JPH04196012A - Dielectric substance polymer and its manufacture - Google Patents
Dielectric substance polymer and its manufactureInfo
- Publication number
- JPH04196012A JPH04196012A JP32254490A JP32254490A JPH04196012A JP H04196012 A JPH04196012 A JP H04196012A JP 32254490 A JP32254490 A JP 32254490A JP 32254490 A JP32254490 A JP 32254490A JP H04196012 A JPH04196012 A JP H04196012A
- Authority
- JP
- Japan
- Prior art keywords
- polymer
- molecular weight
- acrylate
- weight
- polymerization
- 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.)
- Pending
Links
- 229920000642 polymer Polymers 0.000 title claims abstract description 54
- 238000004519 manufacturing process Methods 0.000 title claims description 4
- 239000000126 substance Substances 0.000 title abstract description 3
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 23
- AEPWOCLBLLCOGZ-UHFFFAOYSA-N 2-cyanoethyl prop-2-enoate Chemical compound C=CC(=O)OCCC#N AEPWOCLBLLCOGZ-UHFFFAOYSA-N 0.000 claims abstract description 8
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 19
- 239000000178 monomer Substances 0.000 claims description 13
- 239000002798 polar solvent Substances 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 3
- 239000002904 solvent Substances 0.000 abstract description 9
- 239000010410 layer Substances 0.000 description 25
- 239000000843 powder Substances 0.000 description 16
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 15
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 11
- 239000011159 matrix material Substances 0.000 description 7
- 125000001731 2-cyanoethyl group Chemical group [H]C([H])(*)C([H])([H])C#N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 239000010408 film Substances 0.000 description 6
- 239000004372 Polyvinyl alcohol Substances 0.000 description 5
- 229920002451 polyvinyl alcohol Polymers 0.000 description 5
- 239000011230 binding agent Substances 0.000 description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 4
- 239000003505 polymerization initiator Substances 0.000 description 4
- 230000000379 polymerizing effect Effects 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 239000003990 capacitor Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000010409 thin film Substances 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
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 238000004020 luminiscence type Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 230000001681 protective effect Effects 0.000 description 2
- 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
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- IDCBOTIENDVCBQ-UHFFFAOYSA-N TEPP Chemical compound CCOP(=O)(OCC)OP(=O)(OCC)OCC IDCBOTIENDVCBQ-UHFFFAOYSA-N 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
- 239000002131 composite material Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000007922 dissolution test Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 238000005227 gel permeation chromatography Methods 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229920001223 polyethylene glycol Polymers 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
- 238000007789 sealing Methods 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 230000002269 spontaneous effect Effects 0.000 description 1
Landscapes
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Organic Insulating Materials (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や薄膜コ
ンデンサなどに用いられる誘電体ポリマーと、その製造
方法とに関する。DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a dielectric polymer used in thick film electroluminescent devices, thin film capacitors, etc., and a method for producing the same.
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クスポリマー中に分
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、Ｂ ａ Ｔ Ｉ Ｏ４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
ＥＩ、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 part of a light-emitting layer) in which a phosphor powder such as (Cu) is dispersed in a matrix polymer, or a dielectric powder such as B a T I O4 in a matrix polymer. A dielectric layer as a part of the light-emitting layer dispersed in the light-emitting layer is interposed, 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 EI and devices is easily soluble in highly polar solvents in order to mix and disperse the phosphor powder and dielectric powder, and has a low dielectric constant in order to reduce the driving voltage. High polymers are 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製造する場合、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という方法で合成される。As specific examples of this type of dielectric polymer, cyanoethylated polyvinyl alcohol and cyanoethylated cellulose are conventionally known. For example, when producing cyanoethylated polyvinyl alcohol, acrylonitrile is added to polyvinyl alcohol in the presence of a basic catalyst. It is synthesized by reacting with polyvinyl alcohol, replacing hydrogen in the hydroxyl group of polyvinyl alcohol, and introducing a cyanoethyl group.
〔発明か解決しようとする課題］
しかしながら、従来のこの種の誘電体ポリマーは、」１
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１
０％以」−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、ＥＬ素子のマトリックスポリマ
ーとして使用すると、水分により螢光体か分解されて輝
度が劣化しやすく、発光ノＩ命が短くなってしまうとい
う不具合があった。[Problem to be solved by the invention] However, the conventional dielectric polymer of this type is
As mentioned above, since it is synthesized by replacing the hydrogen of the hydroxyl group with a cyanoethyl group, there is one hydroxyl group remaining unsubstituted in the molecule.
0% or more, and the hygroscopicity increases due to the influence of these residual hydroxyl groups.When used as a matrix polymer for EL devices, the phosphor is easily decomposed by moisture, resulting in deterioration of brightness, and the luminescence There was a problem that his life was shortened.
そこで本発明者らは、予めシアノエチル基が導入されて
いる千ツマ−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、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 cyanoethyl acrylate into which a cyanoethyl group has been introduced in advance, but the conventionally known polycyanoethyl acrylate is a gel-like polymer. Because it is difficult to dissolve in highly polar solvents, it was not suitable as a matrix polymer for EL devices.
本発明はこのような事情に鑑みてなされたもので、その
第１の目的は、誘電率が高くて吸湿性か低く、しかも極
性の高い溶剤に溶けやすい誘電体ポリマーを提供するこ
とにある。また、本発明の第２の目的は、かかる誘電体
ポリマーの製造方法を提供することにある。The present invention was made in view of these circumstances, and its first objective is to provide a dielectric polymer that has a high dielectric constant, low hygroscopicity, and is easily soluble in highly polar solvents. A second object of the present invention is to provide a method for producing such a dielectric polymer.
〔課題を解決するための手段］
」１記した本発明の第１の目的は、ポリシアノエチルア
クリレートの重量平均分子量を１万〜３５０万の範囲内
に設定することによって達成される。[Means for Solving the Problems] The first object of the present invention described in 1 is achieved by setting the weight average molecular weight of polycyanoethyl acrylate within the range of 10,000 to 3,500,000.
また、上記した本発明の第２の１」的は、モノマーとし
ての２−シアノエチルアクリレートの濃度が４０重量％
以下で極性の高い溶剤を溶媒とする重合溶液を用い、こ
れを４．０’Ｃ以］二に加熱してポリシアノエチルアク
リレートを重合することによって達成される。In addition, the second object of the present invention described above is that the concentration of 2-cyanoethyl acrylate as a monomer is 40% by weight.
This is achieved by polymerizing polycyanoethyl acrylate by using a polymerization solution in which a highly polar solvent is used as a solvent and heating the solution to 4.0'C or higher.
〔作用］
予めシアノエチル基を有する２−シアノエチルアクリレ
ート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であって、しかも重
合条件を適宜選択することで分子量の制御が行えるので
、極性の高い溶剤に対して可溶なポリシアノエチルアク
リレートが得られる。[Function] Polycyanoethyl acrylate, which is synthesized by polymerizing 2-cyanoethyl acrylate having a cyanoethyl group in advance, has low hygroscopicity and high dielectric constant because all side chains are composed of cyanoethyl groups, and is a polymer with high dielectric constant. Since the molecular weight can be controlled by appropriately selecting conditions, polycyanoethyl acrylate that is soluble in highly polar solvents can be obtained.
すなわち、分子量が３５０万以下のポリシアノエチルア
クリレートは、アセトンやＮ、Ｎ’ −ジメチルホルム
アミド等の極性の高い溶剤に可溶であり、また、分子量
が１万以」二のポリシアノエチルアクリレートは、螢光
体粉末や誘電体粉末等の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。That is, polycyanoethyl acrylate with a molecular weight of 3.5 million or less is soluble in highly polar solvents such as acetone and N,N'-dimethylformamide, and polycyanoethyl acrylate with a molecular weight of 10,000 or more is soluble in fluorescent solvents. It has sufficient binder function to bind inorganic powders such as optical powder and dielectric powder.
〔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.
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 below.
（実施例１）
冷却管を付けた２０フラスコ（１００ｍＱ）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０．０５ｍｏα、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、６
００Ｃで１０００分間加熱して、試料Ｎｏ、１〜６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。(Example 1) A nitrogen line was connected to a 20 flask (100 mQ) equipped with a cooling tube, and after the inside of the flask was replaced with nitrogen, 0.05 moα of 2-cyanoethyl acrylate monomer distilled by a conventional method was polymerized. By adding 2 mol% of 2,2'-azobisisobutyronitrile as an initiator based on the total amount of monomers and an appropriate amount of dehydrated acetone as a polymerization solvent, six types of solutions with different monomer concentrations depending on the amount of acetone were prepared ( monomer concentration 10 to 45% by weight), respectively.
Heating at 00C for 1000 minutes, sample No. 1 to 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
トロン製の網を用いて濾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 filtered using a 200-mesh Tetron net, and insolubility was determined if there was a mass of polymer that could not be filtered.
さらにまた、ポリマーの重量平均分子量を測定する際に
は、ゲル浸透クロマトグラフィー（東ソ製５Ｃ−８０１
０）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
較正曲線を作成することにより、分子量を算出した。Furthermore, when measuring the weight average molecular weight of the polymer, gel permeation chromatography (Toso 5C-801
0), the molecular weight was calculated by creating a calibration curve using N,N'-dimethylformamide as a solvent and polyethylene glycol as a standard substance.
（実施例２）
実施例１においてモノマー濃度が３５重量％の溶液に対
し、重合温度のみを変更（３０〜６０℃）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。(Example 2) Polymerization was performed using the solution with a monomer concentration of 35% by weight in Example 1 under the same conditions except that only the polymerization temperature was changed (30 to 60°C), and 5 types of samples No. 007 to 11 were prepared. of polymer was obtained. Thereafter, the solubility of each polymer was evaluated and the weight average molecular weight was measured. The results are shown in Table 2.
第 ２ 表
（実施例３）
実施例１において千ツマー濃度が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 (Example 3) In Example 1, polymerization was carried out using the solution with a concentration of 35% by weight except for changing the polymerization time (1 to 24 hours) under the same conditions. Five types of polymers numbered 12 to 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.
第 ３ 表
（実施例４）
重合溶媒としてＮ、Ｎ’−ジメチルホルムアミドを用い
た以外は実施例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。Table 3 (Example 4) The conditions were the same as in Example 1 except that N,N'-dimethylformamide was used as the polymerization solvent, and six types of solutions (monomer Sample No. 17-2 from 10-45% by weight)
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
（実施例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、実施例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 (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 the 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Ｎｏ、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 The present inventor purified the polymer of Sample No. 20 to obtain a polymer having 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。しがし、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７トリツクスボ
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 7 tricks for mixing and dispersing phosphor powder and dielectric powder It is unsuitable as a svolimer.
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、Ｅｌ
、素子の発光層のマトリックスポリマーなどに適用して
優れた効果が期待できる。そして、上記した各実施例の
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
液中のモノマー濃度を４０重量％以下（好ましくは３５
重量％以下）に抑え、がっ重合温度を４０℃以］−（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. With binder function, it can also be used as a dielectric polymer, and El
Excellent effects can be expected when applied to matrix polymers in light-emitting layers of devices. Considering the data of each example described above, in order to polymerize polycyanoethyl acrylate having a weight average molecular weight of 10,000 to 3,500,000,
At least, a highly polar solvent is used as the solvent, and the monomer concentration in the solution is 40% by weight or less (preferably 35% by weight or less).
% by weight or less), and the polymerization temperature must be set to 40°C or higher (preferably 45°C or higher).
次に、前記した各実施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１０種類の試料
を用いて、それぞれ第１図に示す如きＩＥ Ｉ−の螢光
体層を形成し、各Ｅ Ｉ−の輝度半減時間を測定した。Next, among the polymers synthesized in each of the above examples,
Using 10 types of samples with weight average molecular weights of 13,000 to 2,900,000, a phosphor layer of IE I- as shown in Figure 1 was formed, and the luminance half-life time of each E I- was measured. .
すなわち、同図に示すＥＩ−は、透明シート１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
を積属してなる発光層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, EI- 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 1 and a counter electrode 3 made of metal foil such as aluminum. The device is constructed by interposing a light-emitting layer 6 formed by laminating the above layers, and this device is protected by a protective sheet 7 made of a highly moisture-proof transparent resin film and a protective sheet 7 made of an extremely moisture-proof film such as an aluminum composite film. The light-emitting layer 6 is caused to emit light by sealing it with a sheet 8 and applying a predetermined voltage between the picture electrodes 2 and 3 via lead terminals (not shown).
また、このＥＬの螢光体層４は、ＺｎＳ （Ｃｕ）やＺ
ｎＳ（Ｍｎ）などの螢光体粉末と、前記実施例にて合成
した誘電体ポリマーとを、有機溶剤中に混合分散させて
液状組成物となし、これを透明電極２」二にスクリーン
印刷して乾燥させることにより形成した。そして、螢光
体層４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数が１，３万〜２９０万に設定しで
あることから、このポリマーは印刷に好適で、かつ螢光
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
ある。Further, the phosphor layer 4 of this EL is made of ZnS (Cu) or Z
A phosphor powder such as nS (Mn) and the dielectric polymer synthesized in the above example were mixed and dispersed in an organic solvent to form a liquid composition, and this was screen printed on a transparent electrode 2''. It was formed by drying. Since the number of molecules of polycyanoethyl acrylate, which is the matrix polymer of the phosphor layer 4, is set to 1,30,000 to 2,900,000, this polymer is suitable for printing, and the phosphor powder can be sufficiently absorbed. It binds and has good adhesion to the transparent electrode 2.
このようにして作製した１０種類のＥ Ｌ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。10 types of EL produced in this way and conventional EL
Table 6 shows the results of measuring the luminance half-life time (all conditions other than the type of polymer used in the phosphor layer were the same).
同表に明らかなように、螢光体層の７トリツクスボリマ
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 7-trix polymer in 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、誘電体層や一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、また、これを
薄膜コンデンサのポリマー誘電体に適用しても品質の向
上が図れる。Polycyanoethyl acrylate with controlled molecular weight can be expected to have similar effects when used as a matrix polymer for dielectric layers or single-layer light emitting layers, and it can also be used as a polymer dielectric for thin film capacitors to improve quality. can be improved.
以上説明したように、本発明は、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
を溶液重合によって合成し、重合条件を適宜選択するこ
とでその重量平均分子量を１万〜３５０万の範囲内に設
定するというものなので、極性の高い溶剤に溶けやすく
、かつ螢光体粉末や誘電体粉末等の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実用性の高い誘電体
ポリマーが得られ、これを厚膜ＥＬ素子の発光層や薄膜
コンデンサのポリマー誘電体などに適用すれば、その吸
湿性の低さを活かして寿命を大幅に延ばすことができる
。As explained above, the present invention synthesizes polycyanoethyl acrylate, which has the advantages of high dielectric constant and low hygroscopicity, by solution polymerization, and by appropriately selecting polymerization conditions, the weight average molecular weight can be increased from 10,000 to 3,500,000. Therefore, it is a highly practical dielectric polymer that is easily soluble in highly polar solvents and has sufficient binder function to bind inorganic powders such as phosphor powder and dielectric powder. If this is applied to the light-emitting layer of a thick-film EL device or the polymer dielectric of a thin-film capacitor, its low hygroscopicity can be utilized to greatly extend the lifespan.
第１図は本発明の実施例に係るポリマーを使用したＥＬ
の断面図である。
４・・・・・・螢光体層、５・・・・・・誘電体層、６
・・・・・・発光層。
手ん′己ネ［］ｊ−Ｉ土已書（自発）
平成 ３年 １月２２ＢFigure 1 shows an EL using a polymer according to an example of the present invention.
FIG. 4... Fluorescent layer, 5... Dielectric layer, 6
・・・・・・Light-emitting layer. Ten'ki Ne[]j-I Tobinsho (spontaneous) January 22B, 1991
Claims (2)
量を１万〜３５０万の範囲内に設定したことを特徴とす
る誘電体ポリマー。(1) A dielectric polymer characterized in that the weight average molecular weight of polycyanoethyl acrylate is set within the range of 10,000 to 3,500,000.
トの濃度が４０重量％以下で極性の高い溶剤を溶媒とす
る重合溶液を用い、これを４０℃以上に加熱してポリシ
アノエチルアクリレートを重合することを特徴とする誘
電体ポリマーの製造方法。(2) Polycyanoethyl acrylate is polymerized by using a polymerization solution in which the concentration of 2-cyanoethyl acrylate as a monomer is 40% by weight or less and a highly polar solvent, and heating the solution to 40°C or higher. A method for producing a dielectric polymer.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP32254490A JPH04196012A (en) | 1990-11-28 | 1990-11-28 | Dielectric substance polymer and its manufacture |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP32254490A JPH04196012A (en) | 1990-11-28 | 1990-11-28 | Dielectric substance polymer and its manufacture |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH04196012A true JPH04196012A (en) | 1992-07-15 |
Family
ID=18144857
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP32254490A Pending JPH04196012A (en) | 1990-11-28 | 1990-11-28 | Dielectric substance polymer and its manufacture |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH04196012A (en) |
-
1990
- 1990-11-28 JP JP32254490A patent/JPH04196012A/en active Pending
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