benzylalcohol, 7-oxa-bicyclo[4.1.0, hydrogenated bisphenol A diglycidyl ether, A Hydrogenated Bisphenol A F diglycidyl ether, the alicyclic epoxy compound classes such as hydrogenated bisphenol A D diglycidyl ether, BDDE, 1, the aliphatic epoxy compounds such as 6-hexanediol diglycidyl ether, T 55, trihydroxymethylpropanyltri diglycidyl ether, the halogenation epoxy compoundss such as brominated bisphenol A diglycidyl ether, brominated bisphenol F diglycidyl ether, brominated bisphenol S diglycidyl ether, the glycidyl group amine type epoxy compoundss and 9 such as four glycidyl group aminocarbonyl phenyl methane, two [4-(2-glycidoxypropyl propoxyl group)-3, the 5-3,5-dimethylphenyl] Fluorene etc. of 9-have the epoxy compounds of Fluorene skeleton etc.These can use a kind or also two or more can be used in combination.

Above-mentioned curing agent specifically can be enumerated: the amines such as aliphatic amine, aromatic amine, upgrading amine, polyamide, tertiary amine, secondary amine, imidazoles, thio-alcohol, anhydrides, boron trifluoride amine misfit thing, dicyano acid amides and organic acid hydrazides etc.These can use a kind or also two or more can be used in combination.

Epoxy is that the glass transition temperature of resin is preferably 170 DEG C～350 DEG C, is more preferred from 175 DEG C～300 DEG C.8230 types (trade name) the DSC determinator (20 DEG C/min of programming rates) that glass transition temperature for example uses company of science to manufacture is measured.

Be resin as the epoxy with this kind of glass transition temperature, epoxy compounds is preferably the epoxy compounds that uses phenolic varnish type epoxy compounds or have Fluorene skeleton, and curing agent is preferably and uses the combination person who comprises anhydrides.

Above-mentioned luminescence component forms the molecular weight that also depends on this polymer by the concentration of the polymer in resin combination (I), is generally 1 quality %～40 quality %, is preferably 5 quality %～25 quality %.If the concentration of the polymer in constituent (I) is above-mentioned scope, can form and can realize thick-film, be difficult to produce pin hole, and the resin bed of surface smoothness excellence.

In addition, above-mentioned luminescence component forms the molecular weight or the concentration that also depend on polymer (I) with the viscosity of resin combination, is preferably 50mPas～100,000mPas, is more preferred from 500mPas～50,000mPas, You Jia is 1000mPas～20,000mPas.If the viscosity of constituent is above-mentioned scope, the anelasticity excellence of the constituent of resin bed in forming, and easily adjust thickness, therefore easily form resin bed.

[particle (A)]

Above-mentioned resin bed comprises the particle (A) that average grain diameter is 0.1 μ m～5 μ m.Therefore, can give light diffusion function to above-mentioned resin bed, and can improve the outgoing efficiency of light.

The average grain diameter of particle (A) is preferably 0.2 μ m～3 μ m, is more preferred from 0.3 μ m～2 μ m.

In addition, this average grain diameter can be measured by the distribution of particles determinator taking dynamic light scattering method as measuring principle.

Particle (A) can use a kind or also two or more can be used in combination.

Herein in order to give light diffusion function, be preferably the particle that uses particle (A) large with the refringence of above-mentioned polymer (I), this kind of particle can be enumerated: have the particle of high index of refraction or have the particle of low-refraction.

The particle with high index of refraction can use: with as following metal oxide particle (B) and identical particle of illustrative particle etc. (wherein average grain diameter is above-mentioned scope).In addition, the refractive index of the light of the wavelength 632.8nm when particle with low-refraction is 25 DEG C is preferably below 1.55, is more preferred from the particle below 1.50, particularly, is preferably use organic filler.

Organic filler can be enumerated: polymethyl methacrylate (Polymethyl methacrylate, PMMA) particle, polystyrene particle and organic crosslinked particle etc.

Above-mentioned organic crosslinked particle can be manufactured by cross-linkable monomer.This cross-linkable monomer is preferably use: the non-conjugated divinyl compound taking divinylbenzene as representative or the multicomponent methacrylate compound taking trimethylol-propane trimethacrylate, trimethylolpropane triacrylate etc. as representative etc. has the compound of the two keys of more than 2 combined polymerization.Be more preferred from the compound with the two keys of 2 combined polymerizations.

In addition, above-mentioned organic filler, with regard to the viewpoint of low-refraction, can use hollow-particle.

About the addition of particle (A), consider the proportion of particle itself and the refringence with above-mentioned polymer (I), be preferably suitable adjustment, there is no particular restriction, for resin bed being given to physical strength and sufficient light diffusion function, the addition of particle (A) particularly, form solid constituent 100 mass parts with resin combination with respect to above-mentioned luminescence component, be preferably 1 mass parts～2000 mass parts, be more preferred from 2 mass parts～1000 mass parts, special good is 10 mass parts～100 mass parts.

If the allotment amount of particle (A) is above-mentioned scope, can under the state that maintains crack resistance etc., suitably adjust the light diffusion function of resin bed.

In addition, particle (A) used disperses when colloidal sol for solvent, and the allotment amount of above-mentioned particle (A) refers to not solvent-laden quality, and the amount of the contained solvent of this colloidal sol is calculated as the amount of above-mentioned specific solvent.

[metal oxide particle (B)]

In above-mentioned resin bed, in order to obtain the luminescence component of outgoing efficiency excellence of light, be preferably allotment average grain diameter and be 1nm above and be less than the metal oxide particle (B) of 100nm.The refractive index of the light of wavelength 632.8nm when this kind of particle (B) is 25 DEG C is preferably more than 1.75, be more preferred from more than 1.80, special good be more than 1.85 particulate.The resin bed that comprises the particle (B) with this kind of refractive index by use, and can obtain the more excellent luminescence component of outgoing efficiency of light.

In addition, refractive index is for example used prism coupler (prism coupler) Model2010 (trade name, Mai Teliken (Metricon) company manufactures) to measure.

Above-mentioned particle (B) for example can be enumerated: the metal oxide particles such as zirconia, titanium oxide, zinc oxide, tantalum oxide, indium oxide, hafnium oxide, tin oxide, niobium oxide, barium titanate and these compound.Wherein be preferably zirconia (ZrO ₂), titanium oxide (TiO ₂) or barium titanate (BaTiO ₃) particulate, and at the atomic surface-coated silicon dioxide (SiO of titanium oxide ₂), zirconia (ZrO ₂) or aluminium hydroxide (Al (OH) ₃) and suppress the particulate of photocatalyst function of titanium oxide.

If above-mentioned titanium oxide has TiO ₂structure, is not particularly limited, for example, can enumerate: Detitanium-ore-type, rutile-type, brookite type etc., with regard to suppressing the aspect of above-mentioned photocatalyst function and refractive index, the best is rutile-type.

These particles (B) can be used alone a kind, or two or more can be used in combination.

The average grain diameter of above-mentioned particle (B) is preferably 3nm～70nm, is more preferred from 5nm～50nm.If average grain diameter is in above-mentioned scope, can obtain the resin bed that the transparency is excellent.In addition, average grain diameter can be measured by the distribution of particles determinator taking dynamic light scattering method as measuring principle.

Above-mentioned particle (B) can be powder shaped, also can be solvent and disperses colloidal sol.Solvent disperses the contained solvent of colloidal sol for example can enumerate: 2-butanols, methyl alcohol, methyl ethyl ketone, methyl iso-butyl ketone (MIBK), cyclohexanone, METHYLPYRROLIDONE, propylene glycol monomethyl ether, gamma-butyrolacton.

There is no particular restriction for the allotment amount of above-mentioned particle (B), be preferably taking as above-mentioned luminescence component form with the concentration of the polymer in resin combination (I) or the viscosity of luminescence component formation resin combination and use as the amount of above-mentioned scope, particularly, with respect to polymer (I) 100 mass parts, be preferably 0 mass parts～2,000 mass parts, be more preferred from 10 mass parts～1,500 mass parts, You Jia is 30 mass parts～1,000 mass parts, special good is 50 mass parts～500 mass parts.If the allotment amount of particle (B) is above-mentioned scope, can under the state that maintains the transparency or crack resistance etc., obtain the luminescence component of the outgoing efficiency excellence of light.

In addition, particle (B) used disperses when colloidal sol for solvent, and the allotment amount of above-mentioned particle (B) refers to not solvent-laden quality, and the amount of the contained solvent of this colloidal sol is calculated as the amount of above-mentioned specific solvent.

[dispersant]

Above-mentioned luminescence component forms with in resin combination, in order to improve the dispersiveness of above-mentioned particle (A) and/or particle (B), is preferably and comprises various dispersants.

Dispersant can use a kind or also two or more can be used in combination.

Above-mentioned dispersant for example can use aluminium compound.The example of aluminium compound can be enumerated: aluminum alkoxide, beta-diketon aluminium misfit thing.Specifically can enumerate: the alkoxide compounds such as aluminium ethoxide, three (positive propoxy) aluminium, three (isopropoxy) aluminium, three (n-butoxy) aluminium, three (the second butoxy) aluminium, the beta-diketon misfit things such as three (methyl-acetoacetic acid) aluminium, three (oacetic acid) aluminium, aluminium tris(acetylacetonate), two (methyl acetic acid) aluminium of single acetyl acetone, two (ethyl acetic acid) aluminium of single acetyl acetone etc.

The commercially available product of aluminium compound can be enumerated: AIPD, PADM, AMD, ASBD, aluminium ethylate (Aluminium Ethoxide), ALCH, ALCH-50F, ALCH-75, ALCH-TR, ALCH-TR-20, Alumichelate M, Alumichelate D, Alumichelate A (W), surface conditioning agent OL-1000, ALGOMER, ALGOMER800AF, ALGOMER1000SF (be trade name above, river is ground refine (Kawaken Fine Chemicals) (thigh) and manufactured) etc.

Above-mentioned dispersant also can use non-ionic dispersing agent.By using non-ionic dispersing agent, and can improve the dispersiveness of metal oxide particle.Above-mentioned non-ionic dispersing agent is preferably: acid amides amine salt, ethylenediamine expoxy propane-oxirane (propylene oxide-ethylene oxide, PO-EO) condensation product, polyoxyethylene alkane ether, polyethenoxy alkylphenols, alkyl glucoside, polyoxyethylene fatty acid ester, sucrose fatty ester, sorbitan carboxylic esters, polyoxyethylene sorbitan carboxylic ester and the fatty acid alkanol amides of polyxyethylated phosphate, HMW polycarboxylic acids.Te Jia is for enumerating: the phosphate with polyxyethylated structure is non-ionic dispersing agent.The commercially available product of polyxyethylated phosphate can be enumerated: nanmu originally changes into the PLAAD ED151 (trade name) of (thigh) manufacture etc.

The allotment amount of above-mentioned dispersant only otherwise damage effect of the present invention, is not particularly limited, and in the time comprising dispersant, forms the solid constituent 100 quality % with resin combination with respect to above-mentioned luminescence component, for example, be 0.1 quality %～5 quality %.

[dispersing aid]

Above-mentioned luminescence component forms with in resin combination, in order to improve the dispersiveness of particle (A) and/or particle (B), is preferably and also comprises dispersing aid.Dispersing aid can preferably use: be selected from the more than a kind of acetylacetone,2,4-pentanedione and DMA etc.

The allotment amount of above-mentioned dispersing aid only otherwise damage effect of the present invention, is not particularly limited, and in the time comprising dispersing aid, forms the solid constituent 100 quality % with resin combination with respect to above-mentioned luminescence component, for example, be 0 quality %～5 quality %.

[interfacial agent]

Above-mentioned luminescence component forms with in resin combination, with regard to obtaining the viewpoint of the resin bed with uniform thickness, is preferably allotment interfacial agent.Above-mentioned interfacial agent can be enumerated: silicone-based interfacial agent, fluorine are interfacial agent etc.Wherein be preferably silicone-based interfacial agent.

Interfacial agent can use a kind or also two or more can be used in combination.

The example of silicone-based interfacial agent for example can be enumerated: and SH28PA (trade name, eastern beautiful DOW CORNING (Dow Corning Toray) (thigh) is manufactured, dimethyl polysiloxane poly (oxyalkylene) base co-polymer), PAINTAD19, PAINTAD54 (trade name, eastern beautiful DOW CORNING (thigh) is manufactured, dimethyl polysiloxane poly (oxyalkylene) base co-polymer), Silaplane FM0411 (trade name, prompt grace intelligence (JNC) (thigh) is manufactured), SF8428 (trade name, eastern beautiful DOW CORNING (thigh) is manufactured, dimethyl polysiloxane poly (oxyalkylene) base co-polymer (side chain contains OH yl)), BYKUV3510 (trade name, Japanese Bi Ke chemistry (BYK-Chemie Japan) (thigh) is manufactured, dimethyl polysiloxane-poly (oxyalkylene) base co-polymer), DC57 (trade name, eastern beautiful DOW CORNING silicone (Dow Corning Toray Silicone) (thigh) is manufactured, dimethyl polysiloxane-poly (oxyalkylene) base co-polymer), DC190 (trade name, eastern beautiful DOW CORNING silicone (thigh) is manufactured, dimethyl polysiloxane-poly (oxyalkylene) base co-polymer), Silaplane FM-4411, Silaplane FM-4421, Silaplane FM-4425, Silaplane FM-7711, Silaplane FM-7721, Silaplane FM-7725, Silaplane FM-0411, Silaplane FM-0421, Silaplane FM-0425, Silaplane FM-DA11, Silaplane FM-DA21, Silaplane FM-DA26, Silaplane FM0711, Silaplane FM0721, Silaplane FM-0725, Silaplane TM-070l, Silaplane TM-0701T (trade name, prompt grace intelligence (thigh) is manufactured), UV3500, UV3510, UV3530 (trade name, Japanese Bi Ke chemistry (thigh) is manufactured), BY16-004, SF8428 (trade name, eastern beautiful DOW CORNING silicone (thigh) is manufactured), VPS-1001 (trade name, and the pure medicine of light (thigh) is manufactured).

Special good example can be enumerated: Silaplane FM-7711, Silaplane FM-7721, SilaplaneFM-7725, Silaplane FM-0411, Silaplane FM-0421, Silaplane FM-0425, Silaplane FM0711, Silaplane FM0721, Silaplane FM-0725, VPS-1001 (trade name).Also can enumerate in addition: the commercially available product with the silicone compounds of ethene unsaturated group is TegoRad2300,2200N (trade name, the high chemistry of enlightening (Tego Chemie) company manufactures) etc.

Fluorine is that the example of interfacial agent for example can be enumerated: MEGAFAC F-114, MEGAFAC F410, MEGAFAC F411, MEGAFAC F450, MEGAFAC F493, MEGAFAC F494, MEGAFAC F443, MEGAFAC F444, MEGAFAC F445, MEGAFAC F446, MEGAFAC F470, MEGAFAC F471, MEGAFAC F472SF, MEGAFAC F474, MEGAFAC F475, MEGAFAC R30, MEGAFAC F477, MEGAFAC F478, MEGAFAC F479, MEGAFAC F480SF, MEGAFAC F482, MEGAFAC F483, MEGAFAC F484, MEGAFAC F486, MEGAFAC F487, MEGAFAC F559, MEGAFAC F562, MEGAFAC F563, MEGAFAC F172D, MEGAFAC F178K, MEGAFAC F178RM, MEGAFAC ESM-1, MEGAFAC MCF350SF, MEGAFAC BL20, MEGAFAC R08, MEGAFAC R61, MEGAFAC R90 (trade name, large Japanese ink chemistry (Dainippon Ink and Chemicals, DIC) (thigh) is manufactured).

Special good example can be enumerated: MEGAFAC F559, MEGAFAC F562, the MEGAFAC F563 (trade name) with hydrophily base and new oiliness base.

The allotment ratio of above-mentioned interfacial agent forms the solid constituent 100 quality % with resin combination with respect to above-mentioned luminescence component, is preferably 0 quality %～10 quality %, is more preferred from 0.1 quality %～5 quality %, and special good is 0.5 quality %～3 quality %.If the allotment amount of interfacial agent forms and exceedes 10 quality %, the anxiety of the refractive index reduction of rewarding resin bed with the solid constituent 100 quality % of resin combination with respect to above-mentioned luminescence component.

In addition, above-mentioned luminescence component forms with can more containing age resister in resin combination, by containing age resister, and can further improve the durability of the resin bed of gained.

Age resister is preferably and can enumerates: hindered phenol based compound.

In the present invention, spendable hindered phenol based compound can be enumerated: triethylene glycol-bis-[3-(3-the tributyl-5-methyl-4-hydroxy phenyl) propionic ester], 1, 6-hexylene glycol-bis-[3-(3, 5-2 the tributyls-4-hydroxy phenyl) propionic ester], 2, 4-pair-(just pungent sulfenyl)-6-(4-hydroxyl-3, 5-bis-tributyl anilino-s)-3, 5-triazine, pentaerythrite four [3-(3, 5-the tributyl-4-hydroxy phenyl) propionic ester], 1, 1, 3-tri-[2-methyl-4-[3-(3, 5-2 the tributyls-4-hydroxy phenyl) propionyloxy]-5-tributyl phenyl] butane, 2, 2-sulfenyl-diethyl two [3-(3, 5-2 the tributyls-4-hydroxy phenyl) propionic ester], 3-(3, 5-2 the tributyls-4-hydroxy phenyl) propionic acid stearyl), N, N-hexa-methylene two (3, 5-2 the tributyls-4-hydroxyl-hydrocinnamamide), 1, 3, 5-trimethyl-2, 4, 6-tri-(3, 5-2 the tributyls-4-hydroxybenzyl) benzene, three-(3, 5-2 the tributyls-4-hydroxybenzyl)-chlorinated isocyanurates, and 3, two [2-[3-(the 3-the tributyl-4-hydroxy-5-methyl base phenyl) propionyloxies]-1 of 9-, 1-dimethyl ethyl]-2, 4, 8, 10-tetra-oxygen spiral shell [5.5] hendecanes etc.These can use a kind or also two or more can be used in combination.

In the present invention, age resister, with respect to above-mentioned polymer (I) 100 weight portions, is preferably with the amount of 0.01 weight portion～10 weight portion and uses.

[other additives]

Above-mentioned luminescence component formation not damaging in the scope of effect of the present invention, can comprise above-mentioned various additives in addition with resin combination.This kind of additive for example can be enumerated: hardening compound, ultra-violet absorber beyond mentioned component.

[luminescence component forms the manufacture method with resin combination]

Above-mentioned luminescence component form with resin combination can be by above-mentioned polymer (I), particle (A) and other any compositions of allocating be as required mixed and are prepared.Conventionally can polymer (I), particle (A), specific solvent and other any compositions be mixed and be prepared by specific ratio.

Particularly, in order to obtain the high luminescence component of outgoing efficiency of light, be preferably in the constituent high in refractive index (being specially the constituent of the film that can form high index of refraction), allocate above-mentioned particle (A).

As the film of above-mentioned high index of refraction, use the light of wavelength 632.8nm and the refractive index measured, be preferably more than 1.60, be more preferred from more than 1.65, You Jia is more than 1.75, and special good is 1.77～2.0, and the best is 1.80～2.0.

Refractive index can be used prism coupler Model2010 (trade name, Mai Teliken company manufactures) to measure.

Can form the constituent of the film of this kind of high index of refraction, comprise above-mentioned polymer (I), be preferably by comprising the polymer that refractive index is high (I), special good for by comprising polymer (I) 100 mass parts and particle (B) 50 weight portion～500 mass parts obtain by this constituent.

[manufacture method of the 1st resin bed]

There is no particular restriction to form the manufacture method of the 1st resin bed of luminescence component of the present invention, can enumerate: in the time manufacturing above-mentioned luminescence component 10, for example above-mentioned luminescence component formation is directly coated to formation film in the 2nd electrode 17 grades, the method for then removing as required specific solvent from this film with resin combination; Luminescence component is formed and coats and comprise polyethylene terephthalate (polyethylene terephthalate with resin combination, etc. PET) on supporter and form film, then this film self-supporter is peeled off, and lamination is in first-class method of the 2nd electrode 17 etc.

Above-mentioned the 1st resin bed owing to comprising polymer (I), be preferably and comprise polymer (II) or polymer (III), therefore have the tendency that refractive index is high.Therefore it is generally acknowledged, for example, in luminescence component 10, the electrode (refractive index approximately 2.12) that comprises ITO in use is during as the 2nd electrode 17, and the refractive index of the 2nd electrode the 17, the 1st resin bed 18 and air according to this order diminishes.Therefore, can obtain the luminescence component of the outgoing efficiency with high light.

The method that is coated with above-mentioned resin combination and form film can be enumerated: rolling method, intaglio plate rubbing method, spin-coating method, slot coated method and use the method etc. of scraper.

Thickness when being coated with above-mentioned resin combination and forming film is not particularly limited, for example, be 1 μ m～250 μ m, is preferably 2 μ m～150 μ m, is more preferred from 5 μ m～125 μ m.

In addition, there is no particular restriction to remove the method for above-mentioned specific solvent from film, for example, can enumerate the method for film heating.By film is heated, and can make the specific solvent evaporation in this film and remove.As long as the condition of above-mentioned heating is specific solvent evaporation, and suitably definite because of the mode of heat upgrading etc. not produce thermal deformation or various material, for example heating-up temperature is preferably 30 DEG C～300 DEG C, is more preferred from 40 DEG C～250 DEG C, and You Jia is 50 DEG C～230 DEG C.

In addition, be preferably 10 minutes～5 hours heating time.In addition, heating can be carried out above by the two-stage.Particularly, with the temperature of 30 DEG C～150 DEG C after dry 1 minute～2 hours, with 100 DEG C～250 DEG C further heating 10 minutes～2 hours etc.In addition, can under nitrogen environment or under decompression, be dried as required.

The thickness of above-mentioned the 1st resin bed is suitably selected according to desired purposes, is preferably 20nm～100 μ m, is more preferred from 80nm～50 μ m.

In addition, above-mentioned the 1st resin bed pass through the glass transition temperature (Tg) that 8230 types (trade name) DSC determinator (20 DEG C/min of programming rates) that company of science manufactures is measured, be preferably 170 DEG C～350 DEG C, be more preferred from 240 DEG C～330 DEG C, You Jia is 250 DEG C～300 DEG C.If above-mentioned the 1st resin bed has this kind of glass transition temperature, heating or heat treatment can at high temperature carry out forming electrode etc. on this layer time, therefore electrode like this and that obtain is low resistance and high-transmission rate, and can easily manufacture the excellent luminescence component such as outgoing efficiency and durability of light.

The hot strength of above-mentioned the 1st resin bed is preferably 50MPa～200MPa, is more preferred from 80MPa～150MPa.Hot strength can be used cupping machine 5543 (trade name, because Strong (INSTRON) company manufactures) to measure.

The elongation at break of above-mentioned the 1st resin bed is preferably 5%～100%, is more preferred from 15%～100%.Elongation at break can use cupping machine 5543 (trade name, because Strong company manufactures) to measure.

The modulus of elasticity in direct stress of above-mentioned the 1st resin bed is preferably 2.5GPa～4.0GPa, is more preferred from 2.7GPa～3.7GPa.The modulus of elasticity in direct stress can be used cupping machine 5543 (trade name, because Strong company manufactures) to measure.

SSC-5200 type (trade name) TMA (the thermomechanical analysis that use Seiko electronics (Seiko Instruments) company of above-mentioned the 1st resin bed manufactures, thermo-mechanical analysis) the determinator setting-out line coefficient of expansion, be preferably below 80ppm/K, be more preferred from below 75ppm/K.

The humidity expansion coefficient of above-mentioned the 1st resin bed is preferably below 15ppm/%RH, is more preferred from below 12ppm/%RH.Humidity expansion coefficient can use MA (manufacture of Seiko electronics nanosecond science and technology (SII NanoTechnology) company, TMA-SS6100 (trade name)) humidity control option to measure.If the coefficient of expansion of the 1st resin bed is above-mentioned scope, represent dimensional stability (environmental reliability) height, therefore can be more preferably for luminescence component.

The ratio dielectric constant of above-mentioned the 1st resin bed is preferably 2.0～4.0, and being more preferred from 2.3～3.5, You Jia is 2.5～3.2.Can use 4284A type (trade name) LCR (inductance capacitance resistance, LCR) the mensuration meter that Hewlett-Packard (HP) (thigh) manufactures to measure than dielectric constant.If be above-mentioned scope than dielectric constant, the tendency that the luminescence component that comprises above-mentioned the 1st resin bed shows stable luminance is high.

Above-mentioned the 1st resin bed according to the total light transmittance in JIS (Japanese Industrial Standards) K7105 clarity test method, be preferably more than 50%.Total light transmittance can use haze meter SC-3H (trade name must be congratulated testing machine (Suga Test Instruments) (thigh) manufacture) to measure.

Above-mentioned the 1st resin bed is in the time that thickness is 30 μ m, and YI value (yellow colour index) is preferably below 3.0, is more preferred from below 2.5, and You Jia is below 2.0.YI value can be used SM-T type (trade name) the color analyzer that must congratulate testing machine (thigh) manufacture to measure.

Above-mentioned the 1st resin bed in the time that thickness is 30 μ m, by air drier in atmosphere with 230 DEG C of YI values of carrying out after the heating of 1 hour, be preferably below 3.0, be more preferred from below 2.5, You Jia is below 2.0.

In addition, above-mentioned the 1st resin bed, owing to comprising above-mentioned particle (A), is therefore not easy to measure its refractive index.

< the 2nd resin bed >

Luminescence component of the present invention can also comprise the 2nd resin bed.

Above-mentioned the 2nd resin bed is formed at

(c) opposition side of the side that is formed with above-mentioned luminescent layer of above-mentioned the 1st electrode and

(d) at least one of the opposition side of the side that is formed with above-mentioned luminescent layer of above-mentioned the 2nd electrode, is preferably

Between (c ') above-mentioned the 1st electrode and above-mentioned the 1st resin bed and

At least one between (d ') above-mentioned the 2nd electrode and above-mentioned the 1st resin bed,

And comprising the glass transition temperature (Tg) of measuring (DSC, 20 DEG C/min of programming rates) by differential scanning calorimetry is 170 DEG C of above resins, and to use the refractive index of the light measurement of wavelength 632.8nm be more than 1.60.

Above-mentioned the 2nd resin bed is the layer that does not contain above-mentioned particle (A).Therefore,, in the time that the 2nd resin bed is formed to above-mentioned (c ') or (d '), can expect to make electrode surface planarization.

In addition, above-mentioned the 2nd resin bed with regard to obtain high index of refraction layer etc. aspect with regard to, be preferably and comprise above-mentioned particle (B).

Above-mentioned the 2nd resin bed can comprise more than 2 layers in luminescence component of the present invention.Now, the 2nd resin bed that comprises same composition can comprise more than 2 layers in luminescence component of the present invention, and the 2nd resin bed of different compositions also can comprise more than 2 layers in luminescence component of the present invention.

This kind the 2nd resin bed is preferably by the luminescence component that at least contains polymer (I) and specific solvent and forms the layer forming with resin combination.

Form with the contained composition of resin combination and the composition that can contain about this luminescence component, except not containing above-mentioned particle (A), need only identical with illustrated person in the 1st resin bed.

In addition, as long as the manufacture method of the 2nd resin bed is also identical with the manufacture method of the 1st resin bed.

The refractive index of the light measurement of the use wavelength 632.8nm of the 2nd resin bed, is preferably more than 1.60, is more preferred from more than 1.65, and special good is more than 1.75.

If the refractive index of above-mentioned the 2nd resin bed is above-mentioned scope, the outgoing efficiency of the light of the luminescence component of gained uprises.

Owing to comprising above-mentioned polymer (I), therefore can obtain the 2nd resin bed with this kind of refractive index.

In addition, the physical property beyond the refractive index of the 2nd resin bed, as long as identical with the physical property of above-mentioned the 1st resin bed.

< the 3rd resin bed >

Luminescence component of the present invention can also comprise the 3rd resin bed.The 3rd resin bed is not containing above-mentioned particle (A) and above-mentioned particle (B).In addition, be preferably and in fact only wrap resiniferous layer.This kind the 3rd resin bed is by above-mentioned the 1st resin bed and/or the 2nd resin bed and substrate contacts and while arranging, be preferably and be arranged between above-mentioned the 1st resin bed and/or the 2nd resin bed and substrate.

This kind the 3rd resin bed is due to gluing excellence, therefore thinks and can obtain the luminescence component that the long-term reliability of luminescence component is improved.

Above-mentioned the 3rd resin bed can comprise more than 2 layers in luminescence component of the present invention.Now, the 3rd resin bed that comprises same composition can comprise more than 2 layers in luminescence component of the present invention, and the 3rd resin bed of different compositions also can comprise more than 2 layers in luminescence component of the present invention.

It is that the luminescence component of resin forms the layer forming with resin combination that above-mentioned the 3rd resin bed is preferably by comprising above-mentioned epoxy.

Form with the contained composition of resin combination and the composition that can contain about this luminescence component, except not containing above-mentioned particle (A) and above-mentioned particle (B), need only identical with illustrated person in the 1st resin bed.

In addition, as long as the manufacture method of the 3rd resin bed is also identical with the manufacture method of the 1st resin bed.

Moreover, as long as identical with the physical property of above-mentioned the 1st resin bed.

[embodiment]

Below, by embodiment, the present invention is described more specifically, but the present invention is not subject to any restriction of these embodiment.

(1) structural analysis

The structural analysis of the polymer of gained in following synthesis example, by infra-red sepectrometry (Infrared spectroscopy, IR) (attenuate total reflection (Attenuated Total Reflection, ATR) method, fourier transform infrared spectroscopy (Fourier transform infrared spectroscopy, FT-IR), 6700 (trade names, Buddhist nun's high-tensile strength (NICOLET) company manufactures)) and nulcear magnetic resonance (NMR) (nuclear magnetic resonance, NMR) (ADVANCE500 type (trade name), Brooker (BRUKAR) company manufactures) carry out.

(2) weight average molecular weight (Mw)

The weight average molecular weight of the polymer of gained (Mw) in following synthesis example is that HLC-8220 type (trade name) the GPC device (tubing string: TSKgel α-M (trade name), developing solvent: THF) that uses eastern Cao to manufacture is measured.

(3) glass transition temperature (Tg)

In following synthesis example, the glass transition temperature of resin bed for the polymer of gained or luminescence component, is 8230 types (trade name) the DSC determinator that uses company of science to manufacture, and measures with 20 DEG C/min of programming rates.In addition, the glass transition temperature of resin bed for luminescence component, is to use to measure from the strippable substrate resin bed person of forming of attached rewarding luminescence component resin bed.The results are shown in table 1 or table 2.

(4) total light transmittance, mist degree (Haze) value and yellow colour index (YI value)

The strippable substrate resin bed of resin bed for the luminescence component of gained in following embodiment and comparative example, to the luminescence component resin bed of gained, measure total light transmittance, haze value and yellow colour index (YI value) according to JIS K7105 clarity test method.Particularly, use and must congratulate haze meter SC-3H (trade name) the mensuration total light transmittance that testing machine (thigh) is manufactured, use and must congratulate SM-T type (trade name) the color analyzer mensuration YI value (YI before heating) that testing machine (thigh) is manufactured.

In addition, the strippable substrate resin bed of resin bed for the luminescence component of gained in following embodiment and comparative example, with 200 DEG C, the luminescence component of gained is carried out with resin bed in atmosphere by air drier after the heating of 30 minutes, use and must congratulate SM-T type (trade name) the color analyzer that testing machine (thigh) manufactures and measure YI value (heating rear YI).In addition, mensuration is to carry out according to JIS K7105 condition.

The result of total light transmittance, haze value and YI value is shown in to table 1 or table 2.

(5) refractive index

The refractive index of the resin combination of gained in following preparation example, is to form film by removing desolventizing from this resin combination, and uses prism coupler Model2010 (trade name, Mai Teliken company manufactures) to measure the film of gained.In addition, refractive index is to use the light of wavelength 632.8nm to measure.The results are shown in table 1 or table 2.

(6) evaluation of assembly

Use substrate or substrate A with the luminescence component resin bed of gained in following embodiment and comparative example, make respectively organic el element.On each resin bed (being resin bed G while being resin bed E, following embodiment 9 while being resin bed B, following embodiment 7 when following embodiment 6) or through ultraviolet ray (ultraviolet, UV) (only comparative example 1) on the face of ozone clean, forms tin indium oxide (ITO) film as transparent electrode by sputtering method using the thickness of 100nm.In addition, substrate temperature when sputter is made as 160 DEG C.The electrical sheet resistance value of passing through Loresta GP MCP-T610 type (trade name, Mitsubishi Chemical's analytical technology (MITSUBISHI CHEMICAL ANALYTECH) (thigh) is manufactured) mensuration as resistrivity meter of the transparent electrode of gained is 20 Ω/cm ².

On the surface of the transparent electrode of gained, order sequentially forms according to this: the oligomerization anil that comprises as electric hole transport layer (makes aniline pentamer be dissolved in dimethyl formamide (N, N-Dimethyl formamide, DMF) in, in the 5-sulfo group salicylamide person of forming of the 3 times of molar equivalents that wherein adulterate) 70nm thickness layer, as the N that comprises of luminescent layer, N '-bis-(1-naphthyl)-N, N '-diphenyl-1, 1 '-bis-phenyl-4, the layer of the 50nm thickness of 4 '-diamines (α-NPD), comprise three (oxine) aluminium (Alq as electron transfer layer ₃) the layer of 50nm thickness.Then, on electron transfer layer evaporation magnesium-ag alloy layer as negative electrode.The thickness of negative electrode is now made as 200nm.

Transparent electrode and the negative electrode of the organic el element to making like this apply 10V voltage, measure the luminous quantity from substrate A face by the optical diode that uses integrating sphere.In addition, now, will not be made as 1.0 containing luminescence component by the measured value of the assembly of resin bed.The results are shown in table 1 or table 2.

[synthesis example 1]

The synthetic > of < polymer

In the four-hole boiling flask of 3L, add (A) composition: 2,6-difluorobenzonitrile (being also called below " DFBN ") 35.12g (0.253mol), (B) composition: 9,9-two (4-hydroxy phenyl) Fluorene (being also called below " BPFL ") 87.60g (0.250mol), potash 41.46g (0.300mol), DMA (being also called below " DMAc ") 443g and toluene 111g.

Then, thermometer, mixer, three-way cock, Dien-Stark (Dean-Stark) pipe and cooling water pipe with nitrogen ingress pipe are installed in four-hole boiling flask.

Then, will in flask, carry out after nitrogen replacement, at 140 DEG C, make the solution reaction 3 hours of gained, generated water is removed at any time from Dien-Stark pipe.After no longer finding that water generates, make temperature rise to lentamente 160 DEG C, at this temperature, react 6 hours.

Be cooled to after room temperature (25 DEG C), remove generated salt by filter paper, filtrate is dropped in methyl alcohol it is precipitated again, by isolated by filtration by single screening (, residue) from.The screening of gained, with 60 DEG C of one evenings of vacuumize, and is obtained to white powder (polymer) (output 95.67g, productive rate 95%).

Carry out the structural analysis of polymer and the mensuration of weight average molecular weight of gained.As a result, the characteristic absorption of infrared absorption spectroscopy is positioned at 3035cm ^-1(C-H is flexible), 2229cm ^-1(CN), 1574cm ^-1, 1499cm ^-1(absorption of aromatic rings skeleton), 1240cm ^-1(O-), weight average molecular weight is 130,000.The polymer of gained has construction unit (A).

In addition, the glass transition temperature of the polymer of gained is 270 DEG C.

[changing 9]

[preparation example 1]

The mode that makes the polymer of gained in synthesis example 1 become 10 quality % with polymer concentration is dissolved in to the solution (being made as below " resin solution 1 ") forming in cyclohexanone again, be added in sealable polyethylene can, then in the solution of gained,, to add and to carry out surface-treated titanium oxide microparticle (average grain diameter: 15nm) by aluminium hydroxide as the mode of 160 mass parts with respect to these polymer 100 mass parts.Then, add zirconium oxide bead (daily use chemicals pottery (NIKKATO) (thigh) manufactured) 300 mass parts of particle diameter 0.1mm, use coating oscillator (red evil spirit (RED DEVIL) company) vibration 5 hours, after titanium oxide microparticle is disperseed, obtain resin combination 1 by removing zirconium oxide bead.

[embodiment 1]

In above-mentioned resin combination 1, more add the TITANIX JR-1000 (trade name as Titanium particles, Supreme Beingization (TAYCA) (thigh) is manufactured, average grain diameter: 1 μ m), so that in resin combination 1 except the solid constituent of desolventizing and the mass ratio of TITANIX JR-1000 (trade name) are 90/10, then, use homogenizer at room temperature with 10,000rpm stirs 5 minutes, and obtains coating constituent 1 (solid component concentration: 24 quality %).

One side to the alkali-free glass plate as transparency carrier (trade name: EAGLE XG, the manufacture of healthy and free from worry (Corning) company, thickness: 0.7mm) carries out UV (ultraviolet ray) ozone clean (being made as below " substrate A ").This substrate A on the face of UV ozone clean, by the coating constituent 1 of spin-coating method (rotating speed: 1000rpm, rotational time: 10 seconds) coating gained.Use action of forced stirring formula drying machine, with 80 DEG C, by this coated substrates heating 3 minutes, then, with 180 DEG C of heating, after 30 minutes, self-desiccation machine took out, and is cooled to room temperature in atmosphere, and obtains the substrate with luminescence component resin bed 1.

[preparation example 2]

With respect to carried out surface-treated titanium oxide microparticle (average grain diameter: 15nm) 100 weight portions by aluminium hydroxide, adding is DISPERBYK-111 (trade name as the copolymer that comprises acidic group of dispersant, Japan's Bi Ke chemistry (thigh) is manufactured) zirconium oxide bead (daily use chemicals potteries (thigh) manufacture) 200 mass parts of 10 weight portions, cyclohexanone 275 weight portions and particle diameter 0.1mm, use coating oscillator (Hong Mo company) vibration 5 hours, and titanium oxide microparticle is disperseed.Then, in the dispersion liquid of gained, the epoxy compounds that dissolving contains Fluorene base is OGSOL PG-100 (trade name, Osaka gas chemistry (Osaka Gas Chemicals) (thigh) is manufactured, glass transition temperature after sclerosis: 180 DEG C) 36 weight portions and trimellitic anhydride (with the pure pharmaceutical worker's industry of light (thigh) manufacture) 12 weight portions, then zirconium oxide bead is removed and obtained resin combination 2.

[embodiment 2]

In above-mentioned resin combination 2, more add the TITANIX JR-1000 (trade name) as Titanium particles, make in resin combination 2 except the solid constituent of desolventizing and the mass ratio of TITANIX JR-1000 (trade name) be 85/15, then, use homogenizer at room temperature with 10,000rpm stirs 5 minutes, and obtains coating constituent 2 (solid component concentration: 40 quality %).

Use coating constituent 2 to replace coating constituent 1, in addition, in the mode identical with embodiment 1, obtain the substrate with luminescence component resin bed 2.

[preparation example 3]

Use barium titanate fine particle (average grain diameter: 50nm) to replace titanium oxide microparticle (average grain diameter: 15nm), in addition, in the mode identical with preparation example 2, obtain resin combination 3.

[embodiment 3]

Use the resin combination 3 of gained to replace resin combination 2, in addition, in the mode identical with embodiment 2, and obtain coating constituent 3 (solid component concentration 40 quality %).

Use coating constituent 3 to replace coating constituent 1, in addition, in the mode identical with embodiment 1, obtain the substrate with luminescence component resin bed 3.

[preparation example 4]

Replace above-mentioned resin solution 1, and use, to dilute commercially available clear polyimides resin by METHYLPYRROLIDONE be RIKACOAT PN-20 (trade name, use 3,3 ', 4,4 '-diphenyl sulfone-tetracarboxylic acid dianhydride is as 2 compositions systems, the glass transition temperature of acid dianhydride: 270 DEG C, polymer concentration 20 quality %) solution (resin concentration: 10 quality %) that forms, in addition, in the mode identical with preparation example 1, obtain resin combination 4.

[embodiment 4]

Use resin combination 4 to replace resin combination 1, in addition, in the mode identical with embodiment 1, obtain coating constituent 4 (solid component concentration: 24 quality %).

Use coating constituent 4 to replace coating constituent 1, in addition, in the mode identical with embodiment 1, obtain the substrate with luminescence component resin bed 4.

[embodiment 5]

Replace TITANIX JR-1000 (trade name) used in embodiment 2, be SX8782 (P) (trade name and add as the cross-linked styrene-acrylic acid hollow-particle that comprises of polymer composition, JSR (thigh) manufactures, average grain diameter: 1.1 μ m, internal orifice dimension: 0.9 μ m), make in above-mentioned resin combination 2 except the solid constituent of desolventizing and the mass ratio of hollow-particle be 97/3, in addition, in the mode identical with embodiment 2, obtain coating constituent 5 (solid component concentration: 38 quality %).

Use coating constituent 5 to replace coating constituent 1, in addition, in the mode identical with embodiment 1, obtain the substrate with luminescence component resin bed 5.

[embodiment 6]

Substrate A on the face of UV ozone clean, be coated with above-mentioned coating constituent 2 by spin-coating method (rotating speed: 1000rpm, rotational time: 10 seconds).Use action of forced stirring formula drying machine, this coated substrates, with 80 DEG C of heating 3 minutes, is then heated after 30 minutes with 180 DEG C, self-desiccation machine takes out, and is cooled to room temperature in atmosphere, and obtains the substrate with resin bed A.Then,, on the resin bed A with the substrate of resin bed A of gained, be coated with above-mentioned resin combination 1 by spin-coating method (rotating speed: 1000rpm, rotational time: 10 seconds).Use action of forced stirring formula drying machine, the substrate of gained is heated 3 minutes with 80 DEG C, then heat after 30 minutes with 180 DEG C, self-desiccation machine takes out, in atmosphere, be cooled to room temperature, and obtain sequential lamination substrate A according to this, the substrate with luminescence component resin bed 6 of the resin bed A that formed by coating constituent 2 and the resin bed B that formed by resin combination 1.

[preparation example 5]

By make OGSOL PG-10036 weight portion, trimellitic anhydride (manufacturing with the pure pharmaceutical worker's industry of light (thigh)) 12 weight portions and, 3-glycidoxypropyltrimewasxysilane 2 weight portions are dissolved in cyclohexanone 950 weight portions, and obtain resin combination 5.

[embodiment 7]

Substrate A on the face of UV ozone clean, be coated with above-mentioned resin combination 5 by spin-coating method (rotating speed: 2000rpm, rotational time: 10 seconds).Use action of forced stirring formula drying machine, this coated substrates, with 80 DEG C of heating 3 minutes, is then heated after 10 minutes with 180 DEG C, self-desiccation machine takes out, and is cooled to room temperature in atmosphere, and obtains the substrate with resin bed C.Then,, on the resin bed C with the substrate of resin bed C of gained, be coated with above-mentioned coating constituent 2 by spin-coating method (rotating speed: 1000rpm, rotational time: 10 seconds).Use action of forced stirring formula drying machine, by this coated substrates, with 80 DEG C of heating 3 minutes, then with 180 DEG C of heating after 30 minutes, self-desiccation machine took out, and is cooled to room temperature in atmosphere, and obtained the substrate of sequential lamination substrate A, resin bed C and resin bed D according to this.Then,, on the resin bed D of the substrate of gained, be coated with above-mentioned resin combination 1 by spin-coating method (rotating speed: 1000rpm, rotational time: 10 seconds).Use action of forced stirring formula drying machine, this coated substrates is heated after 3 minutes with 80 DEG C, then heat after 30 minutes with 180 DEG C, self-desiccation machine takes out, in atmosphere, be cooled to room temperature, and obtain sequential lamination substrate A, the resin bed C being formed by resin combination 5 according to this, the substrate with luminescence component resin bed 7 of the resin bed D that formed by coating constituent 2 and the resin bed E that formed by resin combination 1.

[embodiment 8]

Replace TITANIX JR-1000 (trade name) used in embodiment 1, and interpolation is as the HPS-0500 (trade name of silicon dioxide granule, manufacture in East Asia synthetic (thigh), average grain diameter: 0.5 μ m), make in above-mentioned resin combination 1 except the solid constituent of desolventizing and the mass ratio of silicon dioxide granule be 90/10, in addition, in the mode identical with embodiment 1, obtain coating constituent 6 (solid component concentration: 24 quality %).Use coating constituent 6 to replace coating constituent 1, in addition, in the mode identical with embodiment 1, obtain the substrate with luminescence component resin bed 8.

[preparation example 6]

Add after OGSOL PG-10066 weight portion, TITANIX JR-1000 (trade name) 18 weight portions and gamma-butyrolacton 400 weight portions as solvent, use homogenizer to stir 5 minutes with 10,000rpm.Then add trimellitic anhydride 16 weight portions, use agitator at room temperature to mix 10 minutes and acquisition resin combination 6 with 200rpm.

[embodiment 9]

Substrate A on the face of UV ozone clean, be coated with above-mentioned resin combination 6 by spin-coating method (rotating speed: 1000rpm, rotational time: 10 seconds).Use action of forced stirring formula drying machine, this coated substrates, with 80 DEG C of heating 3 minutes, is then heated after 10 minutes with 150 DEG C, self-desiccation machine takes out, and is cooled to room temperature in atmosphere, and obtains the substrate with resin bed F.Then,, on the resin bed F with the substrate of resin bed F of gained, be coated with above-mentioned resin combination 1 by spin-coating method (rotating speed: 1000rpm, rotational time: 10 seconds).Use action of forced stirring formula drying machine, this coated substrates is heated 3 minutes with 80 DEG C, then heat after 10 minutes with 180 DEG C, self-desiccation machine takes out, in atmosphere, be cooled to room temperature, and obtain sequential lamination substrate A, the resin bed F being formed by resin combination 6 according to this and the substrate with luminescence component resin bed 9 of the resin bed G that formed by resin combination 1.

[preparation example 7]

The solution (polymer concentration: 22.4 quality %) that use makes the polymer dissolution of gained in synthesis example 1 form in cyclohexanone, in addition, in the mode identical with embodiment 1, obtains resin combination 7.

[embodiment 10]

Use resin combination 7 to replace resin combination 1, in addition, in the mode identical with embodiment 1, obtain coating constituent 7 (solid component concentration 24 quality %).

Use coating constituent 7 to replace coating constituent 1, in addition, in the mode identical with embodiment 1, obtain the substrate with luminescence component resin bed 10.

[comparative example 1]

In the evaluation of said modules, use substrate A.

[preparation example 8]

Replace above-mentioned resin solution 1, be Parapet HR-S (trade name and make commercially available PMMA resin, Kuraray (Kuraray) is manufactured 100 DEG C of (thigh), glass transition temperatures) be dissolved in the solution (resin concentration: 10 quality %) that cyclohexanone forms, in addition, in the mode identical with preparation example 1, obtain resin combination 8.

[comparative example 2]

Use resin combination 8 to replace resin combination 1, in addition, in the mode identical with embodiment 1, obtain coating constituent 8 (solid component concentration 24 quality %).

Substrate A on the face of UV ozone clean, by the coating constituent 8 of spin-coating method (rotating speed: 1000rpm, rotational time: 10 seconds) coating gained.Use action of forced stirring formula drying machine, the coated substrates of gained, with 80 DEG C of heating 3 minutes, is then heated after 30 minutes with 120 DEG C, self-desiccation machine takes out, and is cooled to room temperature in atmosphere, and obtains the substrate with luminescence component resin bed 11.

[comparative example 3]

In embodiment 1, use above-mentioned resin combination 1 (solid component concentration 22 quality %) to replace above-mentioned coating constituent 1, in addition, in the mode identical with embodiment 1, obtain the substrate with luminescence component resin bed 12.

[table 2]

Confirm: the substrate of the application of the invention, and make the face luminosity of the organic el element of first pre-structure significantly increase.

[symbol description]

10,20,30: luminescence component

11,21,31: substrate

13,23,33: the 1 electrodes

15,25,35: luminescent layer

17,27,37: the 2 electrodes

18,28: the 1 resin beds

38, (wherein at least one is the 1st resin bed for 39: the 1 resin beds or the 2nd resin bed.)

Claims

1. a luminescence component, it comprises the 1st electrode, luminescent layer, the 2nd electrode and the 1st resin bed, it is characterized in that: described the 1st electrode, described luminescent layer, described the 2nd electrode according to this sequential lamination form, and described the 1st resin bed is formed at

And comprising the glass transition temperature (Tg) of measuring (DSC, 20 DEG C/min of programming rates) by differential scanning calorimetry is that 170 DEG C of above resin and average grain diameters are the particle (A) of 0.1 μ m～5 μ m.

2. luminescence component according to claim 1, it is that 1nm is above and be less than metal oxide microparticle (B) of 100nm that wherein said the 1st resin bed also comprises average grain diameter.

3. luminescence component according to claim 1 and 2, it more comprises the 2nd resin bed, and described the 2nd resin bed is formed at

4. luminescence component according to claim 3, wherein said the 2nd resin bed is formed at

(c) between described the 1st electrode and described the 1st resin bed and

5. according to the luminescence component described in any one in claim 1-4, wherein said luminescence component is organic electroluminescence assembly.

6. a luminescence component formation resin combination, its in order to form luminescence component as described in any one in claim 1-5 as described in the 1st resin bed.

7. a luminescence component formation resin combination, its in order to form luminescence component as described in any one in claim 3-5 as described in the 2nd resin bed.