JPH08193168A - Biodegradable resin composition - Google Patents
Biodegradable resin compositionInfo
- Publication number
- JPH08193168A JPH08193168A JP623495A JP623495A JPH08193168A JP H08193168 A JPH08193168 A JP H08193168A JP 623495 A JP623495 A JP 623495A JP 623495 A JP623495 A JP 623495A JP H08193168 A JPH08193168 A JP H08193168A
- Authority
- JP
- Japan
- Prior art keywords
- biodegradable
- film
- biodegradable plastic
- polymer composition
- ascidian
- 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
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Biological Depolymerization Polymers (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、生分解性プラスチック
とホヤセルロース繊維を含む崩壊性または生分解性ポリ
マー組成物、及びそれからなる成形物またはフィルムに
関するものである。これらは、優れた機械的強度を有す
る崩壊性または生分解性プラスチック成形物またはフィ
ルムとして、種々の用途に有用である。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a disintegratable or biodegradable polymer composition containing a biodegradable plastic and ascidian cellulose fiber, and a molded product or film comprising the same. These are useful for various applications as a disintegratable or biodegradable plastic molded product or film having excellent mechanical strength.
【０００２】[0002]
【従来の技術】プラスチック廃棄物問題が深刻化してい
る中で、崩壊性プラスチックや生分解性のプラスチック
が開発され、廃棄物問題の解決策として注目されてい
る。崩壊性プラスチックとしては、従来の非分解性プラ
スチックに生分解性を有するでん粉を混入したものがあ
る。また、特開平４−１８２１１２号公報に記載されて
いる脂肪族ポリエステル樹脂をマトリックスとして熱可
塑性樹脂を混合する技術が提案されている。また、生分
解性プラスチックとしては、脂肪族ポリエステル等が提
案されているが、従来の非分解性のプラスチックと比較
してその機械的強度が十分でないため、その成形物は肉
厚になり、微生物により分解するのに要する時間が長い
等の問題がある。それらの問題を解決するため、これら
の生分解性プラスチックに、充填剤として、炭酸カルシ
ウムや含水珪酸マグネシウムを混合する方法（特開平５
−７０６９６号公報）が提案されている。一方、天然の
ポリマーとして有用であると考えられるセルロースは、
その成形性の悪さから、成形物として実用化が困難であ
る。そのため、セルロース誘導体を用いたり、植物繊維
を加水分解して得られた分解物を用いたフィルムが提案
されている（特開平３−２３１９２７号公報）。充填剤
としては、ポリオレフィン系樹脂に木材パルプや繊維化
されたセルロースを主体とする植物繊維（特開昭６０−
１５８２３６号公報）を混合する方法が知られている。
また、生分解性樹脂に、でんぷん、植物体粉末、セルロ
ース繊維等の天然高分子物質を混合する方法（特開平５
−３２０５２４号公報）や、グリコールと脂肪族二塩基
酸類から合成された脂肪族ポリエステルにセルロース系
有機充填剤を配合する方法（特開平６−１７２６２４号
公報）が提案されている。しかしながら、いずれも十分
な機械的強度と生分解性を有する成形物等は得られてい
ない。2. Description of the Related Art While the problem of plastic waste is becoming more serious, collapsible plastics and biodegradable plastics have been developed and are attracting attention as a solution to the waste problem. As the disintegrating plastic, there is a conventional non-degradable plastic mixed with starch having biodegradability. Further, a technique has been proposed in which a thermoplastic resin is mixed with an aliphatic polyester resin as a matrix, which is described in JP-A-4-182112. Further, as the biodegradable plastic, aliphatic polyester and the like have been proposed, but since the mechanical strength thereof is not sufficient as compared with the conventional non-degradable plastic, the molded product becomes thick and the microbial Therefore, there is a problem that the time required for decomposition is long. In order to solve these problems, a method of mixing these biodegradable plastics with calcium carbonate or hydrous magnesium silicate as a filler (Japanese Patent Application Laid-Open No. HEI 5)
-70696 gazette) is proposed. On the other hand, cellulose, which is considered to be useful as a natural polymer,
Due to its poor moldability, it is difficult to put it into practical use as a molded product. Therefore, a film using a cellulose derivative or a decomposed product obtained by hydrolyzing plant fiber has been proposed (JP-A-3-231927). As the filler, a plant fiber mainly composed of wood pulp or fibrous cellulose in a polyolefin resin (JP-A-60-
No. 158236) is known.
In addition, a method of mixing a biodegradable resin with a natural polymer substance such as starch, plant powder, and cellulose fiber (Japanese Patent Application Laid-Open No. Hei 5)
No. 320205), and a method of blending a cellulosic organic filler with an aliphatic polyester synthesized from glycol and an aliphatic dibasic acid (JP-A-6-172624). However, none of them has obtained a molded product having sufficient mechanical strength and biodegradability.
【０００３】[0003]
【発明が解決しようとする課題】本発明の目的は、十分
な機械的強度を持ち、かつ使用後に廃棄する際、微生物
により速やかに崩壊または分解する、生分解性プラスチ
ック組成物及びそれからなる成形物及びフィルムを提供
することにある。DISCLOSURE OF THE INVENTION An object of the present invention is to provide a biodegradable plastic composition having a sufficient mechanical strength and rapidly disintegrated or decomposed by microorganisms when it is discarded after use, and a molded article comprising the same. And to provide a film.
【０００４】[0004]
【課題を解決するための手段】本発明者らは、前記課題
を解決すべく鋭意研究を重ねた結果、ホヤセルロース繊
維を混合することにより前記課題を解決できることを見
いだし、本発明を完成するに至った。即ち、本発明は、
生分解性プラスチックとホヤセルロース繊維を含む崩壊
性または生分解性ポリマー組成物、及び該組成物からな
る成形物及びフィルムである。Means for Solving the Problems As a result of intensive studies to solve the above problems, the present inventors have found that the problems can be solved by mixing ascidian cellulose fiber, and the present invention is completed. I arrived. That is, the present invention
Disintegratable or biodegradable polymer compositions containing biodegradable plastics and ascidian fibers, and molded articles and films comprising the compositions.
【０００５】本発明に係る生分解性プラスチック組成
物、及び成形物及びフィルムは、生分解性プラスチック
とホヤセルロース繊維を含むことを特徴とする。ホヤセ
ルロース繊維は、木材パルプ等から得られるセルロース
繊維に比べ、ヤング率が大きいため、高い剛性を有す
る。生分解性プラスチック中にホヤセルロースを、重量
比で５〜６０％、より好ましくは、１０〜５０％含有さ
せることにより、引張強度、曲げ弾性率等が向上し、十
分な機械的強度を持つ成形物及びフィルムを得ることが
できる。The biodegradable plastic composition, the molded product and the film according to the present invention are characterized by containing a biodegradable plastic and ascidian cellulose fiber. Ascidian cellulose fiber has a higher Young's modulus than cellulose fiber obtained from wood pulp or the like, and thus has high rigidity. Molding having sufficient mechanical strength by increasing the tensile strength, flexural modulus, etc. by containing ascidian cellulose in the biodegradable plastic in a weight ratio of 5 to 60%, more preferably 10 to 50%. Objects and films can be obtained.
【０００６】本発明に係るホヤセルロース繊維は、ホヤ
の外被をカッター等で切断し５〜２０ｍｍ程度の大きさ
にした後、ミキサー等の装置を用いて粉砕し、ビータ等
を用いてミクロフィブリル化することにより、直径０．
１μｍ以下の微細繊維として得られる。タンパク質、脂
肪等を除去するためアルカリや有機溶媒で処理して用い
られることもある。これらの技術は、特開平５−３００
５８６号公報に開示されている。The ascidian cellulose fiber according to the present invention is obtained by cutting the outer cover of the ascidian with a cutter or the like to a size of about 5 to 20 mm, crushing it with a device such as a mixer, and then using a beater or the like to obtain microfibrils. By converting the diameter to 0.
Obtained as fine fibers of 1 μm or less. It may be used after being treated with an alkali or an organic solvent in order to remove proteins, fats and the like. These techniques are disclosed in JP-A-5-300.
It is disclosed in Japanese Patent No. 586.
【０００７】また、本発明に係る生分解性プラスチック
としては、ポリ乳酸、ポリグリコール酸、ポリ−３−ヒ
ドロキシブチレート、ポリ−４−ヒドロキシブチレー
ト、ポリヒドロキシバリレート、ポリエチレンアジペー
ト、ポリカプロラクトン、ポリプロピオラクトン等のポ
リエステル、ポリエチレングリコール等のポリエーテ
ル、ポリグルタミン酸、ポリリジン等のポリアミド、ポ
リビニルアルコール、ポリウレタン等を用いることがで
きる。また、これらの生分解性プラスチックは一種で
も、二種類以上のポリマーのブレンドであってもよい。
また、これらの生分解性プラスチックは二種類以上のコ
ポリマーであってもよい。ポリヒドロキシカルボン酸が
好ましく、ポリ乳酸または乳酸とヒドロキシカルボン酸
のコポリマーがより好ましい。しかしながら、本発明に
係る生分解性プラスチック成形物の主体となる生分解性
プラスチックは特に限定されるものではない。The biodegradable plastics according to the present invention include polylactic acid, polyglycolic acid, poly-3-hydroxybutyrate, poly-4-hydroxybutyrate, polyhydroxyvalerate, polyethylene adipate, polycaprolactone, Polyester such as polypropiolactone, polyether such as polyethylene glycol, polyamide such as polyglutamic acid and polylysine, polyvinyl alcohol, polyurethane and the like can be used. Further, these biodegradable plastics may be one kind or a blend of two or more kinds of polymers.
Further, these biodegradable plastics may be a copolymer of two or more kinds. Polyhydroxycarboxylic acid is preferable, and polylactic acid or a copolymer of lactic acid and hydroxycarboxylic acid is more preferable. However, the biodegradable plastic which is the main component of the biodegradable plastic molding according to the present invention is not particularly limited.
【０００８】本発明に係わる成形物またはフィルムは、
各種の改質材を用いて混合、混練させたものでも良い。
また、本発明に係わる成形物またはフィルムの製造は、
公知の混練技術は全て適用できるが、ホヤセルロース繊
維の特徴を十分に発揮させるために繊維の分散が良好な
方法が好ましい。分解性プラスチックとホヤセルロース
繊維を混合機で均一にして、射出成形、圧縮成形、シー
ト成形、押出成形等し、さらに延伸加工することにより
成形物またはフィルムを製造することができる。The molded article or film according to the present invention is
It may be mixed and kneaded with various modifiers.
Further, the production of the molded product or film according to the present invention,
All known kneading techniques can be applied, but a method in which the fibers are well dispersed is preferable in order to fully exhibit the characteristics of the ascidian cellulose fibers. A degradable plastic and ascidian cellulose fibers are made uniform by a mixer, injection molded, compression molded, sheet molded, extruded, etc., and further stretched to produce a molded product or film.
【０００９】[0009]
【実施例】以下に実施例を示すが、本発明はこれに限定
されるものではない。実施例で用いたホヤセルロース繊
維は以下のようにして得た。ホヤの外被をカッター等で
切断して５〜２０ｍｍ程度の大きさにする。この切断片
をホモジナイザーを用いて１０分間粉砕する。次に還流
装置により０．２５ＮのＮａＯＨ水溶液中で１００℃に
おいて６時間処理しタンパク質を除去した。その後、
０．２５Ｎの塩酸で中和してから蒸留水で洗浄した。ソ
ックスレー抽出器を使用し、エーテルとエタノールの混
合溶液（体積比 １：１）中で２時間、７０℃で加熱処
理した。更に高圧ホモジナイザーにより５００ｋｇｆ／
ｃｍ2の圧力で３０回フィブリル化処理を行った。得ら
れたセルロース質繊維はミクロフィブリル状態まで叩解
されており、繊維径が０．１μｍ、繊維長が８００μｍ
であった。EXAMPLES Examples will be shown below, but the present invention is not limited to these examples. The sea squirt cellulose fibers used in the examples were obtained as follows. The outer cover of the squirt is cut with a cutter or the like to have a size of about 5 to 20 mm. The cut pieces are ground for 10 minutes using a homogenizer. Next, the protein was removed by treatment in a 0.25 N NaOH aqueous solution at 100 ° C. for 6 hours using a reflux apparatus. afterwards,
It was neutralized with 0.25N hydrochloric acid and washed with distilled water. Using a Soxhlet extractor, heat treatment was carried out at 70 ° C. for 2 hours in a mixed solution of ether and ethanol (volume ratio 1: 1). With a high pressure homogenizer, 500 kgf /
Fibrillation treatment was performed 30 times at a pressure of cm 2 . The obtained cellulosic fibers have been beaten to a microfibril state and have a fiber diameter of 0.1 μm and a fiber length of 800 μm.
Met.
【００１０】実施例１ Ｌ−ラクタイド１００部およびオクタン酸第一スズ０．
０１部と、ラウリルアルコール０．０３部を、攪拌器を
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、排気管およびガラス製容器
を介して真空ポンプにより徐々に脱気し反応容器内を３
ｍｍＨｇ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、容器下部からモノ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。このようにし
て得たポリ−Ｌ−乳酸（重量平均分子量１０万）９０部
とホヤセルロース繊維１０部をリボンブレンダーで混合
後、２軸押出機シリンダー温度１７０〜２１０℃の条件
にてペレット化した。該ペレットを８０℃のオーブンで
熱処理し、押出機のシリンダー温度１６０〜２００℃の
条件にて溶融し、押出機先端のＴダイから厚み０．１０
ｍｍのフィルムを得た。同様に、ホヤ繊維が２０及び４
０部のフィルムを得た。Example 1 100 parts of L-lactide and stannous octoate 0.
01 parts and 0.03 parts of lauryl alcohol were sealed in a thick cylindrical polymerization vessel made of stainless steel equipped with a stirrer, deaerated under vacuum for 2 hours, and then replaced with nitrogen gas. The mixture was heated at 200 ° C. for 3 hours with stirring under a nitrogen atmosphere.
While keeping the temperature as it is, gradually degas by a vacuum pump through the exhaust pipe and the glass container, and the inside of the reaction container is cooled to 3
The pressure was reduced to mmHg. After 1 hour from the start of degassing, the distillation of the monomer and low-molecular-weight volatile matter disappeared, so the inside of the container was replaced with nitrogen, and the monomer was extracted from the lower part of the container in a string shape and pelletized to obtain poly-L-lactic acid . 90 parts of the poly-L-lactic acid (weight average molecular weight of 100,000) thus obtained and 10 parts of ascidian cellulose fiber were mixed with a ribbon blender and then pelletized under the conditions of a twin-screw extruder cylinder temperature of 170 to 210 ° C. . The pellets were heat-treated in an oven at 80 ° C., melted under the conditions of an extruder cylinder temperature of 160 to 200 ° C., and a thickness of 0.10 was obtained from the T die at the tip of the extruder.
A film of mm was obtained. Similarly, squirt fibers are 20 and 4
0 part of film was obtained.
【００１１】実施例２ 実施例１に記載のポリ−Ｌ−乳酸７０部とポリカプロラ
クトン（ユニオンカーバイド製：商品名；ＴＯＮＥ，Ｐ
−７８７）３０部のブレンドポリマーを用い、実施例１
と同様に、ホヤセルロース繊維を混合してフィルムを得
た。Example 2 70 parts of poly-L-lactic acid described in Example 1 and polycaprolactone (manufactured by Union Carbide: trade name; TONE, P
-787) Example 1 using 30 parts of blended polymer
In the same manner as above, ascidian fibers were mixed to obtain a film.
【００１２】実施例３ ポリ−３−ヒドロキシブチレート−ポリ−３−ヒドロキ
シバリレート共重合体（ゼネカ（株）製、商品名；バイ
オポール，Ｓ−３０）８０部とホヤ繊維２０部をリボン
ブレンダーで混合後、２軸押出機シリンダー温度１５０
〜１７０℃の条件にてペレット化した。更に、押出機の
シリンダー温度１５０〜１６０℃の条件にて溶融し、押
出機先端のＴダイから厚み０．１０ｍｍのフィルムを得
た。Example 3 Poly-3-hydroxybutyrate-poly-3-hydroxyvalerate copolymer (manufactured by Zeneca Corporation, trade name; Biopol, S-30) 80 parts and squirt fiber 20 parts were ribbons. After mixing with a blender, twin screw extruder cylinder temperature 150
Pelletization was carried out under the condition of 170 ° C. Further, the extruder was melted under the condition of a cylinder temperature of 150 to 160 ° C., and a film having a thickness of 0.10 mm was obtained from the T die at the tip of the extruder.
【００１３】比較例１ 実施例１記載のポリ−Ｌ−乳酸を、２軸押出機シリンダ
ー温度１７０〜２１０℃の条件にてペレット化した。該
ペレットを８０℃のオーブンで熱処理し、押出機のシリ
ンダー温度１６０〜２００℃の条件にて溶融し、押出機
先端のＴダイから厚み０．１０ｍｍのフィルムを得た。Comparative Example 1 The poly-L-lactic acid described in Example 1 was pelletized under the conditions of a twin screw extruder cylinder temperature of 170 to 210 ° C. The pellets were heat-treated in an oven at 80 ° C., melted under the conditions of an extruder cylinder temperature of 160 to 200 ° C., and a film having a thickness of 0.10 mm was obtained from a T die at the tip of the extruder.
【００１４】比較例２ 実施例１記載のポリ−Ｌ−乳酸７０部と実施例２記載の
ポリカプロラクトン３０部のブレンドポリマーを用い、
比較例１と同様に、フィルムを得た。Comparative Example 2 Using a blend polymer of 70 parts of poly-L-lactic acid described in Example 1 and 30 parts of polycaprolactone described in Example 2,
A film was obtained in the same manner as in Comparative Example 1.
【００１５】比較例３ 実施例３記載のポリ−３−ヒドロキシブチレート−ポリ
−３−ヒドロキシバリレート共重合体を、２軸押出機シ
リンダー温度１５０〜１７０℃の条件にてペレット化し
た。更に、押出機のシリンダー温度１５０〜１６０℃の
条件にて溶融し、押出機先端のＴダイから厚み０．１０
ｍｍのフィルムを得た。Comparative Example 3 The poly-3-hydroxybutyrate-poly-3-hydroxyvalerate copolymer described in Example 3 was pelletized under the conditions of a twin-screw extruder cylinder temperature of 150 to 170 ° C. Further, it is melted under the condition that the cylinder temperature of the extruder is 150 to 160 ° C.
A film of mm was obtained.
【００１６】比較例４ 実施例１記載のポリ−Ｌ−乳酸８０部と木材パルプ２０
部をリボンブレンダーで混合後、実施例１と同様に、フ
ィルムを得た。 実施例１−３、比較例１−４で得られたこれらのフィル
ムから試験片を作成して、引張強度、土壌分解性を調べ
た。フィルムサンプルの引張強度は、ＪＩＳ規格Ｋ−６
７３２に準じて測定した。分解性試験は２×５ｃｍの試
験片を採取し、該試験片を温度３５℃、水分３０％の土
壌中に埋設して分解試験を行い、重量の減少率を求め
た。これらの結果を第１表（表１）、第２表（表２）に
示す。Comparative Example 4 80 parts of poly-L-lactic acid described in Example 1 and 20 wood pulps
After mixing the parts with a ribbon blender, a film was obtained in the same manner as in Example 1. Test pieces were prepared from these films obtained in Example 1-3 and Comparative Example 1-4, and the tensile strength and soil degradability were investigated. The tensile strength of the film sample is JIS K-6.
It measured according to 732. In the decomposability test, a 2 × 5 cm test piece was sampled, and the test piece was embedded in soil at a temperature of 35 ° C. and a water content of 30% to perform a decomposition test to determine the weight reduction rate. The results are shown in Table 1 (Table 1) and Table 2 (Table 2).
【００１７】[0017]
【表１】 [Table 1]
【００１８】[0018]
【表２】 [Table 2]
【００１９】実施例４ ポリ−Ｌ−乳酸９０部とホヤ繊維１０部をリボンブレン
ダーで混合後、２軸押出機シリンダー温度１７０〜２１
０℃の条件にてペレット化した。該ペレットを８０℃の
オーブンで熱処理し、（株）日本製鋼所ＪＳＷ−７５射
出成形機を用い、シリンダー温度１６０〜２００℃の条
件にて溶融し、設定温度２０℃の金型に充填し、厚さ１
ｍｍ、深さ３０ｍｍ、底面７５×１００ｍｍの成形物を
得た。成形物から採取した３０×９０ｍｍの試験片の曲
げ弾性率は、１７０００ｋｇ／ｃｍ2 であった。また、
温度３５℃、水分３０％の土壌中に埋設して分解試験を
行ったところ、３カ月で２１％の重量減少率を示した。Example 4 90 parts of poly-L-lactic acid and 10 parts of ascidian fiber were mixed in a ribbon blender, and then the temperature of the twin-screw extruder was 170 to 21.
Pelletization was performed at 0 ° C. The pellets were heat-treated in an oven at 80 ° C, melted under the conditions of a cylinder temperature of 160 to 200 ° C using a Japan Steel Works JSW-75 injection molding machine, and filled in a mold at a set temperature of 20 ° C. Thickness 1
mm, depth 30 mm, and bottom surface 75 × 100 mm were obtained. The flexural modulus of the 30 × 90 mm test piece collected from the molded product was 17,000 kg / cm 2 . Also,
When it was buried in soil at a temperature of 35 ° C. and a water content of 30% and a decomposition test was performed, a weight loss rate of 21% was shown in 3 months.
【００２０】[0020]
【発明の効果】本発明の、生分解性プラスチックとホヤ
セルロース繊維を含む成形物またはフィルムは、十分な
機械的強度と、崩壊性あるいは生分解性速度を持ち、容
器、ボトル、シート、フィルム、積層品、包装材料等の
用途に用いることができる。特に、ショッピングバッ
グ、ゴミ袋、農業用フィルム、化粧品容器、洗剤容器、
漂白剤容器、保冷箱、クッション材、食品包装材料等の
用途に好適である。また、本発明による成形物またはフ
ィルムは、その優れた機械的強度により、肉薄、軽量化
することが可能である。Industrial Applicability The molded article or film containing the biodegradable plastic and the ascidian cellulose fiber of the present invention has sufficient mechanical strength and disintegration or biodegradability, and has a container, a bottle, a sheet, a film, It can be used for applications such as laminated products and packaging materials. In particular, shopping bags, garbage bags, agricultural films, cosmetic containers, detergent containers,
It is suitable for applications such as bleach containers, cold storage boxes, cushioning materials, and food packaging materials. Further, the molded product or film according to the present invention can be made thin and lightweight due to its excellent mechanical strength.
Claims (6)
繊維を含む崩壊性または生分解性ポリマー組成物。1. A disintegratable or biodegradable polymer composition comprising a biodegradable plastic and ascidian fibers.
０％含むことを特徴とする請求項１記載のポリマー組成
物。2. Ascidian cellulose fiber in a weight ratio of 5 to 6
The polymer composition according to claim 1, wherein the polymer composition contains 0%.
カルボン酸である請求項１記載のポリマー組成物。3. The polymer composition according to claim 1, wherein the biodegradable plastic is polyhydroxycarboxylic acid.
乳酸とヒドロキシカルボン酸のコポリマーである請求項
３記載のポリマー組成物。4. The polymer composition according to claim 3, wherein the biodegradable plastic is polylactic acid or a copolymer of lactic acid and hydroxycarboxylic acid.
なる崩壊性または生分解性プラスチック成形物。5. A disintegratable or biodegradable plastic molded product comprising the polymer composition according to any one of claims 1 to 4.
なる崩壊性または生分解性フィルム。6. A disintegratable or biodegradable film comprising the polymer composition according to claim 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP00623495A JP3423094B2 (en) | 1995-01-19 | 1995-01-19 | Biodegradable polymer composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP00623495A JP3423094B2 (en) | 1995-01-19 | 1995-01-19 | Biodegradable polymer composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH08193168A true JPH08193168A (en) | 1996-07-30 |
| JP3423094B2 JP3423094B2 (en) | 2003-07-07 |
Family
ID=11632835
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP00623495A Expired - Fee Related JP3423094B2 (en) | 1995-01-19 | 1995-01-19 | Biodegradable polymer composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3423094B2 (en) |
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH10202690A (en) * | 1997-01-27 | 1998-08-04 | Nissha Printing Co Ltd | Insert film, insert molded product and its manufacture |
| JPH10316739A (en) * | 1997-05-16 | 1998-12-02 | Kanebo Ltd | Refuse sack |
| JP2002121396A (en) * | 2000-10-13 | 2002-04-23 | Yayoi Chemical Industry Co Ltd | Filler for resin and article using the same |
| EP1400328A1 (en) * | 2002-09-18 | 2004-03-24 | Araco Corporation | Fiber board and its producing method |
| WO2005003450A1 (en) * | 2003-07-08 | 2005-01-13 | Kansai Technology Licensing Organization Co., Ltd. | Process for production of aliphatic polyester composition, pulp and cellulosic fiber to be used therein, and process for microfibrillation thereof |
| JP2006089643A (en) * | 2004-09-24 | 2006-04-06 | Mitsubishi Plastics Ind Ltd | Resin composition and molded body thereof |
| JP2007138106A (en) * | 2005-11-22 | 2007-06-07 | Unitika Ltd | Resin composition |
| JP2008024795A (en) * | 2006-07-19 | 2008-02-07 | Kyoto Univ | Microfibrillated cellulose-containing resin molded product with improved strength |
| US7378149B2 (en) | 2001-12-26 | 2008-05-27 | Kansai Technology Licensing Organization Co, Ltd. | High strength material using cellulose microfibrils |
| JP2008150492A (en) * | 2006-12-18 | 2008-07-03 | Daicel Polymer Ltd | Resin composition |
| WO2014034071A1 (en) * | 2012-08-31 | 2014-03-06 | 東レ株式会社 | Thermoplastic resin composition and molded article |
| JP2018511309A (en) * | 2015-03-12 | 2018-04-26 | タイムプラスト インターナショナル，エルエルシー | Composition for plastic degradation |
| KR101877703B1 (en) * | 2018-01-24 | 2018-07-12 | 충남대학교산학협력단 | Manufacturing method of eco-friendly food packaging films using sea squirt shell protein and polylactic acid |
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| US9243128B2 (en) | 2009-12-11 | 2016-01-26 | Kao Corporation | Composite material |
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1995
- 1995-01-19 JP JP00623495A patent/JP3423094B2/en not_active Expired - Fee Related
Cited By (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH10202690A (en) * | 1997-01-27 | 1998-08-04 | Nissha Printing Co Ltd | Insert film, insert molded product and its manufacture |
| JPH10316739A (en) * | 1997-05-16 | 1998-12-02 | Kanebo Ltd | Refuse sack |
| JP2002121396A (en) * | 2000-10-13 | 2002-04-23 | Yayoi Chemical Industry Co Ltd | Filler for resin and article using the same |
| US7378149B2 (en) | 2001-12-26 | 2008-05-27 | Kansai Technology Licensing Organization Co, Ltd. | High strength material using cellulose microfibrils |
| EP1400328A1 (en) * | 2002-09-18 | 2004-03-24 | Araco Corporation | Fiber board and its producing method |
| US7416779B2 (en) | 2002-09-18 | 2008-08-26 | Toyota Auto Body Co. Ltd. | Fiber board and its producing method |
| WO2005003450A1 (en) * | 2003-07-08 | 2005-01-13 | Kansai Technology Licensing Organization Co., Ltd. | Process for production of aliphatic polyester composition, pulp and cellulosic fiber to be used therein, and process for microfibrillation thereof |
| JP2006089643A (en) * | 2004-09-24 | 2006-04-06 | Mitsubishi Plastics Ind Ltd | Resin composition and molded body thereof |
| JP2007138106A (en) * | 2005-11-22 | 2007-06-07 | Unitika Ltd | Resin composition |
| JP2008024795A (en) * | 2006-07-19 | 2008-02-07 | Kyoto Univ | Microfibrillated cellulose-containing resin molded product with improved strength |
| JP2008150492A (en) * | 2006-12-18 | 2008-07-03 | Daicel Polymer Ltd | Resin composition |
| WO2014034071A1 (en) * | 2012-08-31 | 2014-03-06 | 東レ株式会社 | Thermoplastic resin composition and molded article |
| JP5527489B1 (en) * | 2012-08-31 | 2014-06-18 | 東レ株式会社 | Thermoplastic resin composition and molded article |
| JP2018511309A (en) * | 2015-03-12 | 2018-04-26 | タイムプラスト インターナショナル，エルエルシー | Composition for plastic degradation |
| KR101877703B1 (en) * | 2018-01-24 | 2018-07-12 | 충남대학교산학협력단 | Manufacturing method of eco-friendly food packaging films using sea squirt shell protein and polylactic acid |
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