JPH06340753A - Degradable card - Google Patents
Degradable cardInfo
- Publication number
- JPH06340753A JPH06340753A JP5131849A JP13184993A JPH06340753A JP H06340753 A JPH06340753 A JP H06340753A JP 5131849 A JP5131849 A JP 5131849A JP 13184993 A JP13184993 A JP 13184993A JP H06340753 A JPH06340753 A JP H06340753A
- Authority
- JP
- Japan
- Prior art keywords
- acid
- card
- lactic acid
- polymer
- test
- 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
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 claims abstract description 44
- 239000004310 lactic acid Substances 0.000 claims abstract description 20
- 235000014655 lactic acid Nutrition 0.000 claims abstract description 20
- 239000000203 mixture Substances 0.000 claims abstract description 15
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Chemical compound OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 claims abstract description 12
- JVTAAEKCZFNVCJ-REOHCLBHSA-N L-lactic acid Chemical compound C[C@H](O)C(O)=O JVTAAEKCZFNVCJ-REOHCLBHSA-N 0.000 claims abstract description 12
- 229920000747 poly(lactic acid) Polymers 0.000 claims abstract description 11
- 239000004626 polylactic acid Substances 0.000 claims abstract description 11
- 229920001169 thermoplastic Polymers 0.000 claims abstract description 10
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229920001577 copolymer Polymers 0.000 claims abstract description 5
- IWHLYPDWHHPVAA-UHFFFAOYSA-N 6-hydroxyhexanoic acid Chemical compound OCCCCCC(O)=O IWHLYPDWHHPVAA-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229930182843 D-Lactic acid Natural products 0.000 claims abstract description 3
- JVTAAEKCZFNVCJ-UWTATZPHSA-N D-lactic acid Chemical compound C[C@@H](O)C(O)=O JVTAAEKCZFNVCJ-UWTATZPHSA-N 0.000 claims abstract description 3
- 229940022769 d- lactic acid Drugs 0.000 claims abstract description 3
- 229920000642 polymer Polymers 0.000 description 31
- 229960000448 lactic acid Drugs 0.000 description 19
- 238000004519 manufacturing process Methods 0.000 description 16
- 239000010410 layer Substances 0.000 description 9
- 229920005989 resin Polymers 0.000 description 9
- 239000011347 resin Substances 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- WHBMMWSBFZVSSR-UHFFFAOYSA-N R3HBA Natural products CC(O)CC(O)=O WHBMMWSBFZVSSR-UHFFFAOYSA-N 0.000 description 6
- 238000000354 decomposition reaction Methods 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 238000000465 moulding Methods 0.000 description 6
- 239000000123 paper Substances 0.000 description 6
- -1 polyethylene terephthalate Polymers 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- 238000009264 composting Methods 0.000 description 5
- WHBMMWSBFZVSSR-UHFFFAOYSA-M 3-hydroxybutyrate Chemical compound CC(O)CC([O-])=O WHBMMWSBFZVSSR-UHFFFAOYSA-M 0.000 description 4
- REKYPYSUBKSCAT-UHFFFAOYSA-N 3-hydroxypentanoic acid Chemical compound CCC(O)CC(O)=O REKYPYSUBKSCAT-UHFFFAOYSA-N 0.000 description 4
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 4
- 239000010408 film Substances 0.000 description 4
- 229920002472 Starch Polymers 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 238000002485 combustion reaction Methods 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- 229920000728 polyester Polymers 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 229920000915 polyvinyl chloride Polymers 0.000 description 3
- 239000004800 polyvinyl chloride Substances 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 235000019698 starch Nutrition 0.000 description 3
- 239000008107 starch Substances 0.000 description 3
- RKDVKSZUMVYZHH-UHFFFAOYSA-N 1,4-dioxane-2,5-dione Chemical compound O=C1COC(=O)CO1 RKDVKSZUMVYZHH-UHFFFAOYSA-N 0.000 description 2
- FMHKPLXYWVCLME-UHFFFAOYSA-N 4-hydroxy-valeric acid Chemical compound CC(O)CCC(O)=O FMHKPLXYWVCLME-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical group N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000002361 compost Substances 0.000 description 2
- 238000007872 degassing Methods 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 229920000139 polyethylene terephthalate Polymers 0.000 description 2
- 239000005020 polyethylene terephthalate Substances 0.000 description 2
- 239000011241 protective layer Substances 0.000 description 2
- 239000002689 soil Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229920005992 thermoplastic resin Polymers 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- IUPHTVOTTBREAV-UHFFFAOYSA-N 3-hydroxybutanoic acid;3-hydroxypentanoic acid Chemical compound CC(O)CC(O)=O.CCC(O)CC(O)=O IUPHTVOTTBREAV-UHFFFAOYSA-N 0.000 description 1
- SJZRECIVHVDYJC-UHFFFAOYSA-N 4-hydroxybutyric acid Chemical compound OCCCC(O)=O SJZRECIVHVDYJC-UHFFFAOYSA-N 0.000 description 1
- 229940006015 4-hydroxybutyric acid Drugs 0.000 description 1
- JJTUDXZGHPGLLC-IMJSIDKUSA-N 4511-42-6 Chemical compound C[C@@H]1OC(=O)[C@H](C)OC1=O JJTUDXZGHPGLLC-IMJSIDKUSA-N 0.000 description 1
- PHOJOSOUIAQEDH-UHFFFAOYSA-N 5-hydroxypentanoic acid Chemical compound OCCCCC(O)=O PHOJOSOUIAQEDH-UHFFFAOYSA-N 0.000 description 1
- 241000894006 Bacteria Species 0.000 description 1
- 229920013642 Biopol™ Polymers 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- 241000699670 Mus sp. Species 0.000 description 1
- 229920000954 Polyglycolide Polymers 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 238000010533 azeotropic distillation Methods 0.000 description 1
- 229920002988 biodegradable polymer Polymers 0.000 description 1
- 239000004621 biodegradable polymer Substances 0.000 description 1
- 229920006167 biodegradable resin Polymers 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- LQZZUXJYWNFBMV-UHFFFAOYSA-N dodecan-1-ol Chemical compound CCCCCCCCCCCCO LQZZUXJYWNFBMV-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005227 gel permeation chromatography Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- JJTUDXZGHPGLLC-UHFFFAOYSA-N lactide Chemical compound CC1OC(=O)C(C)OC1=O JJTUDXZGHPGLLC-UHFFFAOYSA-N 0.000 description 1
- 238000010169 landfilling Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 229930014626 natural product Natural products 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 238000006384 oligomerization reaction Methods 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920001432 poly(L-lactide) Polymers 0.000 description 1
- 229920001610 polycaprolactone Polymers 0.000 description 1
- 239000004632 polycaprolactone Substances 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 239000004633 polyglycolic acid Substances 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000007142 ring opening reaction Methods 0.000 description 1
- 238000006748 scratching Methods 0.000 description 1
- 230000002393 scratching effect Effects 0.000 description 1
- 239000013535 sea water Substances 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- KSBAEPSJVUENNK-UHFFFAOYSA-L tin(ii) 2-ethylhexanoate Chemical compound [Sn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O KSBAEPSJVUENNK-UHFFFAOYSA-L 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Credit Cards Or The Like (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
- Polyesters Or Polycarbonates (AREA)
Abstract
Description
【0001】[0001]
【産業上の利用分野】本発明は分解性カードに関する。
さらに詳しくは、乳酸ポリマーを主体とする熱可塑性ポ
リマー組成物からなり自然環境下で分解性を有する分解
性カードに関するものである。FIELD OF THE INVENTION This invention relates to degradable cards.
More specifically, the present invention relates to a degradable card which is composed of a thermoplastic polymer composition mainly containing lactic acid polymer and has degradability in a natural environment.
【0002】[0002]
【従来の技術】近年、電話をかけるためにはテレホンカ
ード、電車に乗るためには定期乗車券やオレンジカー
ド、更には、コンビニエンスストアーで買物するための
プリペードカード等様々なカードが利用されている。ま
た、誰でも持っているキャッシュカードやクレジットカ
ード、会社によってはアイデンティフィケーションカー
ド、また、会員証等一人で何枚も持っているのがあたり
まえの時代となった。所持するカードが増えると不用に
なるカードも増えるようになった。従来、これらのカー
ドとしてはポリエチレンテレフタレート、ポリ塩化ビニ
ル等の樹脂類または樹脂類をコーティングした紙から作
られた物がもちいられていた。この中で樹脂から製造さ
れたカードは、他のゴミと一緒に焼却処理し、カロリー
源として有効利用するか、または、埋め立て処分されて
いた。2. Description of the Related Art In recent years, various cards such as telephone cards for making telephone calls, commuter passes and orange cards for boarding trains, and prepaid cards for shopping at convenience stores have been used. . In addition, it has become a common era that everyone has many cash cards, credit cards, identification cards, membership cards, etc. depending on the company. The more cards I have, the more cards I get useless. Heretofore, as these cards, those made of resin such as polyethylene terephthalate or polyvinyl chloride or paper coated with resins have been used. Among them, the card made of resin was incinerated together with other garbage to be effectively used as a calorie source, or was disposed of in landfill.
【0003】しかしながら、樹脂を焼却処理する場合
は、他のゴミに比べて燃焼熱が高く、高カロリーである
ため、燃焼炉が熱負荷に耐えるように設計されたものを
用いなければならず経済的に負担が大きい。また、ポリ
塩化ビニルは燃焼時に有毒な塩化水素を発生するという
問題がある。樹脂を埋め立て処理する場合は、ポリエチ
レンテレフタレート、ポリ塩化ビニル等の樹脂は土壌中
で難分解性であるため、分解されずに残ってしまうとい
う問題がある。紙に樹脂をコーティングしたカードは、
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
いためパルプ回収の工程に共する際に中の紙を取り出し
分離する必要があった。However, when the resin is incinerated, the combustion heat is higher and the calories are higher than those of other wastes, so that the combustion furnace must be designed to withstand the heat load, and it is economical. Burden is heavy. In addition, polyvinyl chloride has a problem that it produces toxic hydrogen chloride during combustion. In the case of landfilling the resin, there is a problem that the resin such as polyethylene terephthalate and polyvinyl chloride is hardly decomposed in the soil and remains without being decomposed. Cards coated with resin on paper are
Since there is no degradability in an alkaline solution for recovering pulp from paper, it was necessary to take out and separate the paper inside during the pulp recovery process.
【0004】特開平5−42786では、生分解性の樹
脂である3−ヒドロキシブチレートと3−ヒドロキシバ
リレートとのランダム共重合ポリエステルや3−ヒドロ
キシブチレート主体のポリエステル、或は、ポリカプロ
ラクトンにでんぷんを混合したもの等でカードを成形し
ている。しかしながら、3−ヒドロキシブチレート等で
成形されたカードは強度が弱く、繰り返し使用を要求さ
れるカードとしては満足できる物ではなかった。また、
でんぷんを添加した樹脂で成形されたカードは、かびが
生えたり、置いておくとねずみがかじってしまう等、到
底使用できる様な物ではなかった。In Japanese Unexamined Patent Publication (Kokai) No. 5-42786, a random copolymerized polyester of 3-hydroxybutyrate and 3-hydroxyvalerate, which is a biodegradable resin, a polyester mainly composed of 3-hydroxybutyrate, or polycaprolactone is used. Cards are molded with a mixture of starch. However, the card formed of 3-hydroxybutyrate or the like has a weak strength and is not satisfactory as a card which requires repeated use. Also,
Cards molded from a resin with starch added were not suitable for use at all, such as mold growing on them and mice scratching when left on them.
【0005】一方、熱可塑性樹脂で生分解性のあるポリ
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%生分、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。しかし、上記分解性のある乳酸系ポリマーを
用いたカードは開発されておらず、自然環境下で容易に
分解し、適度な強度と耐久性を持った優れたカードは現
状では皆無である。On the other hand, polylactic acid or a copolymer of lactic acid and other hydroxycarboxylic acid (hereinafter abbreviated as lactic acid-based polymer) has been developed as a thermoplastic resin biodegradable polymer. These polymers are 100% biodegradable within a few months to a year within the body of an animal, and when placed in soil or seawater, they begin to decompose within a few weeks in a moist environment and within one to several years. Furthermore, the decomposition products have the property that they become lactic acid, carbon dioxide, and water that are harmless to the human body. However, a card using the above-mentioned degradable lactic acid-based polymer has not been developed, and at present there is no excellent card that is easily decomposed in a natural environment and has appropriate strength and durability.
【0006】[0006]
【発明が解決しようとする課題】本発明は、自然環境下
で分解可能であり、充分な強度と耐久性を持ったカード
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 card which can be decomposed in a natural environment and has sufficient strength and durability.
【0007】[0007]
【課題を解決するための手段】本発明者らは、乳酸系ポ
リマーを主成分とする樹脂を用いることにより分解性の
あるカードが得られることを見いだし本発明を完成した
ものである。即ち、本発明は、ポリ乳酸系ポリマーを主
成分とする熱可塑性ポリマー組成物からなる分解性カー
ドである。The present inventors have completed the present invention by finding that a degradable card can be obtained by using a resin containing a lactic acid-based polymer as a main component. That is, the present invention is a degradable card composed of a thermoplastic polymer composition containing a polylactic acid-based polymer as a main component.
【0008】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。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(C
L)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。直接縮合する場合は、乳酸または乳酸
と他のヒドトキシカルボン酸を好ましくは有機溶媒、特
にフェニルエーテル系溶媒の存在下で共沸脱水縮合し、
特に好ましくは共沸により留出した溶媒から水を除き実
質的に無水の状態にした溶媒を反応系に戻す方法によっ
て重合することにより、本発明に適した強度を持つ高分
子量のポリ乳酸が得られる。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 polymer used in the present invention is mainly composed of a polylactic acid-based polymer, and other hydroxycarboxylic acids include glycolic acid, 3-hydroxybutyric acid, 4-hydroxybutyric acid, 4-hydroxyvaleric acid and 5
-Hydroxyvaleric acid, 6-hydroxycaproic acid, etc. are used. The polylactic acid-based polymer is formed by dehydration polycondensation of lactic acid or lactic acid and other hydroxycarboxylic acid directly, or lactide which is a cyclic dimer of lactic acid, or a cyclic ester intermediate of hydroxycarboxylic acid, such as glycolic acid
Glycolide (GLD) which is a monomer and ε-caprolactone (C which is a cyclic ester of 6-hydroxycaproic acid
A ring-opening polymerized product may be used by appropriately using a copolymerizable monomer such as L). When directly condensing, lactic acid or lactic acid and other hydroxycarboxylic acid are azeotropically dehydrated and condensed, preferably in the presence of an organic solvent, particularly a phenyl ether solvent,
Particularly preferably, water is removed from the solvent distilled by azeotropic distillation and the substantially anhydrous solvent is returned to the reaction system to carry out polymerization to obtain a high molecular weight polylactic acid having a strength suitable for the present invention. To be Lactic acid as a raw material is L-
It may be lactic acid or D-lactic acid or a mixture thereof.
【0009】乳酸ポリマーには、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−カプロラクタ
ム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。また、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出来るが、組成物の形
状はペレット、棒状、粉状等で用いられる。ポリマーの
平均分子量は特に限定されない。強度を必要とする用途
には通常5万〜100万程度の物が用いられる。5万以
下の分子量ではフィルムや成形物とするには強度が小さ
い。また、分子量が100万より高いと、溶融状態での
粘度が高く成形加工性に劣る。For the lactic acid polymer, a generally known thermoplastic polymer or plasticizer, and various modifiers are used,
A thermoplastic polymer composition. As the known thermoplastic polymer, degradable substances such as polyglycolic acid and poly ε-caprolactam are preferable. The proportion of the lactic acid-based polymer in the thermoplastic polymer composition may be any proportion depending on the desired degradability, but is generally 50%.
The above is preferable. In addition, all known kneading techniques can be applied to the production of the thermoplastic polymer composition, but the composition is used in the form of pellets, rods, powders, or the like. The average molecular weight of the polymer is not particularly limited. Usually, about 50,000 to 1,000,000 objects are used for applications requiring strength. When the molecular weight is 50,000 or less, the strength is low for forming a film or a molded product. If the molecular weight is higher than 1,000,000, the viscosity in the molten state will be high and the moldability will be poor.
【0010】ポリマーの成形方法は特に限定されない
が、通常、押し出しシート成形、プレス成形等で行わ
れ、必要により延伸することもできる。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、その
いくつかを例示する。 押し出し機 : 40mmφ、50rp
m 押し出し温度 : 190〜220℃ Tダイ : スリット0.2mm、
幅150mm 延伸温度 : 50〜150℃ 延伸倍率 : 3〜8 カードは、磁気記録層と感熱記録層とが非磁性基体の同
一面側に設けられており、通常は第1図に示すように非
磁性体5上にまず磁性塗膜からなる磁気記録層4を形成
し、この上に下地層3、低融点非磁性金属の薄膜からな
る感熱記録層2、保護層1を順次積層するが、その他い
かなる方法により得られた物でも良い。カードに記録す
る方法としては、いかなる方法でも良いが、磁気記録、
LSIによる電子記録、光学的記録による方法等が知ら
れている。以下、実施例により本発明を具体的に説明す
る。The method for molding the polymer is not particularly limited, but it is usually carried out by extrusion sheet molding, press molding or the like, and it may be stretched if necessary. The molding conditions are appropriately determined depending on the molding machine, the type of polymer, etc., and some of them will be exemplified. Extruder: 40mmφ, 50rp
m Extrusion temperature: 190 to 220 ° C. T die: Slit 0.2 mm,
Width 150 mm Stretching temperature: 50 to 150 ° C. Stretching ratio: 3 to 8 In the card, the magnetic recording layer and the heat sensitive recording layer are provided on the same side of the non-magnetic substrate, and as shown in FIG. First, a magnetic recording layer 4 made of a magnetic coating film is formed on a magnetic body 5, and an underlayer 3, a heat-sensitive recording layer 2 made of a thin film of a low melting point nonmagnetic metal, and a protective layer 1 are sequentially laminated on the magnetic recording layer 4. It may be obtained by any method. Any method may be used for recording on the card, but magnetic recording,
Methods such as electronic recording by LSI and optical recording are known. Hereinafter, the present invention will be specifically described with reference to examples.
【0011】[0011]
製造例1 L−ラクタイド216g(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 1 216 g (1.5 mol) of L-lactide, 0.01% by weight of tin octoate, and 0.03 lauryl alcohol
Polymerization% was sealed in a thick cylindrical stainless steel polymerization container equipped with a stirrer, deaerated under vacuum for 2 hours, and then replaced with nitrogen gas. This mixture is stirred under a nitrogen atmosphere for 200
Heated at ° C for 3 hours. While maintaining the temperature as it was, the inside of the reaction vessel was depressurized to 3 mmHg by gradually degassing with a vacuum pump through an exhaust pipe and a glass receiver. One hour after the start of degassing, the distillation of the monomer and low-molecular-weight volatile matter disappeared, so the interior of the container was replaced with nitrogen, and the polymer was extracted from the lower part of the container in the form of a string and pelletized to obtain poly L-lactic acid. The molecular weight of this polymer was about 100,000.
【0012】製造例2 90%L−乳酸10.0kgを150℃/50mmHg
で3時間攪拌しながら水を留出させた後、錫末6.2g
を加え、150℃/30mmHgで更に2時間攪拌して
オリゴマー化した。このオリゴマーに錫末28.8gと
ジフェニルエーテル21.1kgを加え、150℃/3
5mmHgで共沸脱水反応を行い、留出した水と溶媒を
水分離器で分離して溶媒のみを反応機に戻した。2時間
後、反応機に戻す有機溶媒を4.6kgのモレキュラー
シーブ3Aを充填したカラムに通してから反応機に戻る
ようにして、150℃/35mmHgで40時間反応を
行い、平均分子量Mw=100,000のポリ乳酸を得
た。この溶液に脱水したジフェニルエーテル44kgを
加え希釈した後、40℃まで冷却して析出した結晶を濾
過し、60℃/50mmHgで乾燥して、ポリ乳酸粉末
6.1kg(収率85%)を得た。この粉末をペレット
化機で処理しペレット化し、ポリ乳酸を得た。このポリ
マーの分子量は約10万であった。Production Example 2 10.0 kg of 90% L-lactic acid was added at 150 ° C./50 mmHg.
After distilling water while stirring for 3 hours, 6.2 g of tin powder
Was added, and the mixture was stirred at 150 ° C./30 mmHg for 2 hours for oligomerization. 28.8 g of tin powder and 21.1 kg of diphenyl ether were added to this oligomer, and the temperature was changed to 150 ° C / 3.
An azeotropic dehydration reaction was performed at 5 mmHg, the distilled water and the solvent were separated by a water separator, and only the solvent was returned to the reactor. After 2 hours, the organic solvent returned to the reactor was passed through a column packed with 4.6 kg of molecular sieve 3A and then returned to the reactor to carry out a reaction at 150 ° C./35 mmHg for 40 hours, and an average molecular weight Mw = 100. 1,000 polylactic acid was obtained. 44 kg of dehydrated diphenyl ether was added to this solution to dilute it, then cooled to 40 ° C. and the precipitated crystals were filtered and dried at 60 ° C./50 mmHg to obtain 6.1 kg of polylactic acid powder (yield 85%). . The powder was treated with a pelletizer to pelletize polylactic acid. The molecular weight of this polymer was about 100,000.
【0013】製造例3 98%DL−乳酸9.2kgから製造例2と同様にして
ポリDL−乳酸を得、ペレット化した。このポリマーの
平均分子量は約10万であった。Production Example 3 Poly DL-lactic acid was obtained from 98% DL-lactic acid 9.2 kg in the same manner as in Production Example 2 and pelletized. The average molecular weight of this polymer was about 100,000.
【0014】製造例4 L−乳酸10.0kgをL−乳酸5.0kgとグリコー
ル酸5.0kgに変えた他は製造例2と同様にしてL−
乳酸とグリコール酸の共重合体を得、ペレット化した。
このポリマーの平均分子量は約10万であった。 以
下、これらのポリマーを用いて、実施例に示すカードを
試作した。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。Production Example 4 L-lactic acid was replaced with 5.0 kg of L-lactic acid and 5.0 kg of glycolic acid instead of 10.0 kg of L-lactic acid in the same manner as in Production Example 2.
A copolymer of lactic acid and glycolic acid was obtained and pelletized.
The average molecular weight of this polymer was about 100,000. Hereinafter, using these polymers, the card shown in the example was manufactured as a prototype. The 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.
【0015】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/minEquipment: 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
【0016】また、カードの物理的特性は、以下の条件
によって試験を行った。 試験場所の状態: 試験場所は、特に指定がない限り、
JIS Z8703に規定する常温常湿(温度20±1
5℃、湿度65±20%)の状態とする。 試験片: 試験片は、カードに切断する前のシート状の
試験から規定の寸法のものを採る。ただし、特に指定が
ない場合には、製品カード自体とする。 引張強さ: 引張強さ試験は、JIS C 2318の
6.3.3(引張強さ及び伸び率)による。 衝撃強さ: 衝撃強さ試験は、カードを堅固な水平板上
に置き、500gの鋼球を30cmの高さからカードの
中央に落とし、カードの割れ、ひびなどの有無を調べ
る。 耐折強さ: 耐折強さ試験は、JIS P 8115に
よる。 こわさ: こわさ試験は、JIS P 8125を準用
する。The physical characteristics of the card were tested under the following conditions. Test site conditions: Test sites are unless otherwise specified.
Room temperature and normal humidity (Temperature 20 ± 1 specified in JIS Z8703
5 ° C., humidity 65 ± 20%). Specimen: Specimen is taken from the sheet-shaped test before cutting into a card and having the specified dimensions. However, the product card itself is used unless otherwise specified. Tensile Strength: The tensile strength test is based on JIS C 2318, 6.3.3 (tensile strength and elongation). Impact strength: In the impact strength test, the card is placed on a solid horizontal plate, a 500 g steel ball is dropped from the height of 30 cm to the center of the card, and the card is checked for cracks or cracks. Folding endurance: The folding endurance test is based on JIS P8115. Stiffness: JIS P 8125 is applied mutatis mutandis to the stiffness test.
【0017】カビ抵抗性: 試料(50×50mm)を
デシケーター中で乾燥後、重量を測定し、滅菌固化した
培地上に試験片を置き、供試菌の胞子懸濁液をスプレイ
接種し、30℃の恒温槽内で培養し、カビの生育の様子
を観察する。4週間後の試験片を流水下で洗浄し、濾紙
で水分を取り、デシケーター中で乾燥後、重量減少を測
定する。 堆肥中分解性: 試料を温度35℃、湿度30%の堆肥
中に埋設して分解性試験を行い、2カ月後の変化を調べ
る。Mold resistance: After drying a sample (50 × 50 mm) in a desiccator, its weight was measured, a test piece was placed on a sterilized and solidified medium, and a spore suspension of a test bacterium was spray-inoculated to give 30 Incubate in a constant temperature bath at ℃ and observe the growth of mold. After 4 weeks, the test piece is washed under running water, water is taken out with a filter paper, dried in a desiccator, and weight loss is measured. Decomposability in compost: A sample is embedded in compost at a temperature of 35 ° C. and a humidity of 30%, and a decomposability test is performed to examine changes after 2 months.
【0018】実施例1 製造例1のポリマーをプレス成形機で温度200℃、圧
力30トンで5分間加圧し、その後40℃で5分間冷却
することで厚さ188μmの透明なシートが得られた。
得られたシート上に磁性塗膜を塗布乾燥して、厚さ15
μmの磁性塗膜からなる磁気記録層を形成した。次に、
この上に、下地層を2μmの厚さに形成し、この上に感
熱記録層、中間層および保護層を順次形成し感熱記録媒
体を作成した。このカードの引張強さは68N/mm2
であった。衝撃強さ試験は合格、耐折強さは200回以
上、こわさは1.76mN・m以上であった。カビ抵抗
性試験では、4週間後にカビの生育は認められなかっ
た。また、堆肥中分解性試験では、2カ月後には外力に
より容易に形が崩れた。Example 1 The polymer of Production Example 1 was pressed with a press molding machine at a temperature of 200 ° C. and a pressure of 30 tons for 5 minutes, and then cooled at 40 ° C. for 5 minutes to obtain a transparent sheet having a thickness of 188 μm. .
A magnetic coating film is applied on the obtained sheet and dried to give a thickness of 15
A magnetic recording layer composed of a magnetic coating film of μm was formed. next,
An underlying layer having a thickness of 2 μm was formed thereon, and a thermosensitive recording layer, an intermediate layer and a protective layer were sequentially formed on the underlayer to prepare a thermosensitive recording medium. The tensile strength of this card is 68 N / mm 2
Met. The impact strength test passed, the folding endurance was 200 times or more, and the stiffness was 1.76 mN · m or more. In the mold resistance test, mold growth was not observed after 4 weeks. Further, in the composting decomposition test, the shape was easily broken by external force after 2 months.
【0019】実施例2 製造例1のポリマーの代わりに、製造例2のポリマーか
ら実施例1と同様の方法で厚さ188μmのシートを
得、実施例1の方法と同様にして感熱記録媒体を作成し
た。このカードの引張強さは68N/mm2 であった。
衝撃強さ試験は合格、耐折強さは200回以上、こわさ
は1.76mN・m以上であった。カビ抵抗性試験で
は、4週間後にカビの生育は認められなかった。また、
堆肥中分解性試験では、2カ月後には外力により容易に
形が崩れた。Example 2 A sheet having a thickness of 188 μm was obtained from the polymer of Production Example 2 in the same manner as in Example 1 in place of the polymer of Production Example 1, and a thermal recording medium was prepared in the same manner as in Example 1. Created. The tensile strength of this card was 68 N / mm 2 .
The impact strength test passed, the folding endurance was 200 times or more, and the stiffness was 1.76 mN · m or more. In the mold resistance test, mold growth was not observed after 4 weeks. Also,
In the composting decomposition test, the shape was easily destroyed by external force after 2 months.
【0020】実施例3 製造例1のポリマーの代わりに、製造例3のポリマーか
ら実施例1と同様の方法で厚さ188μmのシートを
得、実施例1の方法と同様にして感熱記録媒体を作成し
た。このカードの引張強さは60N/mm2 であった。
衝撃強さ試験は合格、耐折強さは200回以上、こわさ
は1.76mN・m以上であった。カビ抵抗性試験で
は、4週間後にカビの生育は認められなかった。また、
堆肥中分解性試験では、2カ月後には外力により容易に
形が崩れた。Example 3 A sheet having a thickness of 188 μm was obtained from the polymer of Production Example 3 in the same manner as in Example 1 instead of the polymer of Production Example 1, and a thermal recording medium was prepared in the same manner as in Example 1. Created. The tensile strength of this card was 60 N / mm 2 .
The impact strength test passed, the folding endurance was 200 times or more, and the stiffness was 1.76 mN · m or more. In the mold resistance test, mold growth was not observed after 4 weeks. Also,
In the composting decomposition test, the shape was easily destroyed by external force after 2 months.
【0021】実施例4 製造例1のポリマーの代わりに、製造例4のポリマーか
ら実施例1と同様の方法で厚さ188μmのシートを
得、実施例1の方法と同様にして感熱記録媒体を作成し
た。このカードの引張強さは52N/mm2 であった。
衝撃強さ試験は合格、耐折強さは200回以上、こわさ
は1.76mN・m以上であった。カビ抵抗性試験で
は、4週間後にカビの生育は認められなかった。また、
堆肥中分解性試験では、2カ月後には外力により容易に
形が崩れた。Example 4 A sheet having a thickness of 188 μm was obtained from the polymer of Production Example 4 in the same manner as in Example 1 instead of the polymer of Production Example 1, and a thermal recording medium was prepared in the same manner as in Example 1. Created. The tensile strength of this card was 52 N / mm 2 .
The impact strength test passed, the folding endurance was 200 times or more, and the stiffness was 1.76 mN · m or more. In the mold resistance test, mold growth was not observed after 4 weeks. Also,
In the composting decomposition test, the shape was easily destroyed by external force after 2 months.
【0022】実施例5 実施例1と同様のポリ乳酸シートを80℃で1時間再結
晶化して得られたシートを実施例1の方法と同様にして
感熱記録媒体を作成した。このカードの引張強さは78
N/mm2 であった。衝撃強さ試験は合格、耐折強さは
200回以上、こわさは1.76mN・m以上であっ
た。カビ抵抗性試験では、4週間後にカビの生育は認め
られなかった。また、堆肥中分解性試験では、2カ月後
には外力により容易に形が崩れた。Example 5 A polylactic acid sheet similar to that of Example 1 was recrystallized at 80 ° C. for 1 hour to obtain a sheet, and a thermal recording medium was prepared in the same manner as in Example 1. The tensile strength of this card is 78
It was N / mm 2 . The impact strength test passed, the folding endurance was 200 times or more, and the stiffness was 1.76 mN · m or more. In the mold resistance test, mold growth was not observed after 4 weeks. Further, in the composting decomposition test, the shape was easily broken by external force after 2 months.
【0023】比較例1 製造例1のポリマーの代わりに、3ーヒドロキシブチレ
ートと3ーヒドロキシバリレートとのランダム共重合ポ
リエステルであるバイオポール(ICI社製)から実施
例1と同様の方法で厚さ188μmのシートを得、実施
例1の方法と同様にして感熱記録媒体を作成した。この
カードの引張強さは24N/mm2 と弱く、衝撃強さ試
験には合格、耐折強さは200回以上、こわさは0.7
3mN・mと低い値であった。カビ抵抗性試験では、4
週間後にカードの2/3以上の面積にカビが生育してい
た。また、堆肥中分解性試験では、2カ月後には消滅し
ていた。Comparative Example 1 Instead of the polymer of Production Example 1, Biopol (manufactured by ICI), which is a random copolymerized polyester of 3-hydroxybutyrate and 3-hydroxyvalerate, was used in the same manner as in Example 1. A 188 μm-thick sheet was obtained, and a thermal recording medium was prepared in the same manner as in Example 1. This card has a low tensile strength of 24 N / mm 2 , passed the impact strength test, a folding endurance of 200 times or more, and a stiffness of 0.7.
It was a low value of 3 mN · m. 4 in mold resistance test
After a week, mold grew on more than 2/3 of the area of the curd. In the compost-degrading test, it disappeared after 2 months.
【0024】比較例2 製造例1のポリマーの代わりに、でんぷんと変性ポリビ
ニルアルコールを主成分とするマタービー(ノバモント
社製)から実施例1と同様の方法で厚さ188μmのシ
ートを得、実施例1の方法と同様にして感熱記録媒体を
作成した。このカードの引張強さは22N/mm2 と弱
く、衝撃強さ試験には合格、耐折強さは200回以上、
こわさは0.53mN・mと低い値であった。カビ抵抗
性試験では、4週間後にカードの2/3以上の面積にカ
ビが生育していた。また、堆肥中分解性試験では、2カ
月後には消滅していた。Comparative Example 2 A sheet having a thickness of 188 μm was obtained in the same manner as in Example 1 from Matterby (manufactured by Novamont) containing starch and modified polyvinyl alcohol as main components instead of the polymer of Production Example 1. A thermosensitive recording medium was prepared in the same manner as in method 1. This card has a low tensile strength of 22 N / mm 2 , passed the impact strength test, and has a folding strength of 200 times or more,
The stiffness was a low value of 0.53 mN · m. In the mold resistance test, after 4 weeks, mold grew on the area of 2/3 or more of the curd. In the compost-degrading test, it disappeared after 2 months.
【0025】[0025]
【発明の効果】本発明による乳酸系ポリマーを主成分と
する熱可塑性樹脂からなる分解性カードは、十分な強度
と耐久性を持ち、更に廃棄物として地中に埋設されたり
海や川に投棄された場合、紙や木等の天然物と同じよう
に自然環境中で比較的短い期間の内に分解する。Industrial Applicability The degradable card made of a thermoplastic resin containing lactic acid-based polymer as a main component according to the present invention has sufficient strength and durability, and is further buried in the ground as waste or dumped in the sea or river. When decomposed, it decomposes in the natural environment within a relatively short period of time like natural products such as paper and wood.
【図面の簡単な説明】[Brief description of drawings]
【図1】 第1図は、カードの断面図である。FIG. 1 is a cross-sectional view of a card.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.5 識別記号 庁内整理番号 FI 技術表示箇所 C08L 67:04 (72)発明者 鈴木 和彦 神奈川県横浜市栄区笠間町1190番地 三井 東圧化学株式会社内─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. 5 Identification number Reference number within the agency FI Technical display location C08L 67:04 (72) Inventor Kazuhiko Suzuki 1190 Kasama-cho, Sakae-ku, Yokohama-shi, Kanagawa Mitsui Toatsu Chemical Co., Ltd. In the company
Claims (3)
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
マー組成物からなる分解性カード。1. A degradable card 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記載の分解性
カード。2. The degradable card 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記載の分解性カード。3. The hydroxycarboxylic acid is glycolic acid,
Alternatively, the degradable card according to claim 1, which is 6-hydroxycaproic acid.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP13184993A JP3290504B2 (en) | 1993-06-02 | 1993-06-02 | Degradable card |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP13184993A JP3290504B2 (en) | 1993-06-02 | 1993-06-02 | Degradable card |
Publications (2)
Publication Number | Publication Date |
---|---|
JPH06340753A true JPH06340753A (en) | 1994-12-13 |
JP3290504B2 JP3290504B2 (en) | 2002-06-10 |
Family
ID=15067556
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP13184993A Expired - Lifetime JP3290504B2 (en) | 1993-06-02 | 1993-06-02 | Degradable card |
Country Status (1)
Country | Link |
---|---|
JP (1) | JP3290504B2 (en) |
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH06298236A (en) * | 1993-04-13 | 1994-10-25 | Mitsui Toatsu Chem Inc | Throwaway food container |
EP0776927A1 (en) | 1995-11-30 | 1997-06-04 | Mitsui Toatsu Chemicals, Inc. | Stretched film of lactic acid-based polymer |
US6350530B1 (en) | 1996-03-26 | 2002-02-26 | Gunze Limited | Biodegradable card base |
US6544607B1 (en) | 1999-02-18 | 2003-04-08 | Mitsui Chemicals, Inc. | Plasticized polyester compositions and films therefrom |
WO2008065749A1 (en) | 2006-11-30 | 2008-06-05 | Seiko Sato | Plant-derived natural biodegradable material |
-
1993
- 1993-06-02 JP JP13184993A patent/JP3290504B2/en not_active Expired - Lifetime
Cited By (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH06298236A (en) * | 1993-04-13 | 1994-10-25 | Mitsui Toatsu Chem Inc | Throwaway food container |
EP0776927A1 (en) | 1995-11-30 | 1997-06-04 | Mitsui Toatsu Chemicals, Inc. | Stretched film of lactic acid-based polymer |
US5766748A (en) * | 1995-11-30 | 1998-06-16 | Mitsui Chemicals, Inc. | Stretched film of lactic acid-based polymer |
US6350530B1 (en) | 1996-03-26 | 2002-02-26 | Gunze Limited | Biodegradable card base |
US6544607B1 (en) | 1999-02-18 | 2003-04-08 | Mitsui Chemicals, Inc. | Plasticized polyester compositions and films therefrom |
WO2008065749A1 (en) | 2006-11-30 | 2008-06-05 | Seiko Sato | Plant-derived natural biodegradable material |
US8349418B2 (en) | 2006-11-30 | 2013-01-08 | Seiko Sato | Plant-derived natural biodegradable material |
Also Published As
Publication number | Publication date |
---|---|
JP3290504B2 (en) | 2002-06-10 |
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