CN100581304C - Drying agent and field light emission device using the same - Google Patents
Drying agent and field light emission device using the same Download PDFInfo
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- CN100581304C CN100581304C CN200610079446A CN200610079446A CN100581304C CN 100581304 C CN100581304 C CN 100581304C CN 200610079446 A CN200610079446 A CN 200610079446A CN 200610079446 A CN200610079446 A CN 200610079446A CN 100581304 C CN100581304 C CN 100581304C
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Abstract
A water-capturing or drying agent placed in a hermetically sealed field light emission device for maintaining stable light emission of the light emission device not susceptible to moisture and oxygen for long period of time. The drying agent comprises a compound of polymer formed by bonding M constituting a plurality of organometallic compounds wherein M is a trivalent metal atom with an oxygen molecule. The drying agent is placed in the hermetically sealed container, thereby protecting the field light emission device from being adversely affected by damage from trace amounts of moisture permeating from outside the hermetically sealed container and/or adhered to the inner surface thereof.
Description
The cross reference of related application
The application requires Japanese patent application No.2005-085929 number of submitting on March 24th, 2005 and Japanese patent application No.2006-071895 number the priority of submitting on March 16th, 2006.
Explanation about federal funding research
Do not use
Technical field
The present invention relates to a kind of water-capturing agent or drier that can absorb moisture in the closed container that wherein accommodates electronic device for a long time, and to the improvement of thin-film electroluminescent device, described improvement can be made the thin-film electroluminescent device with high stability in enormous quantities, and by using water-capturing agent or drier can make it not be subject to the influence of moisture and oxygen for a long time and keeping stable emission.
Background technology
In general, the electroluminescence device that encapsulates in the closed container comprises the luminescent layer between the paired electrode that is inserted in the airtight container.Two kinds of electroluminescence devices are arranged, and a kind of is the organic El device that comprises mainly the luminescent layer that is made of the fluorescence organic compound, and another kind is the inorganic EL device that comprises mainly the luminescent layer that is made of inorganic phosphor (phosphor).
The organic El device that the fluorescence organic compound constitutes has luminous component, and these parts are by insert the layer structure of the EL layer formation that contains the fluorescence organic compound between positive pole and negative pole.This organic El device is a selfluminous device, its injected hole and electronics in the film that contains the fluorescence organic compound, emitted fluorescence/phosphorescence when being compounded to form exciton each other and utilizing the exciton inactivation.
The inorganic EL device that inorganic phosphor constitutes generally comprises in order bottom electrode, inorganic phosphor, dielectric material and top electrode stacked on upper surface of substrate, by apply high frequency voltage emission light between electrode.
Organic and inorganic EL device is sealed in the container that keeps the ultra micro moisture.Because little moisture has side effects to the characteristic of EL device, therefore generally in closed container, place drier from wherein absorbing and/or removing moisture.Drier is commonly referred to water-capturing agent, because its seizure and absorption are contained in the moisture of the EL device in the closed container.Therefore, the drier that is used in the EL device of the present invention hereinafter is called water-capturing agent or drier.Below explanation is used in the water-capturing agent in the organic El device or the embodiment of drier.
Because the functional part of organic El device very easily is subjected to the infringement of moisture, so functional part is sealed in by in glass or the metal container, is not exposed to the outside.More particularly, functional part is layered in substrate such as on glass, will is placed in the substrate and is adhered in the substrate by glass or metal sealing cap thereon, therefore functional part is limited in the airtight container that is made of substrate and sealing cap.Then, water-capturing agent such as barium monoxide (BaO) or calcium oxide (CaO) be placed in the EL device absorb water, like this, disclosed like that as the open 9-148066 of Japanese patent unexamined, absorption attached to functional part or be present in moisture in the gas or penetrate into sealed container interior by hermetic unit in the closed container.
Shown in Fig. 1 is the section of the structure of organic El device example.Anode 2, the organic layer 3 that comprises organic EL medium and the negative electrode 4 made by nesa coating such as ITO (indium tin oxide target) are layered in the substrate 1 of being made by glass by said sequence and form functional part.Then, the sealing cap 5 that metal is formed is placed on to cover the EL device on the EL device and be connected in the substrate 1 with adhesive 6 and forms closed container.The airtight part that anode 2 and negative electrode 4 pass closed container is hermetically guided to the outside and is driven functional part.Form recess 7 at sealing cap 5 places, the BaO powder is filled in wherein as water-capturing agent or drier 8, and seals with permeable film.In this example, the light that emits from organic layer 3 passes through anode 2 and substrate of glass 1 as shown in Figure 1 according to downward direction.
Shown in Fig. 2 is the section of the structure of another organic El device example, forms the metal sealing cap that recess 10 replaces among Fig. 1 with bore process such as sand-blast, etching method and similar approach in the glass plate one side opposite with functional part.The water-capturing agent that to make by compacting CaO powder and infiltration agent or case type water-capturing agent or drier 12 are bonded in the inner surface of the recess 10 of the closed base 11 that glass makes.The remainder of structure is to shown in Figure 1 similar.In this example, the light of launching from organic layer 3 passes through anode 2 and substrate 1 as shown in Figure 2 according to downward direction.If use light-permeable negative electrode and light-permeable water-capturing agent or drier, the unification compound of the organo-metallic compound shown in the chemical formula (1) for example, also can be disclosed like that as the open 2002-33187 of Japan Patent and the open 2003-144830 of Japan Patent, make the light of launching from organic layer 3 pass through negative electrode 4 and closed base 11.
(Chemical formula 1)
[wherein, R
1, R
2And R
3Be hydrogen atom or alkyl, aryl, cycloalkyl or heterocyclic group with one or more carbon atoms.One or more hydrogen atoms can be replaced by halogen atom in each group.R
1, R
2And R
3Can be mutually different groups maybe can be identical mutually group or each other bonding maybe can be polymer, M is a trivalent metal atom.]
The section of the top emission structure organic El device of the airtight substrate 11 that metal airtight substrate 5 shown in the airtight substrate 13 replacement Fig. 1 of the plate-like that is to use glass to make shown in Fig. 3 and glass are made.Anode 2, organic layer 3 and light-permeable negative electrode 14 according to this sequential cascade in the substrate 1 that glass is made.Form functional part above inorganic water blocking layer 15 is layered in, bond by adhesive layer and airtight substrate 13 on it.Therefore, between substrate 1 and airtight substrate 13, formed and do not had the total solids in space enclosed construction.With the sealer 17 of ultraviolet light polymerization for example epoxy sealent be placed on the edge of adhesive layer 16, with the adhesive layer 16 of 13 of closed base 1 and airtight substrates.In this example, the light of launching from organic layer 3 passes through negative electrode 14, adhesive layer 16 and airtight substrate 13 according to the order that makes progress Fig. 3 as the open 2002-231443 of Japan Patent is disclosed.
Organic El device shown in Figure 1, recess 7 are to form on the sealing cap 5 of the functional part in the sealing substrate 1 by casting die.Organic El device shown in Figure 2, recess 10 forms in airtight substrate 11 by bore process.What fill in the recess 7 or 10 is as the BaO or the CaO powder of catching the water drier in organic El device.The sheet water-capturing agent or the drier that are formed by BaO or CaO powder can be used in recess 7 or 10.Yet, if recess 7 or 10 has been filled the water-capturing agent powder of requirement, the minimum 0.2mm of its thickness, recess 7 or 10 must have the thickness of 0.3-0.5mm at least.Therefore, it is big that the thickness of airtight substrate 11 or sealing cap 5 becomes, the also whole thickening of the thickness of organic El device.
The BaO and the CaO that are used as water-capturing agent or drier in the EL device are easy to disperse, because BaO and CaO are pulverous.Therefore, when they are encapsulated into recess 7 or 10, must forbid disperseing.If BaO or CaO powder adherence are to the zone that will cover, the problem of Chan Shenging is a poor in processability like this, and automation bonding strength difficult and encapsulation reduces.
In the organic El device shown in Figure 3, on the surface of the substrate 1 of a side of stacked functional part anode 2, formed the TFT circuit.Therefore, the light that emits from the organic layer 3 of functional part can not pass anode, but emits from negative electrode 14 by aforesaid airtight substrate 13.As the BaO of water-capturing agent or CaO powder or with the sheet water-capturing agent that BaO or CaO powder are made is not transparent.Therefore in the organic El device as shown in Figure 3, water-capturing agent or drier can not be placed on the negative electrode 14 that light will pass.
In addition, when the unification compound of the organo-metallic compound of light-permeable for example, the compound shown in the chemical formula (1) is dissolved in the solution of making in the organic solvent among the open 2002-33187 of Japan Patent, the inner surface that is coated in the recess 10 that forms by bore mode in airtight substrate 11 can be expected to improve and catch the water-based energy during as water-capturing agent or drier.
Catch the water effect in order to improve, inventor of the present invention after deliberation the conduct tradition shown in the chemical formula (1) catch the molecular structure of the unification compound of water or drier.Inventor of the present invention infers, catching the water effect can make it easily to react with the water capacity by catching that the bonded oxygen molecule improves on water or the drier shown in the chemical formula (1).
The present invention has improved the reliability of EL device by using the organo-metallic compound shown in the chemical formula (5) as catching water or drier:
(chemical formula 5)
Wherein M is a trivalent metal atom.
Form the molecular structure of dimer by the organo-metallic compound shown in the chemical formula of dimerization (1) as the formula (5), produce torsion in the molecule, hydrone becomes and is easy to attack the oxygen atom of dimer cross-linking part.On the other hand, the prior art shown in the chemical formula (1) catch water or drier has hydrophobic substituent in the unification compound.Therefore, hydrone is difficult to approaching.Therefore, the reaction of traditional water-capturing agent or drier and water is difficult to take place, and has reduced thus and has caught water or drying property.
With the reaction equation of water shown in reaction equation (6):
(reaction equation 6)
As above shown in the middle reaction equation (A) of surface chemistry formula (6), dimeric compounds shown in the chemical formula (5) and water reaction form the hexatomic ring monomer shown in chemical formula (1).As a result, the compound in the chemical formula (5) absorbs water, as catching water or drier.In this chemical formula, M is a trivalent metal atom.Then, as above shown in the middle reaction equation (B) of surface chemistry formula (6), the monomer of hexatomic ring and water react.After these react completely and carry out, generate trivalent metal hydroxides M (OH)
3As a result, this compound absorbs water, as catching water or drier.Similarly, along with shown in chemical formula (1) and the carrying out that reacts between trimer, tetramer and the pentamer of organo-metallic compound and the polymer, increased and caught water or drying effect.
Trimeric example is shown in chemical formula (7).
(chemical formula 7)
Wherein M is a trivalent metal atom.
The example of tetramer is shown in chemical formula (8).
(chemical formula 8)
Wherein M is a trivalent metal atom.
Another example of tetramer is shown in chemical formula (9).
(chemical formula 9)
Wherein M is a trivalent metal atom.
Carry out dimerization, trimerizing, four dimerizations, five dimerizations or polymerizable molecular structure by mode as described above, produce torsion in the molecule, hydrone becomes and is easy to attack oxygen atom at crosslink part.On the other hand, water-capturing agent of the prior art or drier have hydrophobic substituent in the chemical formula (1).Thereby hydrone is inaccessible.Therefore, the reaction of traditional water-capturing agent or drier and water is difficult to take place, and has weakened the performance of catching water.
Except the compound shown in the above chemical formula (2) to (4), by having the organo-metallic compound of trivalent metal atom M and various polymer that the oxygen atom bonding obtains produce torsion in their molecule with a plurality of.Therefore, hydrone is easy to attack the oxygen atom at crosslink part, gives and the effect of various party things absorption water.Metallic atom M can be Al, Ga, In, La, Y and other trivalent metal atoms.
R wherein
1, R
2And R
3Being the examples for compounds shown in the substituent chemical formula (1), is following chemical formula (10), those shown in (11) and (12).
(Chemical formula 1 0)
Wherein M is a trivalent metal atom.
(Chemical formula 1 1)
Wherein M is a trivalent metal atom.
(Chemical formula 1 2)
Wherein M is a trivalent metal atom.
In chemical formula, R is a kind of group that is selected from alkyl, aryl, cycloalkyl, heterocyclic radical.Alkyl can exemplify into methyl, ethyl, propyl group, butyl, sec-butyl, the tert-butyl group, amyl group, hexyl, heptyl, octyl group, nonyl, decyl, undecyl, dodecyl, tridecyl, myristyl, pentadecyl, cetyl, heptadecyl, octadecyl, nonadecyl, eicosyl, heneicosyl, docosyl, etc.
Aryl can be phenyl, tolyl, 4-cyano-phenyl, xenyl, neighbour,, right-triphenyl, naphthyl, anthryl, phenanthryl, fluorenyl, 9-phenyl anthryl, 9,10-diphenyl anthryl, pyrenyl, etc.
Cycloalkyl can be cyclopenta, cyclohexyl, norborneol alkyl, adamantyl, 4-methylcyclohexyl, 4-cyanocyclohexanoic base etc.
The example of heterocyclic group can be a pyrrole radicals, pyrrolinyl, pyrazolyl, pyrazolinyl, imidazole radicals, triazolyl, pyridine radicals, pyridazinyl, pyrimidine radicals, pyrazinyl, triazine radical, indyl, benzimidazolyl, purine radicals, quinolyl, isoquinolin, cinorin, quinoxalinyl, the benzoquinoline base, the Fluorenone base, dicyano Fluorenone base, carbazyl oxazolyl oxadiazole base, thiazolyl, thiadiazolyl group benzoxazolyl, benzothiazolyl, the BTA base, dibenzo oxazolyl, the bisbenzothiazole base, the bisbenzimidazole base, Deng.
Summary of the invention
The invention provides the water-capturing agent or the drier that are placed in the airtight container with electronic building brick, be used for absorbing for a long time the moisture in the container.
According to the present invention, a kind of water-capturing agent or drier are provided, it comprises the metallic atom of at least a organo-metallic compound by will having polynary ring (multiple-membered) structure and the polymer that the oxygen molecule bonding forms.More particularly, the present invention relates to a kind of water-capturing agent or drier, it comprises at least a polymer that forms by compound and oxygen atom bonding with a plurality of chemical formulas (1) expression.
(Chemical formula 1)
(R wherein
1, R
2And R
3Be hydrogen atom or alkyl, aryl, cycloalkyl or heterocyclic group with one or more carbon atoms.One or more hydrogen atoms in each group can be replaced by halogen atom.R
1, R
2, and R
3Group differing from each other maybe can be mutually the same group maybe can be mutual bonding maybe can be polymer, M is a trivalent metal atom.〕
The water-capturing agent or the drier of the compound that comprises chemical formula (2) expression are provided according to another aspect of the present invention.
(Chemical formula 2)
(wherein R is hydrogen atom or the alkyl with one or more carbon atoms, aryl, cycloalkyl, heterocyclic group.One or more hydrogen atoms in each group can be replaced by halogen atom.R can be group inequality maybe can be identical group maybe can be mutual bonding maybe can be polymer.N is 0 or more than or equal to 1 integer.M is a trivalent metal atom.〕
According to another aspect of the present invention, provide water-capturing agent or the drier that comprises the compound shown in the chemical formula (3).
(chemical formula 3)
(wherein R is hydrogen atom or the alkyl with one or more carbon atoms, aryl, cycloalkyl, heterocyclic group.One or more hydrogen atoms in each group can be replaced by halogen atom.R group inequality maybe can be identical group maybe can be mutual bonding maybe can be polymer.N is 0 or more than or equal to 1 integer.M is a trivalent metal atom.〕
According to another aspect of the present invention, provide water-capturing agent or the drier that comprises compound shown in the chemical formula (4).
(chemical formula 4)
(wherein R is hydrogen atom or the alkyl with one or more carbon atoms, aryl, cycloalkyl, heterocyclic group.One or more hydrogen atoms in each group can be replaced by halogen atom.R group inequality maybe can be identical group maybe can be mutual bonding maybe can be polymer.m
1, m
2And m
3Be integer more than or equal to 1, and can be different or mutually the same.M is a trivalent metal atom.〕
According to replacement form of the present invention, be provided at the electroluminescence device that has luminescent layer in the closed container of sealing.In this electroluminescence device, will have the metallic atom of organo-metallic compound of polynary ring structure and polymer compound that the oxygen molecule bonding forms and be placed in the container.Being placed on the organo-metallic compound that has polynary ring structure in the container as water-capturing agent or drier is one of compound of chemical formula (2), (3) and (4) expression, and it is to form with the organo-metallic compound with polynary ring structure that at least one metallic atom bonding is represented by a plurality of chemical formulas (1).According to embodiment of the present invention, chemical formula (2), the organo-metallic compound of (3) and (4) expression is placed in the closed container of sealing with ultraviolet curable agent.This is convenient to place water-capturing agent or drier in container.Ultraviolet curable agent preferably has the light-permeable monomer of lipophilic group, makes easily to place water-capturing agent or drier in container, and transparent water-capturing agent or drier is provided in electroluminescence device.
Description of drawings
These and other objects of the present invention, characteristics and advantage become more clear after having read following detailed explanation and accompanying drawing, wherein,
Fig. 1 is the profile of the example of organic El device structure.
Fig. 2 is the profile of another example of organic El device structure.
Fig. 3 be the organic El device structure the profile of another example.
Fig. 4 is the rate variation figure of the light-emitting zone of water-capturing agent shown in chemical formula (1) and (2).
Fig. 5 is water-capturing agent shown in the chemical formula (1) and CaO weight change figure.
Embodiment
The present invention developed have triad and two or more six-membered ring structures organo-metallic compound as novel water-capturing agent or drier.What this novel water-capturing agent had being comparable to or was better than traditional water-capturing agent or drier catches water effect and performance.The novel water-capturing agent or the drier of the application of the invention can suppress the growth of stain, obviously improve the pot-life and the effective service life-span of organic El device.In addition, the good film-forming property of water-capturing agent of the present invention or drier can be coated in the film of boring formation homogeneous on glass by using disperser.Except the disperser painting method, spinner, ink ejecting method, scraping blade method, method for printing screen, lithographic plate printing method and similar approach can be used as painting method.Because novel water-capturing agent of the present invention or drier can form the film of transparent and homogeneous, therefore can see the emission of EL device by hyaline membrane.In addition, can provide effective water-capturing agent of top emission structure organic El device or drier.In addition, water-capturing agent of the present invention or drier can react with moisture, and than conventional powder shape water-capturing agent or the drier moisture of trace in the absorption plant quickly, the growth of stain be can suppress, and the electroluminescence device in closed container or the water-capturing agent or the drier of electronic device are provided for sealing up for safekeeping.
Can clearerly understand the present invention with reference to the following examples.
Embodiment 1 (water-capturing agent or the drier that contain the organo-metallic compound with polynary ring structure of aluminium (Al) formation) as trivalent metal
(synthetic method) stirs down, and with 6.13g three AIPs (AIP), 2.88g is sad and 0.54g water adds and has in the three-neck flask of blender, adds solvent naphtha (mineral sprits) as solvent, strong agitation forms mixture then.Incipient stage, mixture 80 ℃ of heating down, is heated to 150 ℃ at last.Behind the mixture reaction one hour, under reduced pressure, mixture is heated to 120 ℃, removes with vacuum distillation method and desolvate.Mixture is cooled to room temperature then 210 ℃ of reactions three hours.After this, add an amount of n-decane as the solution of solvent with formation 50wt%.
By above-mentioned synthetic method, prepared the water-capturing agent or the drier of the organo-metallic compound that contains aluminium (Al) formation shown in the chemical formula (13) with six-membered ring structure as trivalent metal.
(Chemical formula 1 3)
By prolonging the reaction time, prepare the polymer shown in chemical formula (14), (15) and (16) such as trimer and tetramer:
(Chemical formula 1 4)
Wherein n is 0 or is C more than or equal to 1 integer and R
7H
15
(Chemical formula 1 5)
Wherein n is 0 or is C more than or equal to 1 integer and R
7H
15
(Chemical formula 1 6)
M wherein
1, m
2And m
3Be 0 or be C more than or equal to 1 integer and R
7H
15
(preparation of organic El device and encapsulation)
Cleaning is placed on it in the cold boiler after the substrate of glass of ITO has been installed.Cold boiler is evacuated to 10
-6Holder is that the phthalocyanine blue b evaporation of 20nm is in the substrate of the glass that ITO has been installed with thickness.Then, with α-NPD evaporation of thickness 30nm to phthalocyanine blue b, then with three (oxine) aluminium (Alq of thickness 50nm
3) evaporation is to α-NPD.After this, thickness is that the lithium-aluminium alloy evaporation of 200nm is to Alq
3Go up as top electrode, form device.Then, from the vacuum evaporation device, discharge vacuum system, and under the atmosphere of drying nitrogen, encapsulate.The n-decane solution of above-claimed cpd is being coated under the atmosphere of drying nitrogen in the boring glass substrate (closed base).The closed base that has applied these solution is heated to 150 ℃ with hot plate makes solvent evaporates to solidifying.After the temperature of closed base reduced to room temperature, the edge that the uv-curable epoxy adhesive is coated to closed base was with closed base and device substrate lamination cambium layer shape, and it uses uv radiation curing.After this, device is heated to 100 ℃ with the moisture in the absorption plant in baking oven.
(catching the evaluation of water effect 1)
The luminance of thus obtained organic El device is after microscopically is observed, and it is placed on temperature is that 80 ℃ of humidity are to confirm to catch the water effect in 85% the hot and humid environment.The result as shown in Figure 4.
Through 100 hours, will install from hot and humid environment and take out, with the luminance of microscopic examination device.As a result, non-luminous component does not increase, and does not promptly observe stain, has confirmed that polymeric blends of the present invention plays the effect of water-capturing agent or drier fully.Because water-capturing agent or drier can form the film of transparent and homogeneous, therefore see through the emission that this hyaline membrane has just confirmed the EL device.
The n-decane solution of specified rate is coated to the substrate surface of boring glass in glove box, its dew point is at-80 ℃, and 150 ℃ of dryings obtain hyaline membrane on hot plate then.For relatively, prepared the calcium oxide pastel that contains 50wt% calcium oxide (CaO) powder and 50wt% polymethyl methacrylate.With disperser an amount of pastel is coated in the substrate surface of boring glass and dry under drying condition equably.Two substrates that will scribble this drier are respectively left standstill in air, have observed the variation of weight then.The result as shown in Figure 5.As a result, confirmed that under the polymer situation of using the present invention to synthesize, the needed time of moisture that absorbs specified quantitative shortens.For the generation that suppresses stain and the contraction of growth or negative electrode, promptly suppress because the degeneration of organic El device causes the reduction on the function, moisture in the chemical absorbing sealed tube apace.The water-capturing agent of the present invention exploitation or drier are better than traditional water-capturing agent catching on the water effect, and can remove the trace amounts of moisture in the airtight container of organic light emitting apparatus effectively.
Embodiment 2 (water-capturing agent or the drier that forms with the method beyond the scatter coated also is installed on the organic El device)
The good film-forming property of water-capturing agent of the present invention or drier, the outer method of the enough scatter coated of energy forms the film of homogeneous on the plane surface of notch board or boring glass.Water-capturing agent of the present invention or drier are dissolved in the solvent, form film by spin coating method, spray method, ink ejecting method, scraping blade method, method for printing screen or offset printing method at the upper surface of airtight substrate, and heating is to form membranaceous water-capturing agent that is used for organic El device or drier.Then, use resulting membranaceous water-capturing agent or drier to prepare organic El device.As a result, obtained identical effect with embodiment 1.
Embodiment 3 (water-capturing agent or the drier and the water-capturing agent or the drier that are installed in the UV-cured resin in the organic El device that contain embodiment 1)
By using the mixture of water-capturing agent or drier and UV-cured resin, water-capturing agent that organic El device uses in the present embodiment or drier have the ability that infiltrates through moisture in the closed container that has encapsulated organic El device or absorb the moisture that adheres to airtight container inner surface or EL apparatus function parts that absorbs.Water-capturing agent and UV-cured resin must have enough functions as described below, expect that they have good compatibility each other and also can evenly mix.
(ultraviolet curable agent)
Ultraviolet curable agent contains light-permeable monomer and sensitizer, i.e. Photoepolymerizationinitiater initiater or photopolymerization promoter.Can use acrylate or the methacrylate good as the light-permeable monomer, such as the simple function of chemical formula (17) shown in (23) other polyfunctional acrylic ester (acrylate) or multifunctional methacrylate (methacrylate) outside trifunctional acrylate or methacrylate with the water-capturing agent compatibility of present embodiment.These acrylate or methacrylate can be used alone or in conjunction with each other.
(Chemical formula 1 7)
(Chemical formula 1 8)
(Chemical formula 1 9)
(Chemical formula 2 0)
(Chemical formula 2 1)
(Chemical formula 2 2)
(Chemical formula 2 3)
These ultraviolet curable agents composed as follows described:
(as the acrylate of monomer)
The basic skeleton structure of acrylic acid polymerisable monomer is as described below.
(1) monofunctional acrylate
Monofunctional acrylate is shown in chemical formula (17).By changing the substituent R in the chemical formula (17), just changed such as character such as viscosity, proportion, refractive index and P.I.I. values.The compatibility of these monofunctional acrylates and water-capturing agent changes by R.For example, under the situation by water-capturing agent shown in chemical formula (10) and (11) or drier, externally the alkyl of C and H is contained in the position, and saturated aliphatic molecule has determined the compatibility of water-capturing agent or drier.Good solvent, promptly with the solvent that water-capturing agent or drier have a good compatibility be, for example, hydrocarbon solvent such as hexane, decane etc. or aromatic solvent such as toluene, dimethylbenzene etc.On the other hand, the solvent low with water-capturing agent or drier compatibility is water-soluble solvent, such as acetone, ethanol etc.Therefore preferred, have the two or more saturated hydrocarbyl that R wherein has two or more carbon atoms as the acrylate monomer of water-capturing agent or drier good solvent,, such as methene etc.Specifically, the compound shown in chemical formula (19) has two methenes or still less.The length of the saturated hydrocarbyl in R is long more, easy more dissolving water-capturing agent or drier.
(2) bifunctional acrylate
Bifunctional acrylate's situation and monofunctional acrylate are basic identical.Representative instance is the compound shown in chemical formula (20).Because the compound shown in the chemical formula (20) contains oxygen atom in structure, its with the compatibility of water-capturing agent compare with the compound that contains methene relative poor slightly, but also can use.
(3) trifunctional acrylate
The situation of trifunctional acrylate and polyfunctional acrylic ester is also similar to monofunctional acrylate and bifunctional acrylate's situation.Trifunctional acrylate with methene is shown in chemical formula (22).
(as the methacrylate of monomer)
Consider that the methacrylic acid photopolymerizable monomer is similar to the situation of acrylic acid photopolymerizable monomer as the composition of the water-capturing agent of present embodiment or drier.Basic skeleton structure is as described below.Chemical formula (18) has been represented the general formula of simple function methacrylate.Chemical formula (19) has represented to have the simple function methacrylate of methene as lipophilic group, and it is the saturated hydrocarbyl that contains two or more carbon atoms.Chemical formula (21) has represented to have the difunctionality methacrylate of methene as lipophilic group, and it is saturated hydrocarbyl or the alkyl that replaces.Chemical formula (23) has represented to have the trifunctional methacrylate of methene as lipophilic group, and it is the saturated hydrocarbyl that contains two or more carbon atoms.
(sensitising agent)
Two kinds of sensitising agents are arranged, and a kind of is Photoepolymerizationinitiater initiater, and another kind is a photopolymerization promoter.Photoepolymerizationinitiater initiater is preferably water white.If there is color also no problem, because only add the 1-3wt% of curing agent and because with the cured film bleach that obtains behind the ultraviolet radiation.Be necessary the Photoepolymerizationinitiater initiater of selecting those that organic El device itself is free from side effects.According to reaction mechanism, sensitising agent be divided into as described below two kinds dissimilar.
(1) molecule Schizoid
Styrax acrylic acid ether, benzyl dimethyl ketone acetal, 1-hydroxycyclohexylphenylketone, 2-hydroxy-2-methyl-1-phenyl-propane-1-ketone, diethoxy acetophenone, 2-methyl isophthalic acid-[(4-methyl mercapto) phenyl]-2-moroholino-propane-1-ketone, Dibenzosuberone, 2-hydroxy-2-methyl-1-phenyl-propane-1-ketone, diethoxy acetophenone, trichloroacetophenone.
(2) draw Hydrogen (Photoepolymerizationinitiater initiater+photopolymerization promoter)
Benzophenone and two lignocaine benzophenone, 2,4-diethyl thioxanthone and ESCAROL 507 ester (2, the 4-diethyl thioxanthone can be a fatty amine, for example, triethanolamine), benzyl (from drawing hydrogen atom), 2-alkyl-anthraquinone (from drawing hydrogen atom), 2-chloroanthraquinone (from drawing hydrogen atom) with the simultaneous alkyl of 2-chloroanthraquinone with the simultaneous alkyl of 2-alkyl-anthraquinone with the simultaneous alkyl of benzyl.
(preparation of the water-capturing agent that embodiment 1 synthesizes or the mixture of drier and ultraviolet curable agent)
What use as acrylic monomers is " NK ester " (registered trade mark), is made by SHIN NAKAMURAKAGAKU KOHGYO Co., Ltd.What use as initator is " Irgacure 907 " (registered trade mark), is made by Ciba-Geigy.As the promoter use is triethanolamine.Triethanolamine is 1: 1: 98 with the mixing ratio of " Irgacure 907 " and " NK ester ", forms ultraviolet curable agent.Polymer shown in the chemical formula (1) that the embodiment 1 of adding identical weight ratio synthesizes in this ultraviolet curable agent, stirring and dissolving forms the water-capturing agent or the drier of uv-curable, and the water-capturing agent of the uv-curable that obtains like this or drier are water white liquid.
With reference to the organic El device with example structure shown in Figure 2, the substrate of the formation organic El device of use is similar to embodiment 1.Substrate moves down in the glove box not being exposed to airborne situation, dew point is adjusted to-60 ℃ with nitrogen.The thickness that cleans the notch depth that forms with bore process in advance and be 0.2mm is the sealing substrate of 0.7mm glass, is heated to 150 ℃ and dewaters and put into glove box.With the water-capturing agent synthetic among the embodiment 1 or the mixture of drier and ultraviolet curable agent, be coated in the inner surface of recess by using disperser then, thickness is approximately 8 μ/cm
2, be that the ultraviolet light of 365nm is at 100nW/cm with wavelength
2Radiation 60 seconds.Then, curing mixture sticks to the inner surface of recess with it.Airtight part coating in the recess of airtight substrate contains the ultraviolet light sealer that diameter is 10 μ m beads, and is laminated in the device substrate, with dominant wavelength be the ultraviolet light of 365nm from a side of closed base at 100nW/cm
2Following radiation 60 seconds is with complete closed.
The device that forms like this is placed on beginning accelerated aging test in the environment of 85 ℃ of high temperature and 85% high humility.After carrying out 100 hours, the luminance of device is tested before similar substantially to this.The generation of non-luminous component and growth, promptly stain is suppressed and has confirmed that water-capturing agent of the present invention or drier are enough effective.
Because above water-capturing agent or drier can form homogeneous and hyaline membrane is by the emission of hyaline membrane susceptible of proof EL device.
The device that forms like this is placed on beginning accelerated aging test in the environment of 85 ℃ of high temperature and 85% high humility.After carrying out 100 hours, the light radiation state of device is tested before similar substantially to this.The generation of non-luminous component and growth, promptly stain is suppressed and has confirmed that water-capturing agent of the present invention or drier are enough effective.
Because the water-capturing agent of embodiment 5 or the membranaceous dry element that drier can form transparent and homogeneous can confirm the light emission of EL device by transparent membranaceous dry element.
Below description is contained the water-capturing agent of the organo-metallic compound that the metal outside the Al constitutes as trivalent metal or the example of drying machine with polynary ring structure.
Embodiment 6 (containing water-capturing agent or the drier of Ga) as the organo-metallic compound with six-membered ring structure of trivalent metal formation
(synthetic method) stirs down, and three different third gallium oxides (GIP) of 7.40g, the sad and 0.54g water of 2.88g are joined in the three-neck flask that blender is housed.Then, add solvent naphtha, strong agitation at first is heated to 80 ℃, and slowly rising is heated to 150 ℃ at last.React after 1 hour, be heated to 210 ℃ under the decompression situation and come evaporating solvent.After 3 hours, be cooled to room temperature 210 ℃ of reactions.After this, add the solution of an amount of n-decane as solvent preparation 50%.
By above synthetic method, prepare and contain the drier that gallium (Ga) has replaced the organo-metallic compound with six-membered ring structure shown in Chemical formula 13 that aluminium (Al) constitutes as trivalent metal.
(Chemical formula 2 4)
Wherein R is C
7H
15
Contain gallium (Ga) such as trimer, tetramer etc. and replaced the polymer of aluminium (Al) as trivalent metal (M) by prolonging the reaction time, can synthesizing, it is similar with the compound shown in (16) to chemical formula (14), (15).
(preparation of organic El device and encapsulation)
Be similar to embodiment 2-5, the water-capturing agent of use embodiment 6 or drier prepare organic El device as water-capturing agent or the drier of embodiment 1, and estimate.The emission state of organic El device that used microscopic, and be placed in the environment of 85 ℃ of high temperature and 85% high humility and confirm to catch the water effect.After carrying out 100 hours, will install from this environment and take out, use the emission state of microscopic organic El device.As a result, do not observe non-luminous component, confirmed that drier has fully played the effect of water-capturing agent or drier.
Because the water-capturing agent of embodiment 6 can form the membranaceous dry component of transparent and homogeneous, has confirmed the luminous of organic El device by transparent membranaceous dry component.
Embodiment 7 (containing indium (In) constitutes the organo-metallic compound with polynary ring structure as trivalent metal water-capturing agent or drier)
Stir down, three different third indium oxides of 8.75g, the sad and 0.54g water of 2.88g are joined in the three-neck flask that blender is housed.Then, add solvent naphtha, strong agitation at first is heated to 80 ℃, and progressively raising is heated to 150 ℃ at last.React after 1 hour, be heated to 210 ℃ under the decompression situation and come evaporating solvent.210 ℃ of reactions 3 hours, be cooled to room temperature.After this, add the solution of an amount of n-decane as solvent preparation 50%.
By above synthetic method, prepare and contain the drier that indium (In) has replaced the organo-metallic compound with six-membered ring structure shown in Chemical formula 13 that aluminium (Al) constitutes as trivalent metal.
(Chemical formula 2 5)
Wherein R is C
7H
15
Contain indium (In) such as trimer, tetramer etc. and replaced the polymer of aluminium (Al) as trivalent metal (M) by prolonging the reaction time, can synthesizing, it is similar with the compound shown in (16) to chemical formula (14), (15).
(preparation of organic El device and encapsulation)
Be similar to embodiment 1-5, the water-capturing agent of use embodiment 6 or drier prepare organic El device as water-capturing agent or the drier of embodiment 1, and estimate.The emission state of organic El device that used microscopic, and be placed in the environment of 85 ℃ of high temperature and 85% high humility and confirm to catch the water effect.After carrying out 100 hours, will install from this environment and take out, use the emission state of microscopic organic El device.As a result, do not observe non-luminous component, confirmed that drier has fully played the effect of water-capturing agent or drier.
Because the water-capturing agent of embodiment 7 can form the membranaceous dry component of transparent and homogeneous, has confirmed the luminous of organic El device by transparent membranaceous dry component.
Embodiment 8 (containing yttrium (Y) constitutes the organo-metallic compound that contains polynary ring structure as trivalent metal (M) water-capturing agent or drier)
(synthetic method)
Stir down, three different third yittrium oxide of 7.99g, the sad and 0.54g water of 2.88g are joined in the three-neck flask that blender is housed.Then, add solvent naphtha, strong agitation at first is heated to 80 ℃, and progressively raising is heated to 150 ℃ at last.React after 1 hour, be heated to 210 ℃ under the decompression situation and come evaporating solvent.210 ℃ of reactions 3 hours, be cooled to room temperature.After this, add the solution of an amount of n-decane as solvent preparation 50%.
By above synthetic method, prepare and contain the drier that yttrium (Y) has replaced the organo-metallic compound with six-membered ring structure shown in Chemical formula 13 that aluminium (Al) constitutes as trivalent metal (M).
(Chemical formula 2 6)
Wherein R is C
7H
15
Contain yttrium (Y) such as trimer, tetramer etc. and replaced the polymer of aluminium (Al) as trivalent metal (M) by prolonging the reaction time, can synthesizing, it is similar with the compound shown in (16) to chemical formula (14), (15).
(preparation of organic El device and encapsulation)
Be similar to embodiment 1-5, the water-capturing agent of use embodiment 6 or drier prepare organic El device as water-capturing agent or the drier of embodiment 1, and estimate.The emission state of organic El device that used microscopic is placed in the environment of 85 ℃ of high temperature and 85% high humility and confirms to catch the water effect.After carrying out 100 hours, will install from this environment and take out, use the emission state of microscopic organic El device.As a result, do not observe non-luminous component, confirmed that this drier has fully played the effect of water-capturing agent.
Because the water-capturing agent of embodiment 8 or the membranaceous dry component that drier can form transparent and homogeneous have just confirmed the luminous of organic El device by transparent membranaceous dry component.
Embodiment 9 (containing lanthanum (La) constitutes the organo-metallic compound that contains polynary ring structure as trivalent metal (M) water-capturing agent or drier)
(synthetic method)
Stir down, three different third lanthanas of 9.48g, the sad and 0.54g water of 2.88g are joined in the three-neck flask that blender is housed.Then, add solvent naphtha, strong agitation at first is heated to 80 ℃, and progressively raising is heated to 150 ℃ at last.React after 1 hour, be heated to 210 ℃ under the decompression situation and come evaporating solvent.210 ℃ of reactions 3 hours, be cooled to room temperature.After this, add the solution of an amount of n-decane as solvent preparation 50%.
By above synthetic method, prepare and contain the drier that lanthanum (La) has replaced the organo-metallic compound with six-membered ring structure shown in Chemical formula 13 that aluminium (Al) constitutes as trivalent metal (M).
(Chemical formula 2 7)
Wherein R is C
7H
15
Contain lanthanum (La) such as trimer, tetramer etc. and replaced the polymer of aluminium (Al) as trivalent metal (M) by prolonging the reaction time, can synthesizing, it is similar with the compound shown in (16) to chemical formula (14), (15).
(preparation of organic El device and encapsulation)
Be similar to embodiment 1-5, the water-capturing agent of use embodiment 6 or drier prepare organic El device as water-capturing agent or the drier of embodiment 1, and estimate.The emission state of organic El device that used microscopic is placed in the environment of 85 ℃ of high temperature and 85% high humility and confirms to catch the water effect.After carrying out 100 hours, will install from this environment and take out, use the emission state of microscopic organic El device.As a result, do not observe non-luminous component, confirmed that drier has fully played the effect of water-capturing agent.
Because the water-capturing agent of embodiment 9 or the membranaceous dry component that drier can form transparent and homogeneous have just confirmed the luminous of organic El device by transparent membranaceous dry component.
Determined to have the water of catching effect when containing the water-capturing agent of the organo-metallic compound that Al, Ga, In, Y or La constitute as trivalent metal (M) or drier as mentioned above to organic El device with polynary ring structure.Therefore understood, the organo-metallic compound with polynary ring structure that trivalent metal (M) constitutes plays the effect of water-capturing agent or drier.
Drier of the present invention can be as the water-capturing agent or the drier of the electronic unit in sealing device.According to the present invention, water-capturing agent or drier are placed in the closed container of organic or inorganic EL device, and it mainly is made of fluorescence organic or inorganic compound.Water-capturing agent of the present invention or drier can provide a kind of EL device of low section, and the invasion that it is subjected to water and oxygen for a long time hardly can keep stable emission.In addition, drier of the present invention is a hyaline membrane, fast Absorption water.Therefore, can be as the water-capturing agent or the drier of electronic unit in the airtight container.
Significantly, under the prompting of above-mentioned instruction, can make multiple about improvement of the present invention and variation.Therefore it should be understood that in appended claim scope, the present invention can implement with the mode outside the above-mentioned specific descriptions.
Claims (7)
1. a drier comprises by the polymer with a plurality of compounds shown in the chemical formula (1) and the formation of oxygen atom bonding;
(Chemical formula 1)
Wherein, R
1, R
2And R
3Be hydrogen atom or the alkyl with one or more carbon atoms, aryl, cycloalkyl or heterocyclic radical, one or more hydrogen atoms can be replaced by halogen atom in each group, R
1, R
2And R
3Can be mutually different groups maybe can be identical mutually group or each other bonding maybe can be polymer, M is a trivalent metal atom.
2. a drier comprises the compound shown in the chemical formula (2);
(Chemical formula 2)
Wherein, R is hydrogen atom or the alkyl with one or more carbon atoms, aryl, cycloalkyl or heterocyclic radical, one or more hydrogen atoms can be replaced by halogen atom in each group, R can be mutually different groups maybe can be identical mutually group or each other bonding maybe can be polymer, n is 0 or more than or equal to 1 integer, M is a trivalent metal atom.
3. a drier comprises the compound shown in the chemical formula (3);
(chemical formula 3)
Wherein, R is hydrogen atom or the alkyl with one or more carbon atoms, aryl, cycloalkyl or heterocyclic group, one or more hydrogen atoms can be replaced by halogen atom in each group, R can be mutually different groups maybe can be identical mutually group or each other bonding maybe can be polymer, n is the integer more than or equal to 1, and M is a trivalent metal atom.
4. a drier comprises the compound shown in the chemical formula (4);
(chemical formula 4)
Wherein, R is hydrogen atom or the alkyl with one or more carbon atoms, aryl, cycloalkyl or heterocyclic group, one or more hydrogen atoms can be replaced by halogen atom in each group, R can be mutually different groups maybe can be identical mutually group or each other bonding maybe can be polymer, m
1, m
2And m
3Be integer, and can differ from one another or identical that M is a trivalent metal atom more than or equal to 1.
5. an electroluminescence device comprises drier and the luminescent layer of putting into airtight container, and wherein this drier is selected from as the described compound of claim 1 to 4.
6. an electroluminescence device comprises drier that contains ultraviolet curable agent and the luminescent layer of putting into airtight container, and wherein this drier is selected from the described compound of at least a claim 1 to 4.
7. electroluminescence device as claimed in claim 6, wherein this ultraviolet curable agent is the light-permeable monomer with lipophilic group.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2005085929 | 2005-03-24 | ||
| JP085929/05 | 2005-03-24 | ||
| JP071895/06 | 2006-03-16 |
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| EP2560459A3 (en) * | 2007-02-21 | 2013-04-10 | Ulvac, Inc. | Display device, apparatus for producing display device, and method for producing display device |
| KR20130141381A (en) * | 2012-06-15 | 2013-12-26 | 제이에스알 가부시끼가이샤 | Moisture-capturing agent, composition for forming moisture-capturing body, moisture-capturing body, and electronic device |
| JP5442147B1 (en) | 2013-03-19 | 2014-03-12 | 古河電気工業株式会社 | Transparent resin composition for sealing organic electroluminescent elements, resin sheet for sealing organic electroluminescent elements, and image display device |
| JP6002075B2 (en) * | 2013-04-09 | 2016-10-05 | 双葉電子工業株式会社 | Complex compound, desiccant, sealing structure and organic EL device |
| JP2019177645A (en) | 2018-03-30 | 2019-10-17 | 東洋製罐グループホールディングス株式会社 | Barrier film for electronic device |
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