JPS6139890B2 - - Google Patents
Info
- Publication number
- JPS6139890B2 JPS6139890B2 JP52160443A JP16044377A JPS6139890B2 JP S6139890 B2 JPS6139890 B2 JP S6139890B2 JP 52160443 A JP52160443 A JP 52160443A JP 16044377 A JP16044377 A JP 16044377A JP S6139890 B2 JPS6139890 B2 JP S6139890B2
- Authority
- JP
- Japan
- Prior art keywords
- dope
- casting
- solvent
- methylene chloride
- film
- 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.)
- Expired
Links
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 78
- 238000005266 casting Methods 0.000 claims description 54
- 238000000034 method Methods 0.000 claims description 32
- 239000002904 solvent Substances 0.000 claims description 29
- 229920002284 Cellulose triacetate Polymers 0.000 claims description 23
- NNLVGZFZQQXQNW-ADJNRHBOSA-N [(2r,3r,4s,5r,6s)-4,5-diacetyloxy-3-[(2s,3r,4s,5r,6r)-3,4,5-triacetyloxy-6-(acetyloxymethyl)oxan-2-yl]oxy-6-[(2r,3r,4s,5r,6s)-4,5,6-triacetyloxy-2-(acetyloxymethyl)oxan-3-yl]oxyoxan-2-yl]methyl acetate Chemical compound O([C@@H]1O[C@@H]([C@H]([C@H](OC(C)=O)[C@H]1OC(C)=O)O[C@H]1[C@@H]([C@@H](OC(C)=O)[C@H](OC(C)=O)[C@@H](COC(C)=O)O1)OC(C)=O)COC(=O)C)[C@@H]1[C@@H](COC(C)=O)O[C@@H](OC(C)=O)[C@H](OC(C)=O)[C@H]1OC(C)=O NNLVGZFZQQXQNW-ADJNRHBOSA-N 0.000 claims description 23
- 239000012046 mixed solvent Substances 0.000 claims description 20
- 238000004519 manufacturing process Methods 0.000 claims description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 60
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 27
- 239000000203 mixture Substances 0.000 description 18
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 11
- 238000010438 heat treatment Methods 0.000 description 10
- 229910001220 stainless steel Inorganic materials 0.000 description 8
- 239000010935 stainless steel Substances 0.000 description 8
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 7
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 6
- 230000021736 acetylation Effects 0.000 description 6
- 238000006640 acetylation reaction Methods 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- 239000004014 plasticizer Substances 0.000 description 5
- 230000007423 decrease Effects 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- XZZNDPSIHUTMOC-UHFFFAOYSA-N triphenyl phosphate Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)(=O)OC1=CC=CC=C1 XZZNDPSIHUTMOC-UHFFFAOYSA-N 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 238000007664 blowing Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 2
- NIQCNGHVCWTJSM-UHFFFAOYSA-N Dimethyl phthalate Chemical compound COC(=O)C1=CC=CC=C1C(=O)OC NIQCNGHVCWTJSM-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 229920002301 cellulose acetate Polymers 0.000 description 2
- FLKPEMZONWLCSK-UHFFFAOYSA-N diethyl phthalate Chemical compound CCOC(=O)C1=CC=CC=C1C(=O)OCC FLKPEMZONWLCSK-UHFFFAOYSA-N 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- LPSFUJXLYNJWPX-UHFFFAOYSA-N 1,1'-biphenyl;diphenyl hydrogen phosphate Chemical compound C1=CC=CC=C1C1=CC=CC=C1.C=1C=CC=CC=1OP(=O)(O)OC1=CC=CC=C1 LPSFUJXLYNJWPX-UHFFFAOYSA-N 0.000 description 1
- PZBLUWVMZMXIKZ-UHFFFAOYSA-N 2-o-(2-ethoxy-2-oxoethyl) 1-o-ethyl benzene-1,2-dicarboxylate Chemical compound CCOC(=O)COC(=O)C1=CC=CC=C1C(=O)OCC PZBLUWVMZMXIKZ-UHFFFAOYSA-N 0.000 description 1
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 1
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 1
- YSMRWXYRXBRSND-UHFFFAOYSA-N TOTP Chemical compound CC1=CC=CC=C1OP(=O)(OC=1C(=CC=CC=1)C)OC1=CC=CC=C1C YSMRWXYRXBRSND-UHFFFAOYSA-N 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- HSUIVCLOAAJSRE-UHFFFAOYSA-N bis(2-methoxyethyl) benzene-1,2-dicarboxylate Chemical compound COCCOC(=O)C1=CC=CC=C1C(=O)OCCOC HSUIVCLOAAJSRE-UHFFFAOYSA-N 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- FHHZOYXKOICLGH-UHFFFAOYSA-N dichloromethane;ethanol Chemical compound CCO.ClCCl FHHZOYXKOICLGH-UHFFFAOYSA-N 0.000 description 1
- FBSAITBEAPNWJG-UHFFFAOYSA-N dimethyl phthalate Natural products CC(=O)OC1=CC=CC=C1OC(C)=O FBSAITBEAPNWJG-UHFFFAOYSA-N 0.000 description 1
- 229960001826 dimethylphthalate Drugs 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 150000003014 phosphoric acid esters Chemical class 0.000 description 1
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical class OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- DQWPFSLDHJDLRL-UHFFFAOYSA-N triethyl phosphate Chemical compound CCOP(=O)(OCC)OCC DQWPFSLDHJDLRL-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
- B29C48/07—Flat, e.g. panels
- B29C48/08—Flat, e.g. panels flexible, e.g. films
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/88—Thermal treatment of the stream of extruded material, e.g. cooling
- B29C48/91—Heating, e.g. for cross linking
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/88—Thermal treatment of the stream of extruded material, e.g. cooling
- B29C48/911—Cooling
- B29C48/9135—Cooling of flat articles, e.g. using specially adapted supporting means
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29D—PRODUCING PARTICULAR ARTICLES FROM PLASTICS OR FROM SUBSTANCES IN A PLASTIC STATE
- B29D7/00—Producing flat articles, e.g. films or sheets
- B29D7/01—Films or sheets
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2301/00—Characterised by the use of cellulose, modified cellulose or cellulose derivatives
- C08J2301/08—Cellulose derivatives
- C08J2301/10—Esters of organic acids
- C08J2301/12—Cellulose acetate
Description
本発明は、溶液流延法によるセルローストリア
セテートフイルムの製造方法に関する。さらに詳
しくは、セルローストリアセテートフイルムの強
さ、とくに引裂強さを増大させる方法に関する。
セルローストリアセテートフイルムは、写真用
フイルムベースとして広く利用されている。その
製造には、溶液流延法を一般に使用しており、そ
の方法は、メチレンクロライドを主溶媒とし若干
のメタノールまたはエタノールを加えた混合溶媒
に酢化度60〜62％のセルローストリアセテートお
よび可塑剤を溶解して得たドープを連続的に回転
する無端支持体上にホツパーから均一に流延し、
その支持体上で溶媒を蒸発し、ドープが固化した
後に支持体から剥離し、さらに乾燥を行なつてフ
イルムを得るものである。
近年、セルローストリアセテートドープ中にメ
チレンクロライドの他に非溶媒たとえば、メタノ
ールとシクロヘキサン、エタノールとｎ―フタノ
ールあるいは多量のメタノールまたはエタノール
を加えることによつて、フイルムの製造速度を上
げる方法がとられている。しかし、これらのドー
プでつくつたフイルムは、その強さたとえば引裂
強さがメチレンクロライドと若干のアルコールを
用いた従来のドープでつくつたフイルムより劣つ
ているためこれを改良する試みがなされている。
たとえば、支持体から剥離した後に収縮させつつ
乾燥させることによつてフイルムの強さを改良す
る方法が提案されているけれどもフイルムの強さ
を増すにはこの方法では不充分である。
そこで、本発明者らは、メチレンクロライドの
他に非溶媒を加えたドープでつくつたフイルムを
従来のドープでつくつたフイルムよりも強くする
方法を鋭意研究した結果、かかる非溶媒を加えた
ドープをバンド表面に流延し、流延後３分以内に
このドープ流延層を30〜42℃の温度範囲となるよ
うに加熱し、かつ少なくとも15秒間該ドープ流延
層を該温度範囲に保つことにより従来ドープでつ
くつたフイルムより強いフイルムを得ることを見
い出した。
しかし、流延３分以後からではドープ流延層を
30〜42℃の温度に、あるいは42℃以上の温度に加
熱してもフイルムの強さの向上は見られず、また
流延３分以内でも、ドープ流延層を30〜42℃の温
度に保つ時間が15秒に満たなければ、できたフイ
ルムの強さの増大は見られなかつた。
なお、加熱温度の下限が30℃なのはドープ流延
層を30℃以上に加熱しなければ、いくら保温時間
を長くしてもできたフイルムは、強さの増大が見
られないためである。また、加熱温度の上限が42
℃なのは、種々の方法で流延層の温度を測定した
ところ、流延層の一部が42℃以上になれば流延層
内で発泡することがあり、このようなフイルムは
製品として使用できないためである。
さらに、本発明の方法を用いれば剥離後に収縮
させなくてもフイルムの強さは増大するが、収縮
させれば強さはさらに増大することを見出した。
しかし、本発明の方法を用いなければ剥離後に収
縮させてもフイルムの強さは増大せず逆に低下し
てしまう。
なお、本発明は、ドープ流延層を30〜42℃の温
度に保つので、バンド上での溶媒の蒸発を促進
し、それだけ早くバンド上から剥離でき、フイル
ムの製造速度の上昇にも寄与している。これに対
し従来のバンド製膜機での加熱は、ドープ流延層
への熱供給が充分でなく、流延後３分以内にドー
プ流延層を30〜42℃の温度範囲に少くとも15秒間
保つていなかつた。したがつて、本発明の前述し
た効果は得られなかつた。
次に、本発明のセルローストリアセテートフイ
ルムの製造方法において効果のあるドープはドー
プの混合溶媒としてメチレンクロライドおよびセ
ルローストリアセテートの非溶媒からなる混合溶
媒を用い、かつ該混合溶媒中には該非溶媒を７〜
30重量％含有するものである。
セルローストリアセテートの非溶媒としては、
たとえば炭素原子数１〜８のアルコール、メチル
エチルケトン、メチルイソブチルケトン、酢酸エ
チル、酢酸ブロヒル、モノクロルベンゼン、ベン
ゼン、シクロヘキサン、テトラヒドロフラン、メ
チルセロソルブ、エチレングリコールモノメチル
エーテル等をあげることができ、これらの非溶媒
は、単独もしくは２種以上を適宜組合せて用いる
ことができる。
次に代表的なドープの溶媒組成を示すが、本発
明に使用するドープ溶媒は、これに限定されるも
のではない。
(1) メチレンクロライド（70〜88）
＋メタノール（12〜30）
(2) メチレンクロライド（70〜88）
＋エタノール（12〜30）
(3) メチレンクロライド（77〜91）
＋（メタノール＋プロハノール）（９〜
23）
(4) メチレンクロライド（77〜91）
＋（エタノール＋プロパノール）（９〜
23）
(5) メチレンクロライド（80〜93）
＋（メタノール＋ブタノール）（７〜
20）
(6) メチレンクロライド（80〜93）
＋（エタノール＋ブタノール）（７〜
20）
(7) メチレンクロライド（82〜92）
＋（メタノール＋シクロヘキサン）（８
〜18）
(8) メチレンクロライド（82〜92）
＋（エタノール＋シクロヘキサン）（８
〜18）
なお、括弧内の数字は重量％を示す。また２種
以上の非溶媒を組合せて用いる場合にはその組合
せ量比は任意である。
そして本発明におけるドープ濃度は、ドープの
混合溶媒１に対してセルローストリアセテート
が0.10〜0.40Kgであるのが好ましいセルロースト
リアセテートが0.15〜0.40Kgであればドープを流
延してから剥離するまでの時間の短縮にも寄与
し、さらに好ましい。
また、本発明においてはドープ溶媒として前記
の如きメチレンクロライドとセルロースアセテー
トの非溶媒からなる混合溶媒を用いるが、本発明
の効果を損なわない範囲内でその他の溶媒をごく
少量混合して用いることは本発明に包含される。
さらに、本発明におけるドープ流延層の加熱に
は任意の手段を用いることができるが、代表的な
ものとしては次の如き方法をあげることができ
る。すなわち、
ドープ流延層の加熱方法の第１は、バンド裏面
に加熱液体たとえば温水を接触させる方法であ
る。ドラム式の製膜機には、ドラムの内側に液体
の層を設け、この液体の層をさらに内側から加熱
することによりドープ流延層に均一に熱を伝える
方法がある。しかし、ドラムは非常に高価で、か
つ高精度を必要とし工業的に使用するのは難し
い。これに対してバンド式の製膜機は、外部から
液体の給排を行なうことによりバンド裏面に直接
液体を接触させることが可能で、効率良く簡単
に、しかも均一にドープ流延層に熱伝達すること
が可能で、また設備的に安価である。
ドープ流延層の加熱方法の第２は、バンド裏面
に熱風を吹きつける方法である。熱風は加熱液体
を用いた場合よりも熱伝達効率は良くないが、ド
ープ流延層を30〜42℃の温度に保つことは可能で
しかも装置も簡便である。
ドープ流延層の加熱方法の第３は、流延層表面
に熱風を吹きつける方法である。この方法は、バ
ンド裏面から熱風を吹きつける場合よりも直接的
で熱伝達も効率が良い。
ドープ流延層の加熱は、これら３種類の加熱方
法を適宜組み合わせても良く、そしてバンド上で
これら３種類の加熱方法を適宜組み合わせて用い
ることは単一の加熱方法よりもさらに実用上有効
である。
なお、セルローストリアセテートフイルムには
耐湿性あるいは柔軟性を与える目的で可塑剤を添
加するのが一般的であるが、本発明に使用できる
可塑剤としては、リン酸エステル系では、トリフ
エニルフオスフエート、トリクレジルフオスフエ
ート、トリエチルフオスフエート、ビフエニルジ
フエニルフオスフエート等、フタル酸エステル系
では、ジメチルフタレート、ジエチルフタレー
ト、ジメトキシエチルフタレート等、グリコール
酸エステル系では、メチルフタリルエチルグリコ
レート、エチルフタリルエチルグリコレート等を
単独あるいは併用して用いることができる。ま
た、可塑剤は、セルロースアセテートに対して５
〜30重量％の範囲で使用可能であるけれども、過
剰に用いると乾燥時に可塑剤がフイルムから浸み
出す現象があるので、５〜20重量％を用いるのが
好ましい。
次に本発明の実施例を示す。実施例中の組成は
すべて重量部で示す。
実施例 (1)
酢化度61.4％のセルローストリアセテート100
部とトリフエニルフオスフエート15部を、組成比
を変えたメチレンクロライド、メタノールからな
る混合溶媒550部に溶解し、それぞれドープを得
た。この時、混合溶媒中のメタノールの含有比率
が大きいものはメタノールを２分割し、まずメチ
レンクロライドとメタノールが重量比で９：１か
らなる混合溶媒中にセルローストリアセテートを
溶解し、その後残りのメタノールを加えドープを
得た。
次に、このドープを過後、ステンレス板上に
均一に流延して得たドープ流延層の表面に風速10
m/sの熱風を吹きつけて、混合溶媒組成を違えた
場合、ドープ流延層の保温温度を違えた場合およ
びドープ流延層の保温時期を越えた場合について
のフイルムをそれぞれ0.14mmの厚さで10種類作成
した。これらのフイルムのエレメンドルフ式引裂
試験での測定による引裂強さは、表１、表２、表
３に示す通りである。
この結果、メタノールが12重量％より多い溶媒
組成は、本発明の方法を用いないと引裂強さは低
下するけれども、本発明の方法を用いることによ
りフイルムの引裂強さを増大することができた。
(イ) 表１に示すように溶媒組成の違うドープを流
延して得たドープ流延層を流延直後から１分間
20℃に保温した。
The present invention relates to a method for producing cellulose triacetate film using a solution casting method. More particularly, the present invention relates to a method for increasing the strength, particularly the tear strength, of cellulose triacetate films. Cellulose triacetate film is widely used as a photographic film base. For its production, a solution casting method is generally used, which involves adding cellulose triacetate with an acetylation degree of 60 to 62% and a plasticizer to a mixed solvent of methylene chloride as the main solvent and some methanol or ethanol. The dope obtained by melting is uniformly cast from a hopper onto a continuously rotating endless support.
The solvent is evaporated on the support, and after the dope is solidified, it is peeled off from the support and further dried to obtain a film. In recent years, methods have been taken to increase the production rate of films by adding non-solvents such as methanol and cyclohexane, ethanol and n-phthanol, or large amounts of methanol or ethanol in addition to methylene chloride to the cellulose triacetate dope. . However, films made with these dopes are inferior in strength, such as tear strength, to films made with conventional dopes using methylene chloride and some alcohol, and attempts have been made to improve this.
For example, a method has been proposed in which the strength of the film is improved by shrinking and drying the film after peeling it off from the support, but this method is insufficient to increase the strength of the film. Therefore, the present inventors conducted extensive research into a method to make a film made with a dope containing a non-solvent in addition to methylene chloride stronger than a film made with a conventional dope. Cast the dope onto the band surface, heat the dope cast layer to a temperature range of 30 to 42°C within 3 minutes after casting, and maintain the dope cast layer within the temperature range for at least 15 seconds. It was discovered that a film stronger than that made using conventional doping can be obtained by using this method. However, after 3 minutes of casting, the dope casting layer
No improvement in the strength of the film was observed even when heated to a temperature of 30 to 42 °C or above 42 °C, and even within 3 minutes of casting, the dope cast layer was heated to a temperature of 30 to 42 °C. If the holding time was less than 15 seconds, no increase in the strength of the resulting film was observed. Note that the lower limit of the heating temperature is 30°C because unless the dope cast layer is heated to 30°C or higher, the strength of the resulting film will not increase no matter how long the heat retention time is. Also, the upper limit of heating temperature is 42
℃ The temperature of the cast layer was measured using various methods, and it was found that if a part of the cast layer reached 42℃ or higher, foaming could occur within the cast layer, and such a film could not be used as a product. It's for a reason. Furthermore, it has been found that by using the method of the present invention, the strength of the film can be increased even without shrinkage after peeling, but that the strength can be further increased if the film is shrunk.
However, if the method of the present invention is not used, the strength of the film will not increase but will decrease even if it is shrunk after peeling. In addition, in the present invention, since the dope casting layer is kept at a temperature of 30 to 42°C, the evaporation of the solvent on the band is promoted, and the layer can be peeled off from the band more quickly, which also contributes to increasing the production speed of the film. ing. On the other hand, heating in conventional band film forming machines does not provide enough heat to the dope casting layer, and the dope casting layer is heated to a temperature range of 30 to 42℃ within 3 minutes after casting at least 15℃. I couldn't keep it for seconds. Therefore, the above-mentioned effects of the present invention could not be obtained. Next, the dope that is effective in the method for producing a cellulose triacetate film of the present invention uses a mixed solvent of methylene chloride and a non-solvent of cellulose triacetate as a mixed solvent of the dope, and the mixed solvent contains 7 to 70% of the non-solvent.
It contains 30% by weight. As a non-solvent for cellulose triacetate,
Examples include alcohols having 1 to 8 carbon atoms, methyl ethyl ketone, methyl isobutyl ketone, ethyl acetate, brohylacetate, monochlorobenzene, benzene, cyclohexane, tetrahydrofuran, methyl cellosolve, ethylene glycol monomethyl ether, etc., and these nonsolvents , can be used alone or in an appropriate combination of two or more. Next, typical dope solvent compositions are shown, but the dope solvent used in the present invention is not limited thereto. (1) Methylene chloride (70-88) + methanol (12-30) (2) Methylene chloride (70-88) + ethanol (12-30) (3) Methylene chloride (77-91) + (methanol + prohanol) (9～
23) (4) Methylene chloride (77-91) + (ethanol + propanol) (9-
23) (5) Methylene chloride (80~93) + (methanol + butanol) (7~
20) (6) Methylene chloride (80-93) + (ethanol + butanol) (7-
20) (7) Methylene chloride (82-92) + (methanol + cyclohexane) (8
~18) (8) Methylene chloride (82~92) + (ethanol + cyclohexane) (8
~18) The numbers in parentheses indicate weight %. Further, when two or more types of nonsolvents are used in combination, the ratio of the amounts of the combination is arbitrary. In the present invention, the dope concentration is preferably 0.10 to 0.40 kg of cellulose triacetate per 1 part of the dope mixed solvent, and if the cellulose triacetate is 0.15 to 0.40 kg, the time required from casting the dope to peeling it off is It also contributes to shortening of , which is more preferable. Further, in the present invention, a mixed solvent consisting of a non-solvent of methylene chloride and cellulose acetate as described above is used as the dope solvent, but it is possible to mix a very small amount of other solvents within the range that does not impair the effects of the present invention. Included in the present invention. Furthermore, any means can be used to heat the dope cast layer in the present invention, but the following methods can be cited as typical ones. That is, the first method of heating the dope casting layer is to bring a heating liquid, such as hot water, into contact with the back surface of the band. In drum-type film forming machines, there is a method in which a liquid layer is provided inside the drum, and this liquid layer is further heated from the inside to uniformly transfer heat to the dope casting layer. However, drums are very expensive and require high precision, making them difficult to use industrially. On the other hand, a band-type film forming machine allows the liquid to be brought into direct contact with the back side of the band by supplying and discharging the liquid from the outside, thereby efficiently, easily, and evenly transferring heat to the dope casting layer. It is possible to do this, and the equipment is inexpensive. The second heating method for the dope casting layer is to blow hot air onto the back surface of the band. Although the heat transfer efficiency of hot air is not as good as that of heated liquid, it is possible to maintain the dope casting layer at a temperature of 30 to 42°C, and the equipment is simple. The third heating method for the dope casting layer is a method of blowing hot air onto the surface of the casting layer. This method is more direct and more efficient in heat transfer than blowing hot air from the back of the band. The dope casting layer may be heated by appropriately combining these three types of heating methods, and using an appropriate combination of these three types of heating methods on the band is more practically effective than using a single heating method. be. Generally, a plasticizer is added to cellulose triacetate film for the purpose of imparting moisture resistance or flexibility, but the plasticizers that can be used in the present invention include triphenyl phosphate in the case of phosphate esters. , tricresyl phosphate, triethyl phosphate, biphenyl diphenyl phosphate, etc. Phthalate esters include dimethyl phthalate, diethyl phthalate, dimethoxyethyl phthalate, etc. Glycolic esters include methyl phthalyl ethyl glyco ester, ethyl phthalyl ethyl glycolate, etc. can be used alone or in combination. In addition, the plasticizer is 5% for cellulose acetate.
Although it can be used in a range of 30% by weight, it is preferable to use 5 to 20% by weight because if it is used in excess, the plasticizer will ooze out from the film during drying. Next, examples of the present invention will be shown. All compositions in the examples are given in parts by weight. Example (1) Cellulose triacetate 100 with acetylation degree of 61.4%
and 15 parts of triphenyl phosphate were dissolved in 550 parts of a mixed solvent consisting of methylene chloride and methanol with different composition ratios to obtain dopes. At this time, if the methanol content ratio in the mixed solvent is high, divide the methanol into two parts, first dissolve cellulose triacetate in a mixed solvent consisting of methylene chloride and methanol in a weight ratio of 9:1, and then dissolve the remaining methanol. Got added dope. Next, after passing this dope, the surface of the dope cast layer obtained by uniformly casting the dope on a stainless steel plate was coated with a wind speed of 10
By blowing hot air at a speed of m/s, films with a thickness of 0.14 mm were obtained for different mixed solvent compositions, different heat retention temperatures of the dope cast layer, and cases where the heat retention period of the dope cast layer was exceeded. I created 10 types. The tear strengths of these films as measured by the Elmendorf tear test are shown in Tables 1, 2, and 3. As a result, the tear strength of a film containing more than 12% by weight of methanol would decrease if the method of the present invention was not used, but the tear strength of the film could be increased by using the method of the present invention. . (b) As shown in Table 1, the dope cast layer obtained by casting dopes with different solvent compositions was cast for 1 minute immediately after casting.
The temperature was kept at 20℃.
【表】
(ロ) ドープ溶媒がメチレンクロライド407部（74
重量％）メタノール143部（26重量％）からな
るドープを流延して得たドープ流延層を流延直
後から１分間表２に示した温度に保温した。[Table] (b) Dope solvent is 407 parts of methylene chloride (74 parts
Immediately after casting, a dope cast layer obtained by casting a dope consisting of 143 parts (26 weight %) of methanol was kept at the temperature shown in Table 2 for 1 minute.
【表】
(ハ) 表２と同じドープを流延して得たドープ流延
層を表３に示した保温時期に40℃に保温した。[Table] (c) A dope cast layer obtained by casting the same dope as in Table 2 was kept at 40°C during the heat retention period shown in Table 3.
【表】
実施例 (2)
酢化度61.8％のセルローストリアセテート100
部とトリフエニルフオスフエート15部を組成比を
変えたメチレンクロライドエタノールからなる混
合溶媒650部に実施例(1)と同様に溶解させ、ドー
プを得た。
次にこのドープをろ過してステンレス板上に均
一に流延した後、ステンレス板の裏面に直接温水
を接触させて混合溶媒組成を違えた場合、ドープ
流延層の保温温度を違えた場合およびドープ流延
層の保温期間を違えた場合についてのフイルムを
それぞれ0.14mmの厚さで10種類作成した。これら
のフイルムの引裂強さは、表４，表５，表６に示
す通りである。
この結果、エタノールが12重量％より多い溶媒
組成のものは、本発明の方法を用いないと引裂強
さは低下するけれども、本発明の方法を用いるこ
とにより引裂強さを増大することができた。
(イ) 表４に示すように溶媒組成の違うドープを流
延して得たドープ流延層を流延２分後から１分
間27℃に保温した。[Table] Example (2) Cellulose triacetate 100 with acetylation degree of 61.8%
In the same manner as in Example (1), 15 parts of triphenyl phosphate and 15 parts of triphenyl phosphate were dissolved in 650 parts of a mixed solvent of methylene chloride ethanol with different composition ratios to obtain a dope. Next, after filtering this dope and uniformly casting it on a stainless steel plate, hot water was brought into direct contact with the back side of the stainless steel plate to change the composition of the mixed solvent, or to change the heat retention temperature of the dope casting layer. Ten types of films with a thickness of 0.14 mm were prepared for different heat retention periods of the dope casting layer. The tear strengths of these films are shown in Tables 4, 5, and 6. As a result, for solvent compositions containing more than 12% ethanol by weight, the tear strength would decrease if the method of the present invention was not used, but the tear strength could be increased by using the method of the present invention. . (a) As shown in Table 4, dope cast layers obtained by casting dopes with different solvent compositions were kept at 27° C. for 1 minute from 2 minutes after casting.
【表】
(ロ) ドープ溶媒がメチレンクロライド546部（84
重量％）エタノール104部（16重量％）からな
るドープを流延して得たドープ流延層を流延２
分後から１分間表５に示した温度に保温した。[Table] (b) Dope solvent is 546 parts of methylene chloride (84 parts
A dope-casting layer obtained by casting a dope consisting of 104 parts (16% by weight) of ethanol (weight%) was cast in a dope-casting layer 2.
After 1 minute, the temperature was maintained at the temperature shown in Table 5 for 1 minute.
【表】
(ハ) 表５と同じドープを流延して得たドープ流延
層を表６に示した保温時期に42℃に保温した。[Table] (c) A dope cast layer obtained by casting the same dope as in Table 5 was kept at 42°C during the heat retention period shown in Table 6.
【表】
実施例 (3)
酢化度60.4％のセルローストリアセテート100
部とトリフエニルフオスフエート15部を組成比を
変えたメチレンクロライド、メタノール、イソプ
ロパノールからなる混合溶媒450部のうち、ま
ず、メチレンクロライド、メタノールの混合溶媒
中にセルローストリアセテートを溶解し、その後
イソプロパノールを加えドープを得た。
次に、このドープをろ過後、ステンレス板上に
均一に流延して得たドープ流延層表面に風速10
m/sの熱風を吹きつけ、さらにステンレス板の裏
面には直接温水を接触させて、混合溶媒組成を違
えた場合、ドープ流延層の保温温度を越えた場
合、およびドープ流延層の保温時期を違えた場合
についてのフイルムをそれぞれ0.14mmの厚さで９
種類作成した。これらのフイルムの引裂強さは、
表７、表８、表９に示す通りである。
この結果、メタノールとイソプロパノールが一
緒で９重量％より多い溶媒組成のものは、本発明
の方法を用いないと引裂強さは低下するけれど
も、本発明の方法を用いることにより引裂強さを
増大することができた。
(イ) 表７に示すように溶媒組成の違うドープを流
延して得たドープ流延層を、流延30秒後から２
分間25℃に保温した。[Table] Example (3) Cellulose triacetate 100 with acetylation degree of 60.4%
First, cellulose triacetate was dissolved in the mixed solvent of methylene chloride and methanol, and then the isopropanol was dissolved. Got added dope. Next, after filtering this dope, the dope was uniformly cast on a stainless steel plate.
m/s of hot air is blown, and the back side of the stainless steel plate is brought into direct contact with hot water. 9 films each with a thickness of 0.14 mm for different times.
Created a type. The tear strength of these films is
As shown in Table 7, Table 8, and Table 9. As a result, solvent compositions containing more than 9% by weight of methanol and isopropanol together exhibit increased tear strength by using the method of the present invention, although tear strength decreases when the method of the present invention is not used. I was able to do that. (b) As shown in Table 7, the dope cast layer obtained by casting dopes with different solvent compositions was
The temperature was kept at 25°C for minutes.
【表】
(ロ) ドープ溶媒がメチレンクロライド369部（82
重量％）メタノール18部（４重量％）イソプロ
パノール63部（14重量％）からなるドープを流
延して得たドープ流延層を流延30秒後から２分
間表８に示した温度に保温した。[Table] (b) Dope solvent is 369 parts of methylene chloride (82 parts
After 30 seconds of casting, the dope cast layer obtained by casting a dope consisting of 18 parts (4 weight %) of methanol and 63 parts (14 weight %) of isopropanol was kept at the temperature shown in Table 8 for 2 minutes after casting. did.
【表】
(ハ) 表８と同じドープを流延して得たドープ流延
層を表９に示した保温時期に33℃に保温した。[Table] (c) A dope cast layer obtained by casting the same dope as in Table 8 was kept at 33°C during the heat retention period shown in Table 9.
【表】
実施例 ４
酢化度61.4％のセルローストリアセテート100
部とトリフエニルフオスフエート15部を組成比を
変えたメチレンクロライド、エタノール、ｎ―ブ
タノールからなる混合溶媒600部のうち、まず、
メチレンクロライド、エタノールの混合溶媒中に
セルローストリアセテートを溶解し、その後ｎ―
ブタノールを加えドープを得た。
次に、このドープをろ過してスチレン板上に均
一に流延した後、ステンレス板裏面に風速10m/s
の熱風を吹きつけて、混合溶媒の組成を違えた場
合、ドープの保温温度を違えた場合およびドープ
流延層の保温時期を違えた場合についてのフイル
ムをそれぞれ0.14mmの厚さで９種類作成した。こ
れらのフイルムの引裂強さは、表10、表11、表12
に示す通りである。
この結果、エタノールとｎ―ブタノールが一緒
で７重量％より多い溶媒組成のものは、本発明の
方法を用いないと引裂強さは低下するけれども、
本発明の方法を用いることにより引裂強さを増大
することができた。
(イ) 表10に示すように溶媒組成の違うドープを流
延して得たドープ流延層を、流延後保温しなか
つた。[Table] Example 4 Cellulose triacetate 100 with acetylation degree of 61.4%
First, out of 600 parts of a mixed solvent consisting of methylene chloride, ethanol, and n-butanol with different composition ratios,
Cellulose triacetate was dissolved in a mixed solvent of methylene chloride and ethanol, and then n-
Butanol was added to obtain a dope. Next, after filtering this dope and uniformly casting it on a styrene plate, the back side of the stainless steel plate was coated with air at a speed of 10 m/s.
Nine types of films were created with a thickness of 0.14 mm each for different compositions of mixed solvents, different dope insulating temperatures, and different dope insulating times. did. The tear strength of these films is shown in Table 10, Table 11, and Table 12.
As shown. As a result, although solvent compositions containing more than 7% by weight of ethanol and n-butanol together will have lower tear strength if the method of the present invention is not used,
By using the method of the invention it was possible to increase the tear strength. (a) As shown in Table 10, dope cast layers obtained by casting dopes with different solvent compositions were not kept warm after casting.
【表】
(ロ) ドープ溶媒がメチレンクロライド528部（88
重量％）エタノール24部（４重量％）ｎ―ブタ
ノール48部（８重量％）からなるドープを流延
して得たドープ流延層を、流延１分後から２分
間表11に示した温度に保温した。[Table] (b) The dope solvent is 528 parts of methylene chloride (88 parts
Table 11 shows the dope cast layer obtained by casting a dope consisting of 24 parts (4 wt%) ethanol and 48 parts (8 wt%) n-butanol for 2 minutes starting from 1 minute after casting. kept at temperature.
【表】
(ハ) 表11と同じドープを流延して得たドープ流延
層を表12に示した保温時期に41℃に保温した。[Table] (c) A dope cast layer obtained by casting the same dope as in Table 11 was kept at 41°C during the heat retention period shown in Table 12.
【表】
実施例 ５
酢化度60.4％のセルローストリアセテート100
部とトリフエニルフオスフエート15部を組成比を
変えたメチレンクロライド、メタノール、シクロ
ヘキサンからなる混合溶媒620部のうち、まずメ
チレンクロライド、メタノールの混合溶媒中にセ
ルローストリアセテートを溶解し、その後シクロ
ヘキサンを加えたドープを得た。
次に、このドープをろ過後、ステンレス板上に
均一に流延して得たドープ流延層表面およびステ
ンレス板裏面に風速10m/sの熱風を吹きつけて、
混合溶媒組成を違えた場合、ドープ流延層の保温
時期を違えた場合についてのフイルムをそれぞれ
0.14mmの厚さで９種類作成した。これらのフイル
ムの引裂強さは表13，表14，表15に示す通りであ
る。
この結果、メタノールとシクロヘキサンが一緒
で８重量％より多い溶媒組成のものは、方発明の
方法を用いないと引裂強さは、低下するけれども
本発明の方法を用いることにより引裂強さを増大
することができた。
(イ) 表13に示すように溶媒組成の違うドープを流
延して得たドープ流延層を、流延30秒後から１
分間25℃に保温した。[Table] Example 5 Cellulose triacetate 100 with acetylation degree of 60.4%
First, cellulose triacetate was dissolved in a mixed solvent of methylene chloride and methanol, and then cyclohexane was added. Got some dope. Next, after filtering this dope, hot air at a wind speed of 10 m/s was blown onto the surface of the dope cast layer obtained by uniformly casting it on a stainless steel plate and the back surface of the stainless steel plate.
Films with different mixed solvent compositions and with different heat retention times for the dope casting layer are shown.
Nine types were created with a thickness of 0.14 mm. The tear strengths of these films are shown in Tables 13, 14, and 15. As a result, for solvent compositions containing more than 8% by weight of methanol and cyclohexane together, the tear strength is increased by using the method of the present invention, although the tear strength is decreased if the method of the present invention is not used. I was able to do that. (b) As shown in Table 13, the dope cast layer obtained by casting dopes with different solvent compositions was
The temperature was kept at 25°C for minutes.
【表】
(ロ) ドープ溶媒がメチレンクロライド558部（90
重量％）メタノール31部（５重量％）シクロヘ
キサン31部（５重量％）からなるドープを流延
して得たドープ流延層を、流延30秒後から１分
間表14に示した温度に保温した。[Table] (b) Dope solvent is 558 parts of methylene chloride (90 parts
After 30 seconds of casting, the dope cast layer obtained by casting a dope consisting of 31 parts (5 weight%) of methanol and 31 parts (5 weight%) of cyclohexane was heated to the temperature shown in Table 14 for 1 minute after the casting. I kept it warm.
【表】
(ハ) 表14と同じドープを流延して得たドープ流延
層を表15に示した保温時期に40℃に保温した。[Table] (c) A dope cast layer obtained by casting the same dope as in Table 14 was kept at 40°C during the heat retention period shown in Table 15.
Claims (1)
フイルムの製造方法において、ドープの混合溶媒
としてセルローストリアセテートの非溶媒および
メチレンクロライドを用い、かつ該混合溶媒中に
該非溶媒を７〜30重量％含有したドープをバンド
表面に流延してドープ流延層となし、流延後３分
以内に該ドープ流延層を30〜42℃の温度範囲とな
るように加熱し、かつ少なくとも15秒間該ドープ
流延層を該温度範囲に保つことを特徴とするセル
ローストリアセテートフイルムの製造方法。1. In a method for producing a cellulose triacetate film by a solution casting method, a non-solvent of cellulose triacetate and methylene chloride are used as a mixed solvent of the dope, and a dope containing 7 to 30% by weight of the non-solvent in the mixed solvent is applied to the band surface. Within 3 minutes after casting, the dope cast layer is heated to a temperature range of 30 to 42°C, and the dope cast layer is heated for at least 15 seconds to form a dope cast layer. A method for producing a cellulose triacetate film characterized by maintaining the film within a temperature range.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP16044377A JPS5514201A (en) | 1977-12-28 | 1977-12-28 | Method of manufacturing cellulose triacetate film |
| GB7850087A GB2013559B (en) | 1977-12-28 | 1978-12-28 | Process for preparing cellulose triacetate films |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP16044377A JPS5514201A (en) | 1977-12-28 | 1977-12-28 | Method of manufacturing cellulose triacetate film |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5514201A JPS5514201A (en) | 1980-01-31 |
| JPS6139890B2 true JPS6139890B2 (en) | 1986-09-06 |
Family
ID=15715032
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP16044377A Granted JPS5514201A (en) | 1977-12-28 | 1977-12-28 | Method of manufacturing cellulose triacetate film |
Country Status (2)
| Country | Link |
|---|---|
| JP (1) | JPS5514201A (en) |
| GB (1) | GB2013559B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0708135A1 (en) | 1994-10-20 | 1996-04-24 | Fuji Photo Film Co., Ltd. | Cellulose triacetate film and process for producing the same |
Families Citing this family (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS58156612A (en) * | 1982-03-12 | 1983-09-17 | ギユンタ−・フエルスタ− | Guide limitting apparatus for running road |
| JPS59185628A (en) * | 1983-04-06 | 1984-10-22 | Agency Of Ind Science & Technol | Film manufacturing device |
| JPS60162105U (en) * | 1985-03-20 | 1985-10-28 | 草竹 杉晃 | Piece stop block |
| US4631157A (en) * | 1985-09-16 | 1986-12-23 | Bend Research, Inc. | Production of permeable cellulose triacetate membranes |
| JP2559073B2 (en) * | 1990-04-19 | 1996-11-27 | 富士写真フイルム株式会社 | Method for producing cellulose triacetate film |
| JP2597235B2 (en) * | 1990-11-30 | 1997-04-02 | 富士写真フイルム株式会社 | Casting method for optical film |
| US5494114A (en) * | 1993-01-06 | 1996-02-27 | Globe Fire Sprinkler Corporation | Fire extinguisher sprinkler construction |
| EP0647671B1 (en) * | 1993-10-08 | 1998-07-15 | Teijin Limited | Method of producing an acylated cellulose film |
| US5695694A (en) * | 1993-10-08 | 1997-12-09 | Teijin Limited | Method of producing an acylated cellulose film |
| US5529737A (en) * | 1994-09-16 | 1996-06-25 | Eastman Kodak Company | Process for making cellulose triacetate photographic film base |
| US6599458B1 (en) | 1994-10-20 | 2003-07-29 | Fuji Photo Film Co., Ltd. | Cellulose triacetate film and process for producing the same |
| JPH106351A (en) * | 1996-06-26 | 1998-01-13 | Konica Corp | Preparation of cellulose triacetate film and preparation of member for liquid crystal displaying |
-
1977
- 1977-12-28 JP JP16044377A patent/JPS5514201A/en active Granted
-
1978
- 1978-12-28 GB GB7850087A patent/GB2013559B/en not_active Expired
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0708135A1 (en) | 1994-10-20 | 1996-04-24 | Fuji Photo Film Co., Ltd. | Cellulose triacetate film and process for producing the same |
Also Published As
| Publication number | Publication date |
|---|---|
| GB2013559B (en) | 1982-06-03 |
| GB2013559A (en) | 1979-08-15 |
| JPS5514201A (en) | 1980-01-31 |
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