JP2988783B2 - Recovered paper binding strap - Google Patents
Recovered paper binding strapInfo
- Publication number
- JP2988783B2 JP2988783B2 JP17978192A JP17978192A JP2988783B2 JP 2988783 B2 JP2988783 B2 JP 2988783B2 JP 17978192 A JP17978192 A JP 17978192A JP 17978192 A JP17978192 A JP 17978192A JP 2988783 B2 JP2988783 B2 JP 2988783B2
- Authority
- JP
- Japan
- Prior art keywords
- lactic acid
- acid
- production example
- paper binding
- recovered
- 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 - Lifetime
Links
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W90/00—Enabling technologies or technologies with a potential or indirect contribution to greenhouse gas [GHG] emissions mitigation
- Y02W90/10—Bio-packaging, e.g. packing containers made from renewable resources or bio-plastics
Description
【０００１】[0001]
【産業上の利用分野】本発明は回収古紙の結束紐に関す
る。さらに詳しくは、乳酸ポリマーを主体とする熱可塑
性ポリマーでできたアルカリ溶液中での分解性を有する
回収古紙結束紐に関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a tying cord of recovered waste paper. More specifically, the present invention relates to a tied cord of recovered waste paper having a decomposability in an alkaline solution made of a thermoplastic polymer mainly composed of a lactic acid polymer.
【０００２】[0002]
【従来の技術】近年、森林資源の保護のために一度使っ
た後の紙は再びパルプ原料として回収利用されることが
多くなった。従来、これら回収古紙を結束するための紐
としてはポリエチレン、ポリプロピレン、ポリエチレン
テレフタレート、ポリ塩化ビニル等の樹脂類から作られ
た物が用いられている。2. Description of the Related Art In recent years, paper once used for the protection of forest resources has often been recovered and used again as a pulp raw material. Heretofore, strings made of resins such as polyethylene, polypropylene, polyethylene terephthalate, and polyvinyl chloride have been used as strings for binding these recovered waste papers.
【０００３】しかし樹脂から製造された結束紐は、古紙
からパルプを回収するアルカリ溶液中での分解性が無
く、混入するとパルプ中に樹脂破片が残るためパルプ回
収の工程に共する際に古紙から分離する必要があった。[0003] However, the binding cord made of resin has no decomposability in an alkaline solution for recovering pulp from waste paper, and if mixed, resin fragments remain in the pulp. It needed to be separated.
【０００４】一方、熱可塑性樹脂で分解性のあるポリマ
ーとして、ポリ乳酸または乳酸とその他のヒドロキシカ
ルボン酸のコポリマー（以下乳酸系ポリマーと略称す
る）が開発されている。これらのポリマーは、動物の体
内で数カ月から１年で１００％分解し、又、土壌や海水
中に置かれた場合、湿った環境下では数週間で分解を始
め１年から数年で消滅し、さらに分解生成物は、人体に
無害な乳酸と二酸化炭素と水になるという特性を有して
いる。On the other hand, polylactic acid or a copolymer of lactic acid and another hydroxycarboxylic acid (hereinafter abbreviated as a lactic acid-based polymer) has been developed as a decomposable polymer with a thermoplastic resin. These polymers degrade 100% in the body of animals in months to a year, and when placed in soil or seawater, begin to degrade in a few weeks in moist environments and disappear in one to several years. In addition, the decomposition products have the property of becoming lactic acid, carbon dioxide, and water that are harmless to the human body.
【０００５】ポリ乳酸は、通常ラクタイドと呼ばれる乳
酸の環状２量体から合成され、その製造法に関してはＵ
ＳＰ１，９９５，９７０、ＵＳＰ２，３６２，５１１、
ＵＳＰ２，６８３，１３６に開示されている。また乳酸
とその他のヒドロキシカルボン酸のコポリマーは、通常
乳酸の環状２量体であるラクタイドとヒドロキシカルボ
ン酸の環状エステル中間体（通常グリコール酸の２量体
であるグリコライド）から合成され、その製造方法に関
しては、ＵＳＰ３，６３６，９５６とＵＳＰ３，７９
７，４９９に開示されている。[0005] Polylactic acid is synthesized from a cyclic dimer of lactic acid, usually called lactide.
SP1,995,970, USP2,362,511,
No. 2,683,136. Also, a copolymer of lactic acid and another hydroxycarboxylic acid is synthesized from a cyclic ester intermediate of lactide, which is a cyclic dimer of lactic acid, and a cyclic ester of hydroxycarboxylic acid (glycolide, which is a dimer of glycolic acid). Regarding the method, USP 3,636,956 and USP 3,795
7,499.
【０００６】しかし、上記乳酸系ポリマーを用いた、内
容物である古紙と分離する必要がなく一緒にパルプ回収
工程に共することが出来る回収古紙結束紐は知られてい
なかった。However, there has been no known recovered tying cord using the above-mentioned lactic acid-based polymer, which can be used together with the pulp recovery step without having to be separated from waste paper as the content.
【０００７】[0007]
【発明が解決しようとする課題】本発明は、内容物であ
る古紙と共にパルプ回収工程に共することが出来る回収
古紙結束紐を提供することにある。SUMMARY OF THE INVENTION It is an object of the present invention to provide a recovered paper binding strap which can be used in a pulp recovery step together with waste paper as a content.
【０００８】[0008]
【課題を解決するための手段】本発明者らは、上記課題
を解決するために鋭意検討した結果、乳酸系ポリマーが
アルカリ溶液中で容易に分解して消滅することを見いだ
し本発明を完成したものである。Means for Solving the Problems The inventors of the present invention have conducted intensive studies to solve the above problems, and as a result, have found that a lactic acid-based polymer is easily decomposed and disappeared in an alkaline solution, and completed the present invention. Things.
【０００９】即ち、本発明は、ポリ乳酸または乳酸とヒ
ドロキシカルボン酸のコポリマーを主成分とする熱可塑
性ポリマー組成物でできた回収古紙結束紐である。That is, the present invention is a recovered paper tying cord made of a thermoplastic polymer composition containing polylactic acid or a copolymer of lactic acid and hydroxycarboxylic acid as a main component.
【００１０】本発明に用いられるポリマーは、ポリ乳酸
系ポリマーが主成分として用いられ、その他のヒドロキ
シカルボン酸としては、グリコール酸、３−ヒドロキシ
酪酸、４−ヒドロキシ酪酸、４−ヒドロキシ吉草酸、５
−ヒドロキシ吉草酸、６−ヒドロキシカプロン酸等が用
いられる。As the polymer used in the present invention, a polylactic acid-based polymer is used as a main component, and other hydroxycarboxylic acids include glycolic acid, 3-hydroxybutyric acid, 4-hydroxybutyric acid, 4-hydroxyvaleric acid,
-Hydroxyvaleric acid, 6-hydroxycaproic acid and the like are used.
【００１１】ポリ乳酸系ポリマーは、乳酸または乳酸と
他のヒドロキシカルボン酸から直接脱水重縮合するか、
乳酸の環状２量体であるラクタイドまたはヒドロキシカ
ルボン酸の環状エステル中間体、例えばグリコール酸の
２量体であるグリコライド（ＧＬＤ）や６−ヒドロキシ
カプロン酸の環状エステルであるε−カプロラクトン
（ＣＬ）等の共重合可能なモノマーを適宜用いて開環重
合させた物でもよい。原料としての乳酸は、Ｌ−乳酸ま
たはＤ−乳酸またはそれらの混合物のいずれでもよい。The polylactic acid-based polymer may be directly dehydrated and polycondensed from lactic acid or lactic acid and another hydroxycarboxylic acid,
Lactide as a cyclic dimer of lactic acid or cyclic ester intermediate of hydroxycarboxylic acid, for example, glycolide (GLD) as a dimer of glycolic acid or ε-caprolactone (CL) as a cyclic ester of 6-hydroxycaproic acid And the like, and may be a product obtained by ring-opening polymerization using a copolymerizable monomer as appropriate. Lactic acid as a raw material may be either L-lactic acid or D-lactic acid or a mixture thereof.
【００１２】乳酸系ポリマーには、通常公知の熱可塑性
ポリマーまたは可塑剤、さらに各種の改質剤を用いて、
熱可塑性ポリマー組成物とする。公知の熱可塑性ポリマ
ーとしては、ポリグリコール酸、ポリε−カプロラクト
ン等の分解性の物が好ましい。熱可塑性ポリマー組成物
中の乳酸系ポリマーの占める割合は、目的とする分解性
より任意の割合の物が用いられるが、一般的には５０％
以上が好ましい。又熱可塑性ポリマー組成物の製造は、
公知の混練技術はすべて適用できるが、組成物の形状は
ペレット、棒状、紛状等で用いられる。The lactic acid-based polymer can be prepared by using a generally known thermoplastic polymer or a plasticizer and various modifiers.
It is a thermoplastic polymer composition. As the known thermoplastic polymer, a decomposable substance such as polyglycolic acid and polyε-caprolactone is preferable. The proportion of the lactic acid-based polymer in the thermoplastic polymer composition may be an arbitrary proportion depending on the intended degradability, but is generally 50%.
The above is preferred. The production of the thermoplastic polymer composition
All known kneading techniques can be applied, but the composition is used in the form of pellets, rods, powders, and the like.
【００１３】本発明の回収古紙結束紐は、通常の加工方
で製造される物で、断面が円形、矩形、等の単一の繊維
状の物、これら繊維状のものをよりあわせた物、テープ
状の物等でも良い。本発明による熱可塑性ポリマー組成
物を用いて紐を得るには、該組成物を押出機で加熱溶融
し、Ｔダイからフィルム状に押出し、薄いフィルムに延
伸する方法で得られたリボン状のフィルムをロールに巻
取る方法が一般的であるが、この他いずれの方法でも構
わない。[0013] The recovered used paper binding strap of the present invention is manufactured by a normal processing method, and is a single fibrous material having a circular or rectangular cross section, a material obtained by combining these fibrous materials, A tape-shaped thing etc. may be sufficient. In order to obtain a string using the thermoplastic polymer composition according to the present invention, the composition is heated and melted by an extruder, extruded into a film form from a T-die, and stretched into a thin film to obtain a ribbon-like film. Is generally wound on a roll, but any other method may be used.
【００１４】本発明の乳酸系ポリマーから得られる結束
紐の成形条件は成形機、ポリマーの種類等によって適宜
決定されるが、例えば、下記の条件が使用される。 押出し機 ；４０ｍｍφ、５０ｒｐ
ｍ 押出し温度 ；１７０〜２５０℃ Ｔダイ ；スリット０．２ｍｍ、
幅１５０ｍｍ 延伸温度 ；８０〜１００℃ 延伸倍率 ；３〜８The conditions for forming the binding cord obtained from the lactic acid-based polymer of the present invention are appropriately determined depending on the molding machine, the type of the polymer, and the like. For example, the following conditions are used. Extruder: 40mmφ, 50rpm
m Extrusion temperature; 170-250 ° C T-die; slit 0.2 mm
Width 150mm Stretching temperature; 80-100 ° C Stretching ratio; 3-8
【００１５】[0015]
製造例１ Ｌ−ラクタイド１０ｋｇ（１．５モル）およびオクタン
酸スズ０．０１重量％と、ラウリルアルコール０．０３
重合％を、攪拌機を備えた肉厚の円筒型ステンレス製重
合容器へ封入し、真空で２時間脱気した後窒素ガスで置
換した。この混合物を窒素雰囲気下で攪拌しつつ２００
℃で３時間加熱した。温度をそのまま保ちながら、排気
管及びガラス製受器を介して真空ポンプにより徐々に脱
気し反応容器内を３ｍｍＨｇまで減圧にした。脱気開始
から１時間後、モノマーや低分子量揮発分の留出がなく
なったので、容器内を窒素置換し、容器下部からポリマ
ーを紐状に抜き出してペレット化し、ポリＬ−乳酸を得
た。このポリマーの分子量は約１０万であった。Production Example 1 L-lactide 10 kg (1.5 mol), tin octoate 0.01% by weight, lauryl alcohol 0.03
The polymerization% was sealed in a thick-walled cylindrical stainless steel polymerization vessel equipped with a stirrer, degassed under vacuum for 2 hours, and then replaced with nitrogen gas. The mixture is stirred for 200 hours under a nitrogen atmosphere.
Heated at C for 3 hours. While maintaining the temperature as it was, the air was gradually degassed by a vacuum pump through an exhaust pipe and a glass receiver, and the pressure inside the reaction vessel was reduced to 3 mmHg. One hour after the start of the degassing, the distillation of the monomer and low-molecular-weight volatiles was stopped. The inside of the container was replaced with nitrogen, and the polymer was drawn out from the lower part of the container in a string form and pelletized to obtain poly-L-lactic acid. The molecular weight of this polymer was about 100,000.
【００１６】製造例２ Ｌ−ラクタイド１０ｋｇをＬ−ラクタイド５ｋｇとＤ−
ラクタイド５ｋｇに変えたほかは製造例１と同様にして
ペレット化し、ポリＤＬ−乳酸を得た。このポリマーの
分子量は約１０万であった。Production Example 2 10 kg of L-lactide was combined with 5 kg of L-lactide and D-lactide.
Pelletization was performed in the same manner as in Production Example 1 except that the lactide was changed to 5 kg to obtain poly-DL-lactic acid. The molecular weight of this polymer was about 100,000.
【００１７】製造例３〜４ Ｌ−ラクタイド１０ｋｇをＬ−ラクタイド５ｋｇとヒド
ロキシカルボン酸成分５ｋｇに変えた他は製造例１と同
様にしてペレット化し、Ｌ−ラクタイドとヒドロキシカ
ルボン酸共重合体を得た。ヒドロキシカルボン酸性分が
グリコライドの場合を製造例３（平均分子量１０万）、
同じくヒドロキシカルボン酸性分がε−カプロラクトン
の場合を製造例４（平均分子量７万）とした。Production Examples 3-4 Pelletization was carried out in the same manner as in Production Example 1 except that 10 kg of L-lactide was changed to 5 kg of L-lactide and 5 kg of a hydroxycarboxylic acid component to obtain a copolymer of L-lactide and hydroxycarboxylic acid. Was. Production Example 3 (average molecular weight 100,000) in the case where the hydroxycarboxylic acid component is glycolide,
Similarly, the case where the hydroxycarboxylic acid component was ε-caprolactone was designated as Production Example 4 (average molecular weight 70,000).
【００１８】尚、ポリマーの平均分子量（重量平均分子
量）はポリスチレンを標準としてゲルパーミエーション
クロマトグラフィーにより以下の条件で測定した。 装置 ：島津ＬＣ−１０ＡＤ 検出器：島津ＲＩＤ−６Ａ カラム：日立化成ＧＬ−Ｓ３５０ＤＴ−５、ＧＬ−Ｓ３
７０ＤＴ−５ 溶媒 ：クロロホルム 濃度 ：１％ 注入量：２０μｌ 流速 ：１．０ｍｌ／ｍｉｎThe average molecular weight (weight average molecular weight) of the polymer was measured by gel permeation chromatography using polystyrene as a standard under the following conditions. Apparatus: Shimadzu LC-10AD Detector: Shimadzu RID-6A Column: Hitachi Chemical GL-S350DT-5, GL-S3
70DT-5 Solvent: chloroform Concentration: 1% Injection volume: 20 μl Flow rate: 1.0 ml / min
【００１９】実施例１ 製造例１で得られたポリＬ−乳酸と、製造例２で得られ
たポリＤＬ−乳酸を８０：２０で混合し、スリット０．
２ｍｍ、幅１５０ｍｍのＴダイを備えた４０ｍｍφの押
出し機を用い、押出し温度２００℃、回転数５０ｒｐｍ
で押出し加工し、つずいて８０℃で５倍に延伸すること
により厚さ３０μｍ、幅５０ｍｍのフィルム状紐を得
た。Example 1 The poly-L-lactic acid obtained in Production Example 1 and the poly-DL-lactic acid obtained in Production Example 2 were mixed at a ratio of 80:20.
Using an extruder having a diameter of 40 mm and a T-die having a width of 2 mm and a width of 150 mm, an extrusion temperature of 200 ° C. and a rotation speed of 50 rpm
And then stretched 5 times at 80 ° C. to obtain a film string having a thickness of 30 μm and a width of 50 mm.
【００２０】実施例２ 製造例１で得られたポリＬ−乳酸と、製造例２で得られ
たポリＤＬ−乳酸を５０：５０で混合し、押出し温度を
１９０℃にした以外は実施例１と同様にして厚さ３０μ
ｍ、幅５０ｍｍのフィルム状紐を得た。Example 2 Example 1 was repeated except that the poly-L-lactic acid obtained in Production Example 1 and the poly-DL-lactic acid obtained in Production Example 2 were mixed at a ratio of 50:50, and the extrusion temperature was changed to 190 ° C. 30μ in thickness
m, a film-like string having a width of 50 mm was obtained.
【００２１】実施例３ 製造例１で得られたポリＬ−乳酸と、製造例２で得られ
たポリＤＬ−乳酸を２０：８０で混合し、押出し温度を
１８０℃にした以外は実施例１と同様にして厚さ３０μ
ｍ、幅５０ｍｍのフィルム状紐を得た。Example 3 Example 1 was repeated except that the poly-L-lactic acid obtained in Production Example 1 and the poly-DL-lactic acid obtained in Production Example 2 were mixed at a ratio of 20:80 and the extrusion temperature was adjusted to 180 ° C. 30μ in thickness
m, a film-like string having a width of 50 mm was obtained.
【００２２】比較例１ 製造例１で得られたポリＬ−乳酸と、製造例２で得られ
たポリＤＬ−乳酸の代わりにポリヒドロキシブチレート
とポリヒドロキシバレレート共重合体を用い、押出し温
度１５０℃、延伸温度６０℃にした以外は実施例１と同
様にして厚さ３０μｍ、幅５０ｍｍのフィルム状紐を得
た。Comparative Example 1 Polyhydroxybutyrate and polyhydroxyvalerate copolymer were used in place of the poly L-lactic acid obtained in Production Example 1 and the poly DL-lactic acid obtained in Production Example 2, and the extrusion temperature was changed. A film string having a thickness of 30 μm and a width of 50 mm was obtained in the same manner as in Example 1 except that the stretching temperature was 150 ° C. and the stretching temperature was 60 ° C.
【００２３】比較例２ 製造例１で得られたポリＬ−乳酸と、製造例２で得られ
たポリＤＬ−乳酸の代わりにポリエチレンを用い、押出
し温度２００℃、延伸温度１００℃にした以外は実施例
１と同様にして厚さ３０μｍ、幅５０ｍｍのフィルム状
紐を得た。Comparative Example 2 Polyethylene was used instead of the poly L-lactic acid obtained in Production Example 1 and the poly DL-lactic acid obtained in Production Example 2, except that the extrusion temperature was 200 ° C. and the stretching temperature was 100 ° C. A film string having a thickness of 30 μm and a width of 50 mm was obtained in the same manner as in Example 1.
【００２４】実施例及び比較例で得た各々のフィルム状
紐を用い、引っ張り強度試験と下記の実用試験を行っ
た。結果を表−１（表１）に示す。Using each of the film-like cords obtained in Examples and Comparative Examples, a tensile strength test and the following practical tests were performed. The results are shown in Table 1 (Table 1).
【００２５】実施例４ 製造例２で得たポリＤＬ乳酸を用い、押出し温度を１８
０℃、延伸温度７０℃にした以外は、実施例１と同様に
して厚さ３０μｍ、幅５０ｍｍのフィルム状紐を得た。Example 4 The poly-DL-lactic acid obtained in Production Example 2 was used at an extrusion temperature of 18
A film string having a thickness of 30 μm and a width of 50 mm was obtained in the same manner as in Example 1 except that the stretching temperature was set to 0 ° C. and the stretching temperature was set to 70 ° C.
【００２６】実施例５ 製造例３で得たＬ−ラクタイドとグリコライドのコポリ
マーを用い、押出し温度１５０℃、延伸温度６０℃にし
た以外は、実施例１と同様にして厚さ３０μｍ、幅５０
ｍｍのフィルム状紐を得た。Example 5 The same procedure as in Example 1 was carried out except that the extrusion temperature was 150 ° C. and the stretching temperature was 60 ° C., using the copolymer of L-lactide and glycolide obtained in Production Example 3, and the thickness was 30 μm and the width was 50 μm.
mm film string was obtained.
【００２７】実施例６ 製造例４で得たＬ−ラクタイドとε−カプロラクトンの
コポリマーを用い、押出し温度１５０℃、延伸温度６０
℃にした以外は、実施例１と同様にして厚さ３０μｍ、
幅５０ｍｍのフィルム状紐を得た。Example 6 Using the copolymer of L-lactide and ε-caprolactone obtained in Production Example 4, an extrusion temperature of 150 ° C. and a stretching temperature of 60 were used.
Except that the temperature was 30 ° C., except that the temperature was 30 ° C.
A film-like string having a width of 50 mm was obtained.
【００２８】実施例４〜６で得た各々の袋状容器を用
い、引っ張り強度試験と実用試験を行った。結果を表−
２（表２）に示す。 実用テスト 実施例及び比較例で得られたフィルム状紐を用い、坪量
６５ｇ／ｍ2、２００ｍｍ×２００ｍｍの上質紙２０枚
を結束した。これを温度６０℃の１Ｎ水酸化ナトリウム
水溶液中に浸漬し１時間攪拌する。Using each of the bag-shaped containers obtained in Examples 4 to 6, a tensile strength test and a practical test were performed. Table-Results
2 (Table 2). Practical Test Using the film-like cords obtained in the examples and comparative examples, 20 high-quality papers having a basis weight of 65 g / m 2 and a size of 200 mm × 200 mm were bound. This is immersed in a 1N aqueous solution of sodium hydroxide at a temperature of 60 ° C. and stirred for 1 hour.
【００２９】[0029]
【表１】 [Table 1]
【００３０】[0030]
【表２】 [Table 2]
【００３１】[0031]
【発明の効果】本発明による乳酸系ポリマーを主体とす
る熱可塑性樹脂組成物からなる回収古紙結束紐は、内容
物である古紙と分離する必要がなく、そのまま一緒にパ
ルプ回収工程に共することができ、古紙回収作業の手間
を大幅に簡素化できるものである。According to the present invention, the recovered used paper binding string made of the thermoplastic resin composition mainly containing a lactic acid-based polymer according to the present invention does not need to be separated from the used waste paper, and can be used together with the pulp recovery process as it is. This greatly simplifies the work of collecting used paper.
フロントページの続き (58)調査した分野(Int.Cl.6，ＤＢ名) B65D 63/10 Continuation of front page (58) Field surveyed (Int.Cl. 6 , DB name) B65D 63/10
Claims (3)
ルボン酸のコポリマーを主成分とする熱可塑性ポリマー
組成物からなる回収古紙結束紐。1. A recovered used paper binding cord comprising a thermoplastic polymer composition containing polylactic acid or a copolymer of lactic acid and another hydroxycarboxylic acid as a main component.
の混合物であることを特徴とする請求項１記載の回収古
紙結束紐。2. The recovered used paper binding string according to claim 1, wherein the lactic acid is L-lactic acid, D-lactic acid or a mixture thereof.
または６−ヒドロキシカプロン酸であることを特徴とす
る請求項１記載の回収古紙結束紐。3. The method of claim 1, wherein the hydroxycarboxylic acid is glycolic acid,
The recovered used paper binding strap according to claim 1, wherein the binding strap is 6-hydroxycaproic acid.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP17978192A JP2988783B2 (en) | 1992-07-07 | 1992-07-07 | Recovered paper binding strap |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP17978192A JP2988783B2 (en) | 1992-07-07 | 1992-07-07 | Recovered paper binding strap |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0632365A JPH0632365A (en) | 1994-02-08 |
| JP2988783B2 true JP2988783B2 (en) | 1999-12-13 |
Family
ID=16071784
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP17978192A Expired - Lifetime JP2988783B2 (en) | 1992-07-07 | 1992-07-07 | Recovered paper binding strap |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2988783B2 (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3330712B2 (en) * | 1994-01-11 | 2002-09-30 | 三菱樹脂株式会社 | Method for producing polylactic acid-based film |
| JPH07205278A (en) * | 1994-01-11 | 1995-08-08 | Mitsubishi Plastics Ind Ltd | Production of stretched film of polylactic acid polymer |
| JP2003002984A (en) * | 2002-06-14 | 2003-01-08 | Mitsubishi Plastics Ind Ltd | Polylactic acid film |
-
1992
- 1992-07-07 JP JP17978192A patent/JP2988783B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0632365A (en) | 1994-02-08 |
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