JPH04198389A - Electro-luminescent element of thick film - Google Patents
Electro-luminescent element of thick filmInfo
- Publication number
- JPH04198389A JPH04198389A JP2322542A JP32254290A JPH04198389A JP H04198389 A JPH04198389 A JP H04198389A JP 2322542 A JP2322542 A JP 2322542A JP 32254290 A JP32254290 A JP 32254290A JP H04198389 A JPH04198389 A JP H04198389A
- Authority
- JP
- Japan
- Prior art keywords
- polymer
- acrylate
- polycyanoethyl
- dielectric
- molecular weight
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 229920000642 polymer Polymers 0.000 claims abstract description 60
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims abstract description 20
- 239000000843 powder Substances 0.000 claims description 15
- 239000000178 monomer Substances 0.000 abstract description 14
- 239000002904 solvent Substances 0.000 abstract description 9
- AEPWOCLBLLCOGZ-UHFFFAOYSA-N 2-cyanoethyl prop-2-enoate Chemical compound C=CC(=O)OCCC#N AEPWOCLBLLCOGZ-UHFFFAOYSA-N 0.000 abstract description 4
- 239000000126 substance Substances 0.000 abstract description 4
- 238000000354 decomposition reaction Methods 0.000 abstract description 3
- 238000010528 free radical solution polymerization reaction Methods 0.000 abstract description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 19
- 238000006116 polymerization reaction Methods 0.000 description 17
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical class CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 9
- 239000011159 matrix material Substances 0.000 description 9
- 239000000203 mixture Substances 0.000 description 8
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 239000002798 polar solvent Substances 0.000 description 6
- 125000001731 2-cyanoethyl group Chemical group [H]C([H])(*)C([H])([H])C#N 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 239000004372 Polyvinyl alcohol Substances 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 239000003505 polymerization initiator Substances 0.000 description 4
- 229920002451 polyvinyl alcohol Polymers 0.000 description 4
- ZMXDDKWLCZADIW-UHFFFAOYSA-N Vilsmeier-Haack reagent Natural products CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 239000011230 binding agent Substances 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 230000000379 polymerizing effect Effects 0.000 description 3
- 230000001681 protective effect Effects 0.000 description 3
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 2
- 229910002012 Aerosil® Inorganic materials 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 239000004373 Pullulan Substances 0.000 description 2
- 229920001218 Pullulan Polymers 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 239000011888 foil Substances 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- -1 polyethylene Polymers 0.000 description 2
- 235000019423 pullulan Nutrition 0.000 description 2
- KXJGSNRAQWDDJT-UHFFFAOYSA-N 1-acetyl-5-bromo-2h-indol-3-one Chemical compound BrC1=CC=C2N(C(=O)C)CC(=O)C2=C1 KXJGSNRAQWDDJT-UHFFFAOYSA-N 0.000 description 1
- WYGWHHGCAGTUCH-UHFFFAOYSA-N 2-[(2-cyano-4-methylpentan-2-yl)diazenyl]-2,4-dimethylpentanenitrile Chemical compound CC(C)CC(C)(C#N)N=NC(C)(C#N)CC(C)C WYGWHHGCAGTUCH-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 101150096839 Fcmr gene Proteins 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 238000011088 calibration curve Methods 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000007278 cyanoethylation reaction Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000003989 dielectric material Substances 0.000 description 1
- 238000007922 dissolution test Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000005227 gel permeation chromatography Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 238000004020 luminiscence type Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
Landscapes
- Electroluminescent Light Sources (AREA)
- Luminescent Compositions (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は、厚膜エレクトロルミネッセンス素子に係り、
特に、その発光層に用いられるマトリックスポリマーと
しての誘電体ポリマーに関する。[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to a thick film electroluminescent device,
In particular, it relates to a dielectric polymer as a matrix polymer used in the light emitting layer.
有機厚膜型のエレクトロルミネッセンス（以下ＥＬと略
称）素子は、その透明電極と対向電極との間に、Ｚｎ５
（Ｃｕ）などの螢光体粉末をマトリゲスポリマー中に分
散させた発光層（もしくは発光層の一部ととしての螢光
体層）や、ＢａＴｉ０゜などの誘電体粉末をマトリック
スポリマー中に分散させた発光層の一部としての誘電体
層を介設し、両電極間に所定の電圧を印加して発光層を
発光させるようになっている。そして、かかるＥＬ素子
の発光層に用いられる誘電体ポリマーとしては、螢光体
粉末や誘電体粉末を混合分散させるため極性の高い溶剤
に溶けやすく、かつ駆動電圧を低減化するため誘電率の
高いポリマーが選択される。An organic thick-film electroluminescent (hereinafter abbreviated as EL) element uses Zn5 between its transparent electrode and counter electrode.
A light-emitting layer (or a phosphor layer as a part of the light-emitting layer) in which a phosphor powder such as (Cu) is dispersed in a matrix polymer, or a dielectric powder such as BaTi0° in a matrix polymer. A dielectric layer is interposed as a part of the light emitting layer, and a predetermined voltage is applied between both electrodes to cause the light emitting layer to emit light. The dielectric polymer used in the light-emitting layer of such an EL device is easily soluble in highly polar solvents in order to mix and disperse the phosphor powder and dielectric powder, and has a high dielectric constant in order to reduce the driving voltage. A polymer is selected.
この種の誘電体ポリマーの具体例としては、従来、シア
ノエチル化ポリビニルアルコールやシアノエチル化セル
ロースなどが知られており、例えばシアノエチル化ポリ
ビニルアルコールを合成する場合、ポリビニルアルコー
ルにアクリロニトリルを塩基性触媒の存在下で反応させ
、ポリビニルアルコールの水酸基の水素を置換してシア
ノエチル基を導入する。As specific examples of this type of dielectric polymer, cyanoethylated polyvinyl alcohol and cyanoethylated cellulose are conventionally known. For example, when synthesizing cyanoethylated polyvinyl alcohol, acrylonitrile is added to polyvinyl alcohol in the presence of a basic catalyst. to replace hydrogen in the hydroxyl group of polyvinyl alcohol and introduce a cyanoethyl group.
しかしながら、従来の厚膜ＥＬ素子に用いられている誘
電体ポリマーは、上記したように水酸基の水素をシアノ
エチル基に置換して合成されるため、分子内に置換され
ずに残る水酸基が１０３以上存在してしまい、この残存
水酸基の影響で吸湿性が高まることから、水分により発
光層中の螢光体が分解されて輝度が劣化しやすく、発光
寿命が短くなってしまうという不具合があった。However, the dielectric polymer used in conventional thick-film EL devices is synthesized by replacing the hydrogen of the hydroxyl group with a cyanoethyl group as described above, so there are 103 or more hydroxyl groups that remain unsubstituted in the molecule. The remaining hydroxyl groups increase hygroscopicity, which causes the phosphor in the light-emitting layer to be decomposed by moisture, resulting in easy deterioration of brightness and shortening of light-emitting life.
そこで本発明者らは、予めシアンエチル基が導入されて
いるモノマーを重合して合成されるポリシアノエチルア
クリレートに着目したが、従来知られているボリシアノ
エチルアクレリートはゲル状ポリマーであって、極性の
高い溶剤に溶けにくいため、厚膜ＥＬ素子のマトリック
スポリマーとしては適さなかった。Therefore, the present inventors focused on polycyanoethyl acrylate, which is synthesized by polymerizing monomers into which cyanethyl groups have been introduced in advance, but the conventionally known polycyanoethyl acrylate is a gel-like polymer and has a polar It was not suitable as a matrix polymer for thick-film EL devices because it was difficult to dissolve in solvents with high concentrations.
本発明はこのような事情に鑑みてなされたもので、その
目的は、発光層中の誘電体ポリマーの吸湿性が低くて発
光寿命が長い厚ＭＥＬ素子を提供することにある。The present invention has been made in view of the above circumstances, and its purpose is to provide a thick MEL element in which the dielectric polymer in the light emitting layer has low hygroscopicity and has a long light emission life.
［課題を解決するための手段１
上記した本発明の目的は、発光層中の誘電体ポリマーの
少なくとも一部に、重量平均分子量が１万〜３５０万の
ポリシアノエチルアクリレートを用いることによって達
成される。[Means for Solving the Problems 1 The above object of the present invention is achieved by using polycyanoethyl acrylate having a weight average molecular weight of 10,000 to 3,500,000 for at least a portion of the dielectric polymer in the light emitting layer. .
〔作用］
予めシアンエチル基を有するモノマーを重合して合成さ
れるポリシアノエチルアクリレートは、側鎖がすべてシ
アノエチル基からなるため吸湿性が低く、かつ誘電率の
高いポリマーなので、発光寿命を延ばすことができ、か
つ駆動電圧を低減化することができる。そして、このポ
リシアノエチルアクリレートの分子量が１万〜３５０万
の範囲内に設定してあれば、極性の高い溶剤に対して可
溶で、かつ無機粉末を結着させるのに十分なバインダ機
能を有するので、螢光体粉末や誘電体粉末を容易に混合
分散させることができる。[Function] Polycyanoethyl acrylate, which is synthesized by polymerizing monomers having cyanethyl groups in advance, has low hygroscopicity because all side chains are composed of cyanoethyl groups, and is a polymer with a high dielectric constant, so it can extend the luminescent life. In addition, the driving voltage can be reduced. If the molecular weight of this polycyanoethyl acrylate is set within the range of 10,000 to 3,500,000, it is soluble in highly polar solvents and has sufficient binder function to bind inorganic powders. Therefore, fluorescent powder and dielectric powder can be easily mixed and dispersed.
［実施例］
以下、本発明の実施例を図表に基づいて詳細に説明する
。[Example] Hereinafter, an example of the present invention will be described in detail based on diagrams.
まず、本発明に係ねる誘電体ポリマーについて説明する
。First, the dielectric polymer according to the present invention will be explained.
本発明者らは、モノマーとして２−シアノエチルアクリ
レートを用い、極性の高い溶剤を溶媒とする溶液重合を
行うことにより、誘電体ポリマーとしてのポリシアノエ
チルアクリレートを合成することとし、重合条件を主に
設定することで当該ポリマーの分子量を制御した。なお
、ポリマーの分子量に影響を与える重合条件としては、
重合溶媒の種類、重合溶液中のモノマー濃度、重合温度
、重合時間、重合開始剤の種類などが挙げられる。The present inventors decided to synthesize polycyanoethyl acrylate as a dielectric polymer by performing solution polymerization using 2-cyanoethyl acrylate as a monomer and a highly polar solvent, and mainly set the polymerization conditions. By doing so, the molecular weight of the polymer was controlled. The polymerization conditions that affect the molecular weight of the polymer are as follows:
Examples include the type of polymerization solvent, monomer concentration in the polymerization solution, polymerization temperature, polymerization time, and type of polymerization initiator.
次に具体例を示す。A specific example is shown next.
（具体例１）
冷却管を付けた２０フラスコ（２００ｍＡ）に窒素ライ
ンを接続し、フラスコ内を窒素置換した後、ここに、通
常の方法で蒸留した２−シアノエチルアクリレートモノ
マーを０．０５ｍｏｆｆ、重合開始剤として２，２′−
アゾビスイソブチロニトリルをモノマー全量に対し２モ
ル％、重合溶媒として脱水処理をしたアセトンを適量加
え、アセトンの量に応じてモノマー濃度が異なる６種類
の溶液（モノマー濃度１０〜４５重量％）をそれぞれ、
６０℃で１０００分間加熱して、試料ＮＣＬｌ〜６の６
種類のポリマー（ポリシアノエチルアクリレート）を重
合した。しかる後、合成されたポリマーのアセトンに対
する溶解性の評価と、このポリマーの重量平均分子量の
測定とを行った。その結果を第１表に示す。(Specific Example 1) A nitrogen line was connected to a 20 flask (200 mA) equipped with a cooling tube, and after replacing the inside of the flask with nitrogen, 0.05 moff of 2-cyanoethyl acrylate monomer distilled in a conventional manner was added to the flask and polymerized. 2,2'- as initiator
Add 2 mol% of azobisisobutyronitrile based on the total amount of monomers and an appropriate amount of dehydrated acetone as a polymerization solvent to create 6 types of solutions with different monomer concentrations depending on the amount of acetone (monomer concentration 10 to 45% by weight). respectively,
Heating at 60°C for 1000 minutes, sample NCLl~6
A variety of polymers (polycyanoethyl acrylate) were polymerized. Thereafter, the solubility of the synthesized polymer in acetone was evaluated and the weight average molecular weight of this polymer was measured. The results are shown in Table 1.
なお、重合温度の６０℃は、重合開始剤の半減時間が約
１０００分間となる温度である。Note that the polymerization temperature of 60° C. is a temperature at which the half-life time of the polymerization initiator is about 1000 minutes.
また、ポリマーの溶解性を評価する際には、ポリマーを
過剰のメタノール中で精製し、これを真空乾燥してメタ
ノールを除去したポリマー１ｇと、５ｇのアセトンとを
混合し、２４時間後、この混合物を２００メツシユのテ
トロン類の網を用いて滴化するというテストを行い、濾
過できないポリマーの固まりがある場合を不溶性と判断
した。In addition, when evaluating the solubility of a polymer, 1 g of the polymer purified in excess methanol and vacuum-dried to remove methanol is mixed with 5 g of acetone, and after 24 hours, the A test was conducted in which the mixture was made into droplets using a 200-mesh Tetoron net, and if there was a lump of polymer that could not be filtered, it was determined that the mixture was insoluble.
さらにまた、ポリマーの重量平均分子量の測定は、温度
５０℃でゲル浸透グロマトグラフイ−（東ソ製５Ｃ−８
０１０）、５０万のカラムを用い、溶媒としてＮ、Ｎ’
−ジメチルホルムアミド、標準物質としてポリエチレ
ングリコールを使用して較正曲線を作成して分子量を算
出した。Furthermore, the weight average molecular weight of the polymer was measured using gel permeation chromatography (Toso 5C-8) at a temperature of 50°C.
010), using a 500,000 column, N and N' as solvents.
- Dimethylformamide and polyethylene glycol were used as a standard substance to create a calibration curve and calculate the molecular weight.
第 １ 表
（具体例２）
具体例１において千ツマー濃度が３５重量％の溶液に対
し、重合温度のみを変更（３０〜６０’Ｃ）して他は同
様の条件で重合を行い、試料Ｎ００７〜１１の５種類の
ポリマーを得た。しかる後、各ポリマーの溶解性の評価
および重量平均分子量の測定を行った。その結果を第２
表に示す。Table 1 (Specific Example 2) In Specific Example 1, polymerization was carried out using a solution with a concentration of 35% by weight, except that only the polymerization temperature was changed (30 to 60'C), and other conditions were the same. Five types of polymers ranging from 1 to 11 were obtained. Thereafter, the solubility of each polymer was evaluated and the weight average molecular weight was measured. The result is the second
Shown in the table.
第 ２ 表
（具体例３）
具体例１においてモノマー濃度が３５重量％の溶液に対
し、重合時間のみを変更（１〜２４時間）して他は同様
の条件で重合を行い、試料Ｎｏ、１２〜１６の５種類の
ポリマーを得た。しかる後、各ポリマーの溶解性の評価
および重量平均分子量の測定を行った。その結果を第３
表に示す。Table 2 (Specific Example 3) In Specific Example 1, a solution with a monomer concentration of 35% by weight was polymerized under the same conditions except that only the polymerization time was changed (1 to 24 hours). Five types of polymers of ~16 were obtained. Thereafter, the solubility of each polymer was evaluated and the weight average molecular weight was measured. The result is the third
Shown in the table.
（具体例４）
重合溶媒としてＮ、Ｎ’−ジメチルホルムアミドを用い
た以外は具体例１と同様の条件に設定し、溶媒の量に応
じてモノマー濃度が異なる６種類の溶液（モノマー濃度
１０〜４５重量％）からそれぞれ、試料Ｎｏ、１７〜２
２の６種類のポリマーを得た。しかる後、各ポリマーの
溶解性の評価および重量平均分子量の測定を行った。そ
の結果を第４表に示す。(Specific Example 4) The conditions were the same as those in Specific Example 1 except that N,N'-dimethylformamide was used as the polymerization solvent, and six types of solutions with different monomer concentrations depending on the amount of solvent (monomer concentration 10 to 10) were prepared. 45% by weight) from sample No. 17 to 2, respectively.
Six types of polymers of 2 were obtained. Thereafter, the solubility of each polymer was evaluated and the weight average molecular weight was measured. The results are shown in Table 4.
第 ４ 表
（具体例５）
重合開始剤として２，２′−アゾビス（２，４−ジメチ
ルバレロニトリル）を用い、かつ重合温度を、この重合
開始剤の半減時間が１０００分間となる温度（５０℃）
に設定した以外は、具体例１と同様の条件で重合を行い
、モノマー濃度が異なる６種類の溶液（モノマー濃度１
０〜４５重量％）からそれぞれ、試料Ｎｏ、２３〜２８
の６種類のポリマーを得た。しかる後、各ポリマーの溶
解性の評価および重量平均分子量の測定を行った。その
結果を第５表に示す。Table 4 (Specific Example 5) 2,2'-azobis(2,4-dimethylvaleronitrile) was used as a polymerization initiator, and the polymerization temperature was set at a temperature at which the half-life time of this polymerization initiator was 1000 minutes (50 ℃)
Polymerization was carried out under the same conditions as in Example 1, except that 6 types of solutions with different monomer concentrations (monomer concentration 1
Sample No. 23-28 from 0-45% by weight), respectively.
Six types of polymers were obtained. Thereafter, the solubility of each polymer was evaluated and the weight average molecular weight was measured. The results are shown in Table 5.
第 ５ 表
なお、本発明者は試料Ｎ ｏ 、 ２０のポリマーを
精製して重量平均分子量が３５０万のポリマーを得たが
、このポリマーも溶解テストの結果、溶液となり得るこ
とを確認した。Table 5 Note that the present inventor purified the polymer of sample No. 20 to obtain a polymer with a weight average molecular weight of 3.5 million, and as a result of a dissolution test, it was confirmed that this polymer could also be turned into a solution.
上記から明らかなように、２−シアノエチルアクリレー
トを溶液重合して得られるポリマー（ポリシアノエチル
アクリレート）の分子量は、重合条件を変更することに
よって制御することができ、また、ポリマーの重量平均
分子量が３５０万以下であればアセトンのような極性の
高い溶剤に溶解することがわかる。しかし、このポリマ
ーの重量平均分子量が１万に満たないと、無機粉末を結
着させるのに十分なバインダ機能が得られないので、螢
光体粉末や誘電体粉末を混合分散させるマトリックスポ
リマーとしては不適である。As is clear from the above, the molecular weight of the polymer (polycyanoethyl acrylate) obtained by solution polymerizing 2-cyanoethyl acrylate can be controlled by changing the polymerization conditions, and the weight average molecular weight of the polymer is 350. It can be seen that if it is less than 10,000 yen, it will dissolve in a highly polar solvent such as acetone. However, if the weight average molecular weight of this polymer is less than 10,000, it will not have sufficient binder function to bind the inorganic powder, so it cannot be used as a matrix polymer for mixing and dispersing phosphor powder or dielectric powder. Not suitable.
したがって、誘電率が高く吸湿性が低いという長所を有
するポリシアノエチルアクリレートは、重合条件を適宜
選択して重量平均分子量を１万〜３５０万の範囲内に設
定してやれば、極性の高い溶剤に可溶でバインダ機能も
十分な誘電体ポリマーとして使用することができ、厚ｆ
ｆＫＥＬ素子の発光層のマトリックスポリマーに適用し
て優れた効果が期待できる。なお、上記の範囲のポリシ
アノエチルアクリレートの誘電率は１７〜２４の範囲で
あった。そして、上記した各具体例のデータを考察する
と、重量平均分子量が１万〜３５０万のポリシアノエチ
ルアクリレートを重合するためには、少なくとも、溶媒
として極性の高い溶剤を用い、かつ溶液中の千ツマー濃
度を４０重量％以下（好ましくは３５重量％以下）に抑
え、かつ重合温度を４０”Ｃ以上（好ましくは４５℃以
上）に設定する必要がある。Therefore, polycyanoethyl acrylate, which has the advantages of high dielectric constant and low hygroscopicity, can be soluble in highly polar solvents by appropriately selecting polymerization conditions and setting the weight average molecular weight within the range of 10,000 to 3,500,000. It also has sufficient binder function and can be used as a dielectric polymer, with a thickness f
Excellent effects can be expected when applied to the matrix polymer of the light-emitting layer of fKEL devices. Note that the dielectric constant of the polycyanoethyl acrylate in the above range was in the range of 17 to 24. Considering the data of each specific example above, in order to polymerize polycyanoethyl acrylate with a weight average molecular weight of 10,000 to 3,500,000, at least a highly polar solvent must be used as the solvent, and It is necessary to suppress the concentration to 40% by weight or less (preferably 35% by weight or less) and set the polymerization temperature to 40''C or higher (preferably 45°C or higher).
次に、前記した各具体例にて合成したポリマーのうち、
重量平均分子量が１．３万〜２９０万の】０種類の試料
を用いて、それぞれ第１図に示す如きＥＬの螢光体層を
形成し、各ＥＬの輝度半減時間を測定した。Next, among the polymers synthesized in each of the specific examples described above,
Using 0 kinds of samples having a weight average molecular weight of 13,000 to 2,900,000, EL phosphor layers as shown in FIG. 1 were formed, and the luminance half-life time of each EL was measured.
すなわち、同図に示すＥＬは、透明シートｌの片面に形
成された透明電極２と、アルミニウムなどの金属箔から
なる対向電極３との間に、螢光体層４と誘電体層５とを
積層してなる発光層６を介設して素子が構成され、この
素子を、防湿性の高い透明樹脂フィルムからなる保護シ
ート７と、アルミ複合フィルムなどの防湿性の極めて高
いフィルムからなる保護シート８とによって密封被覆し
、図示せぬリード端子を介して画電極２，３間に所定の
電圧を印加することにより、発光層６を発光させるとい
うものである。That is, the EL shown in the figure has a phosphor layer 4 and a dielectric layer 5 between a transparent electrode 2 formed on one side of a transparent sheet l and a counter electrode 3 made of metal foil such as aluminum. An element is constructed by interposing a laminated light emitting layer 6, and this element is covered with a protective sheet 7 made of a highly moisture-proof transparent resin film and a protective sheet made of an extremely moisture-proof film such as an aluminum composite film. The light-emitting layer 6 is caused to emit light by applying a predetermined voltage between the picture electrodes 2 and 3 via lead terminals (not shown).
詳述すると、まず、螢光体粉末としてＺｎ （Ｃｕ）２
００ ｇ、上記の試料Ｎｌｌの誘電体ポリマー４０ｇを
γ−ブチロラクトン６０ｇに溶解、分散した溶液１００
ｇと、アエロジルＩｇをγ−ブチロラクトン４０ｇに分
散した分散液４１ｇとを均一に混合分散し、液状組成物
とした。この液状組成物をスクリーン印刷で透明シート
ｌの透明電極２上に印刷塗布し、乾燥して厚さ約３０μ
ｍの螢光体層４を形成した。To explain in detail, first, Zn (Cu)2 was used as a phosphor powder.
00 g, a solution of 40 g of the dielectric polymer of the above sample Nll dissolved and dispersed in 60 g of γ-butyrolactone.
g and 41 g of a dispersion of Aerosil Ig dispersed in 40 g of γ-butyrolactone were uniformly mixed and dispersed to obtain a liquid composition. This liquid composition was applied by screen printing onto the transparent electrode 2 of the transparent sheet 1, and dried to a thickness of about 30 μm.
A phosphor layer 4 of m was formed.
次に、前記と同じ試料隘１の誘電体ポリマー４０ｇをγ
−ブチロラドタン６０ｇに溶解、分散した溶液と、アエ
ロジル１ｇをγ−ブチロラクトン６０ｇに分散した分散
液とを均一に混合分散して液状組成物とし、この液状組
成物を上記蛍光体層４上に印刷塗布し、乾燥して厚さ５
０μｍの誘電体層５を形成した。Next, 40 g of the dielectric polymer in sample size 1 as above was
- A solution dissolved and dispersed in 60 g of butyroradane and a dispersion of 1 g of Aerosil dispersed in 60 g of γ-butyrolactone are uniformly mixed and dispersed to form a liquid composition, and this liquid composition is printed and coated on the phosphor layer 4. and dry to a thickness of 5
A dielectric layer 5 having a thickness of 0 μm was formed.
螢光体層４、誘電体層５のマトリックスポリマーとなる
ポリシアノエチルアクリレートの分子量が１．３万〜２
９０万に設定しであることがら、このポリマーは印刷に
好適で、かつ蛍光体層４においては螢光体粉末を十分に
結着して透明電極２との密着性も良好であった。The molecular weight of polycyanoethyl acrylate, which is the matrix polymer of the phosphor layer 4 and dielectric layer 5, is 13,000 to 2.
900,000, this polymer was suitable for printing, and in the phosphor layer 4, the phosphor powder was sufficiently bound and the adhesion to the transparent electrode 2 was also good.
次に、上記の誘電体層５上にアルミニウム箔の対向電極
３を設け、これらの積層物をポリエチレンフィルム７お
よびポリエチレンテレフタレート／アルミニウム複合フ
ィルム８の一対の保護シートで被覆密閉したＥＬ素子を
製造した。Next, a counter electrode 3 made of aluminum foil was provided on the dielectric layer 5, and the laminate was covered and sealed with a pair of protective sheets of a polyethylene film 7 and a polyethylene terephthalate/aluminum composite film 8 to produce an EL device. .
更に、第６表に示す試料宛２〜患２６について ・も上
記の方法でＥＬ素子を製造した。Furthermore, EL devices for samples 2 to 26 shown in Table 6 were also manufactured by the above method.
また、上記の試料の他に、本発明の誘電体ポリマーを他
の誘電体ポリマーと混合して適用したＥＬ素子を製造し
た。即ち、前述した方法と同様に、たたし、誘電体ポリ
マーとして、シアノエチル化プルラン（シアンエチル化
率が約９０％）６５重量部と試料隘１の誘電体（３５重
量）とのブレンドポリマーを用いてＥＬ素子を製造した
。In addition to the above-mentioned samples, EL devices were also manufactured in which the dielectric polymer of the present invention was mixed with other dielectric polymers. That is, in the same manner as in the method described above, a blend polymer of 65 parts by weight of cyanoethylated pullulan (cyanoethylation rate is about 90%) and the dielectric material of sample size 1 (35 parts by weight) was used as a dielectric polymer. An EL device was manufactured using the above method.
このようにして作製した１１種類のＥＬと従来のＥＬ（
ただし螢光体層に用いたポリマーの種類以外の条件はす
べて同じ）について、その輝度半減時間を測定した結果
を第６表に示す。Eleven types of EL produced in this way and conventional EL (
Table 6 shows the results of measuring the luminance half-life time under all conditions (all conditions other than the type of polymer used in the phosphor layer being the same).
同表に明らかなように、螢光体層のマトリックスポリマ
ーとして、側鎖がすべてシアノエチル基からなり吸湿性
が低いポリシアノエチルアクリレートを用いたＥＬは、
螢光体粉末の水分による分解が抑制されて発光寿命が飛
躍的に延びることがわかる。As is clear from the same table, the EL using polycyanoethyl acrylate, which has all side chains composed of cyanoethyl groups and has low hygroscopicity, as the matrix polymer of the phosphor layer,
It can be seen that the decomposition of the phosphor powder due to moisture is suppressed and the luminescence life is dramatically extended.
なお、分子量を制御したポリシアノエチルアクリレート
は、螢光体層、誘電体層のいずれが一方に用いてもその
効果が期待でき、また−層構造の発光層のマトリックス
ポリマーとして用いても同様の効果が期待できる。Polycyanoethyl acrylate with a controlled molecular weight can be expected to have the same effect whether it is used in either the phosphor layer or the dielectric layer, and the same effect can be expected when it is used as a matrix polymer in the light emitting layer of a -layer structure. can be expected.
また、シアノエチルセルロースやシアノエチルプルラン
などの結晶性のポリマーとのブレンドにおいても、分子
量を制御したポリシアノエチルアクリレートが良好な溶
解性を示すことがら良好な分散状態を得ることができる
。Further, even in a blend with a crystalline polymer such as cyanoethyl cellulose or cyanoethyl pullulan, a good dispersion state can be obtained since polycyanoethyl acrylate with a controlled molecular weight exhibits good solubility.
以上説明したように、本発明にょる厚膜ＥＬ素子は、発
光層中のポリマーとして、螢光体層や誘電体層を混合分
散させるうえで好適となるように分子量を制御したポリ
シアノエチルアクリレートを用いており、このポリマー
は吸湿性が低いので水分による螢光体の分解が抑えられ
、そのため発光寿命を大幅に延ばすことができるという
顕著な効果を奏する。As explained above, the thick film EL device according to the present invention uses polycyanoethyl acrylate, whose molecular weight is controlled so as to be suitable for mixing and dispersing the phosphor layer and the dielectric layer, as the polymer in the light emitting layer. Since this polymer has low hygroscopicity, the decomposition of the phosphor due to moisture is suppressed, which has the remarkable effect of significantly extending the luminescent lifetime.
第１図は本発明の実施例に係るＥＬの断面図である。
２・・・・・透明電極、３・・・・・対向電極、４・・
・・・螢光体層、５・・・・・・誘電体層、６・・・・
・・発光層。
＃１図
２ 透 明１？ネセ
３・対画を詩
４・蛍人Ａｊ、９
５ １−き電イネ４か
６ ダ尤層
手続補正書（師）
平成 ３年 １月２２日FIG. 1 is a sectional view of an EL according to an embodiment of the present invention. 2...Transparent electrode, 3...Counter electrode, 4...
... Fluorescent layer, 5... Dielectric layer, 6...
...Light-emitting layer. #1 Figure 2 Transparent 1? Nese 3・Taiga wo Poem 4・Horujin Aj, 9 5 1-Kiden Ine 4 or 6 Da-Yuu Proceedings Amendment (Teacher) January 22, 1991
Claims (1)
粉末や誘電体粉末を分散せしめた発光層を介設し、上記
両電極間に電圧を印加して上記発光層を発光させる厚膜
エレクトロルミネツセンス素子において、上記発光層中
の誘電体ポリマーの少なくとも一部に、重量平均分子が
１万〜３５０万のポリシアノエチルアクリレートを用い
たことを特徴とする厚膜エレクトロルミネツセンス素子
。A thick-film electroluminescent layer is provided between a transparent electrode and a counter electrode, and a light-emitting layer in which fluorescent powder or dielectric powder is dispersed in a dielectric polymer is interposed, and a voltage is applied between the two electrodes to cause the light-emitting layer to emit light. 1. A thick film electroluminescent device, characterized in that polycyanoethyl acrylate having a weight average molecular weight of 10,000 to 3,500,000 is used for at least a portion of the dielectric polymer in the luminescent layer.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2322542A JP2644623B2 (en) | 1990-11-28 | 1990-11-28 | Thick film electroluminescent element |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2322542A JP2644623B2 (en) | 1990-11-28 | 1990-11-28 | Thick film electroluminescent element |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH04198389A true JPH04198389A (en) | 1992-07-17 |
| JP2644623B2 JP2644623B2 (en) | 1997-08-25 |
Family
ID=18144835
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2322542A Expired - Fee Related JP2644623B2 (en) | 1990-11-28 | 1990-11-28 | Thick film electroluminescent element |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2644623B2 (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20000072077A (en) * | 2000-07-24 | 2000-12-05 | 허석철 | high polymer of organic- dispersed electroluminescent lamp |
| WO2004019347A1 (en) * | 2002-08-23 | 2004-03-04 | Agfa-Gevaert | Layer configuration comprising an electron-blocking element |
| US6977390B2 (en) | 2002-08-23 | 2005-12-20 | Agfa Gevaert | Layer configuration comprising an electron-blocking element |
| US7307276B2 (en) | 2002-08-23 | 2007-12-11 | Agfa-Gevaert | Layer configuration comprising an electron-blocking element |
| CN114094181A (en) * | 2020-08-25 | 2022-02-25 | 深圳市比亚迪锂电池有限公司 | Lithium ion electrolyte, preparation method and lithium ion battery |
-
1990
- 1990-11-28 JP JP2322542A patent/JP2644623B2/en not_active Expired - Fee Related
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20000072077A (en) * | 2000-07-24 | 2000-12-05 | 허석철 | high polymer of organic- dispersed electroluminescent lamp |
| WO2004019347A1 (en) * | 2002-08-23 | 2004-03-04 | Agfa-Gevaert | Layer configuration comprising an electron-blocking element |
| WO2004019348A1 (en) * | 2002-08-23 | 2004-03-04 | Agfa-Gevaert | Layer configuration comprising an electron-blocking element |
| US6977390B2 (en) | 2002-08-23 | 2005-12-20 | Agfa Gevaert | Layer configuration comprising an electron-blocking element |
| US7307276B2 (en) | 2002-08-23 | 2007-12-11 | Agfa-Gevaert | Layer configuration comprising an electron-blocking element |
| CN114094181A (en) * | 2020-08-25 | 2022-02-25 | 深圳市比亚迪锂电池有限公司 | Lithium ion electrolyte, preparation method and lithium ion battery |
| CN114094181B (en) * | 2020-08-25 | 2024-05-14 | 深圳市比亚迪锂电池有限公司 | Lithium ion electrolyte, preparation method and lithium ion battery |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2644623B2 (en) | 1997-08-25 |
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