JPH0593318A - Microorganism degradable conjugate fiber and its nonwoven fabric - Google Patents
Microorganism degradable conjugate fiber and its nonwoven fabricInfo
- Publication number
- JPH0593318A JPH0593318A JP3277247A JP27724791A JPH0593318A JP H0593318 A JPH0593318 A JP H0593318A JP 3277247 A JP3277247 A JP 3277247A JP 27724791 A JP27724791 A JP 27724791A JP H0593318 A JPH0593318 A JP H0593318A
- Authority
- JP
- Japan
- Prior art keywords
- poly
- fiber
- give
- conjugate fiber
- caprolactone
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
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- Nonwoven Fabrics (AREA)
- Biological Depolymerization Polymers (AREA)
- Artificial Filaments (AREA)
- Multicomponent Fibers (AREA)
- Spinning Methods And Devices For Manufacturing Artificial Fibers (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、熱接着性を有する微生
物分解性複合繊維及びそれを用いた不織布に関するもの
である。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a heat-adhesive microbial degradable composite fiber and a nonwoven fabric using the same.
【０００２】[0002]
【従来の技術】従来、漁業や農業、土木用として用いら
れる産業資材用繊維としては、強度及び耐候性の優れた
ものが要求されており、主としてポリアミド、ポリエス
テル、ビニロン、ポリオレフィン等からなるものが使用
されている。しかし、これらの繊維は自己分解性がな
く、使用後、海や山野に放置すると種々の公害を引き起
こすという問題がある。この問題は、使用後、焼却、埋
め立てあるいは回収再生により処理すれば一応解決され
るが、これらの処理には多大の費用を要するため、現実
には海や山野に放置され、景観を損なうばかりでなく、
鳥や海洋生物、ダイバー等に絡みついて殺傷したり、船
のスクリューに絡みついて船舶事故を起こしたりする事
態がしばしば発生している。2. Description of the Related Art Conventionally, fibers having excellent strength and weather resistance are required as fibers for industrial materials used for fishing, agriculture, and civil engineering, and those mainly composed of polyamide, polyester, vinylon, polyolefin and the like are required. It is used. However, these fibers are not self-degradable, and there is a problem in that they cause various pollution when left in the sea or mountains after use. This problem can be solved by incineration, landfilling or recovery and recycling after use, but since such processing requires a large amount of money, it is actually left in the sea or mountains and damages the landscape. Without
It often happens that birds, marine life, and divers get entangled and killed, or they get entangled with the screw of a ship and cause a ship accident.
【０００３】また、使い捨ておむつ、使い捨ておしぼり
や生理用ナプキンについても主として経済性からポリオ
レフィン、ポリエステル、ポリアミド等の合成繊維が使
用されているが、これらは自然分解性に乏しいため、使
用後は止むを得ず焼却されているのが現状である。Also, for disposable diapers, disposable towels and sanitary napkins, synthetic fibers such as polyolefins, polyesters and polyamides are mainly used because of their economical efficiency. However, since these are not naturally degradable, they must be stopped after use. The current situation is that it is incinerated without getting it.
【０００４】このような問題を解決する方法として、自
然分解性（微生物分解性又は生分解性又は加水分解性）
の素材を用いることが考えられる。As a method for solving such a problem, there is a natural degradability (biodegradability, biodegradability or hydrolysis).
It is possible to use the material of.
【０００５】従来、自然分解性ポリマーとして、セルロ
ーズやキチン等の多糖類、カット・グット（腸線）や再
生コラーゲン等の蛋白質やポリペプチド（ポリアミノ
酸）、微生物が自然界で作るポリ−３−ヒドロキシブチ
レートのようなポリ（β−ヒドロキシアルカノエート)
又はその共重合体、ポリグリコリドやポリラクチドのよ
うなポリ（α−オキシ酸) 、ポリ−ε−カプロラクトン
のようなポリ（ω−ヒドロキシアルカノエート) 等の合
成脂肪族ポリエステル等がよく知られている。Conventionally, as naturally degradable polymers, polysaccharides such as cellulose and chitin, proteins and polypeptides (polyamino acids) such as cut gut (intestinal line) and regenerated collagen, and poly-3-hydroxybutyrate produced by microorganisms in nature. Rate-like poly (β-hydroxyalkanoate)
Also known are copolymers thereof, poly (α-oxy acids) such as polyglycolide and polylactide, and synthetic aliphatic polyesters such as poly (ω-hydroxyalkanoate) such as poly-ε-caprolactone. ..
【０００６】しかし、一般的にセルローズ等の多糖類は
自然分解速度が比較的遅く、ごみ埋立地のように十分に
土壌と接触することの少ない場合には、数年間もその形
態をとどめている場合が多く、現実に問題となってい
る。また、一般的に多糖類は熱可塑性でないため、その
加工や用途において一部に制限を受けるという問題があ
った。However, in general, polysaccharides such as cellulose have a relatively slow rate of spontaneous decomposition, and remain in the form for several years when they do not come into sufficient contact with soil such as landfill sites. Often this is a real problem. Further, since polysaccharides are generally not thermoplastic, there is a problem in that they are partially limited in their processing and uses.
【０００７】また、その他のポリマーから繊維を製造す
る場合にも、湿式紡糸法で製造しなければならなかった
り、素材のコストが極めて高いため製造原価が高価にな
ったり、高強度の繊維を得ることができなかったりする
という問題があった。Also, when fibers are produced from other polymers, they must be produced by a wet spinning method, the cost of materials is extremely high, the production cost is high, and fibers of high strength are obtained. There was a problem that I could not do it.
【０００８】ポリ−ε−カプロラクトンやポリ−β−プ
ロピオラクトンは、比較的安価な完全生分解性の合成高
分子であり溶融紡糸が可能であるが、融点が60〜100℃
と低いために、その用途が一部制限されるという問題が
あった。したがって、これらの単独成分からなる繊維
は、ホットメルトタイプの繊維状接着剤とはなり得て
も、熱接着温度で実用上十分な力学的強度を保持するよ
うな熱接着性繊維とはなり得ないという限界があった。Poly-ε-caprolactone and poly-β-propiolactone are relatively inexpensive and completely biodegradable synthetic polymers that can be melt-spun, but have a melting point of 60 to 100 ° C.
Therefore, there was a problem in that its use was partially limited. Therefore, a fiber composed of these single components may be a hot-melt type fibrous adhesive, but may be a heat-adhesive fiber that retains practically sufficient mechanical strength at the heat-bonding temperature. There was a limit that there was no.
【０００９】また、ポリ (β−ヒドロキシアルカノエー
ト) 又はその共重合体は熱可塑性であるが、実際に溶融
紡糸をしても曳糸性に乏しく、低い強度レベルの糸条し
か得られないという問題があった。Further, although poly (β-hydroxyalkanoate) or its copolymer is thermoplastic, it has a poor spinnability even when actually melt-spun, and only a yarn having a low strength level can be obtained. There was a problem.
【００１０】さらに、安価な自然崩壊性の素材として、
ポリエチレンに澱粉を配合したものが検討されており、
直鎖状低密度ポリエチレンに澱粉を約６％配合して製膜
したフィルムが買物袋として一部実用化されている。し
かし、このような澱粉を配合したポリエチレンから繊維
を製造しても、強度等の機械的特性が著しく劣ったもの
となり、高強度を必要とする産業資材用として使用する
ことはできない。また、ポリエチレン成分が完全に生分
解されないために、根本的な解決策とはなり得ない。Further, as an inexpensive material which is naturally disintegrating,
A mixture of polyethylene and starch is being studied,
A film formed by mixing linear low-density polyethylene with about 6% starch has been partially put into practical use as a shopping bag. However, even if fibers are produced from polyethylene mixed with such starch, the mechanical properties such as strength are remarkably inferior and cannot be used for industrial materials requiring high strength. It also cannot be a fundamental solution because the polyethylene component is not completely biodegradable.
【００１１】[0011]
【発明が解決しようとする課題】本発明は、比較的安価
で、かつ、実用に供することができる一定の耐熱性と強
度を有し、自然界で完全に分解される熱接着性を有する
複合繊維及びそれを用いた熱接着不織布を提供しようと
するものである。DISCLOSURE OF THE INVENTION The present invention is a composite fiber which is relatively inexpensive, has a certain level of heat resistance and strength that can be put to practical use, and has thermal adhesiveness that is completely decomposed in the natural world. And a heat-bonded nonwoven fabric using the same.
【００１２】[0012]
【課題を解決するための手段】本発明は、上記課題を解
決するものであり、その要旨は、(1) ポリ（β−ヒドロ
キシアルカノエート) 又はその共重合体を芯成分とし、
ポリ−ε−カプロラクトン及び／又はポリ−β−プロピ
オラクトンを鞘成分とする微生物分解性複合繊維及び
(2)この複合繊維を用いて製造した熱接着不織布にあ
る。なお、本発明の複合繊維には、芯鞘成分それぞれの
基本特性を損なわない範囲内で少量の他の微生物分解性
成分を含有するものも含まれる。Means for Solving the Problems The present invention is to solve the above problems, and its gist is (1) poly (β-hydroxyalkanoate) or a copolymer thereof as a core component,
Microbiodegradable composite fiber containing poly-ε-caprolactone and / or poly-β-propiolactone as a sheath component, and
(2) A heat-bonded non-woven fabric manufactured using this composite fiber. The conjugate fiber of the present invention also includes those containing a small amount of other microbial-degradable component within the range that does not impair the basic characteristics of each core-sheath component.
【００１３】以下、本発明について詳細に説明する。本
発明において芯成分として用いられるポリ（β−ヒドロ
キシアルカノエート) 又はその共重合体としては、ポリ
−３−ヒドロキシプロピオネート、ポリ−３−ヒドロキ
シブチレート、ポリ−３−ヒドロキシカプロレート、ポ
リ−３−ヒドロキシヘプタノエート、ポリ−３−ヒドロ
キシオクタノエート及びこれらとポリ−３−ヒドロキシ
バリレートやポリ−４−ヒドロキシブチレートとの共重
合体等が挙げられる。この中でも、最も好ましいものは
ポリ−３−ヒドロキシブチレートとポリ−３−ヒドロキ
シバリレートとの共重合体及びポリ−３−ヒドロキシブ
チレートとポリ−４−ヒドロキシブチレートとの共重合
体である。芯成分には、鞘成分の融点より高い100℃以
上の融点を有するものを使用することが望ましい。The present invention will be described in detail below. Examples of the poly (β-hydroxyalkanoate) used as the core component in the present invention or a copolymer thereof include poly-3-hydroxypropionate, poly-3-hydroxybutyrate, poly-3-hydroxycaprolate, Examples thereof include poly-3-hydroxyheptanoate, poly-3-hydroxyoctanoate, and copolymers of these with poly-3-hydroxyvalerate and poly-4-hydroxybutyrate. Among these, the most preferable are copolymers of poly-3-hydroxybutyrate and poly-3-hydroxyvalerate and copolymers of poly-3-hydroxybutyrate and poly-4-hydroxybutyrate. .. It is desirable to use a core component having a melting point of 100 ° C. or higher, which is higher than that of the sheath component.
【００１４】一方、鞘成分として用いられるポリ−ε−
カプロラクトン又はポリ−β−プロピオラクトンは、JI
S K 6760に準じて測定したメルトフローレート（単位：
ｇ／10min)が25以下、好ましくは10以下のものが適当で
ある。On the other hand, poly-ε-used as a sheath component
Caprolactone or poly-β-propiolactone is JI
Melt flow rate measured according to SK 6760 (unit:
A value of g / 10 min) of 25 or less, preferably 10 or less is suitable.
【００１５】本発明の複合繊維において、芯鞘複合比は
１／５〜５／１、好ましくは２／３〜３／２とするのが
望ましい。In the composite fiber of the present invention, the core-sheath composite ratio is preferably 1/5 to 5/1, more preferably 2/3 to 3/2.
【００１６】本発明の複合繊維は、ポリ（β−ヒドロキ
シアルカノエート) 又はその共重合体を芯成分とし、高
重合度のポリ−ε−カプロラクトン及び／又はポリ−β
−プロピオラクトンを鞘成分として、溶融紡糸し、延伸
することにより製造することができる。The composite fiber of the present invention comprises poly (β-hydroxyalkanoate) or its copolymer as a core component and has a high degree of polymerization of poly-ε-caprolactone and / or poly-β.
-Propiolactone can be produced by melt spinning and stretching with a sheath component.
【００１７】溶融紡糸の温度は、使用する芯鞘両成分の
組成や重合度により異なるが200〜300℃とすることが望
ましい。紡糸温度が200℃未満では溶融押出しが困難で
あり、300℃を超えると熱分解が顕著となり高強度の繊
維を得ることが困難となる。The temperature of melt spinning varies depending on the composition of both core-sheath components used and the degree of polymerization, but is preferably 200 to 300 ° C. If the spinning temperature is less than 200 ° C, melt extrusion is difficult, and if it exceeds 300 ° C, thermal decomposition becomes remarkable and it becomes difficult to obtain high-strength fibers.
【００１８】溶融紡出された糸条は、空冷又は水冷後、
一旦巻き取った後又は巻き取らずにそのまま、１段又は
２段以上の冷延伸もしくは熱延伸に供される。全延伸倍
率は、目的とする繊維 (フイラメント又はステープル)
の要求性能により異なるが、3.0ｇ／ｄ以上の引張強度
を維持するには2.0〜3.2倍に延伸することが必要であ
る。The melt spun yarn is air-cooled or water-cooled,
After being wound once or without being wound, it is subjected to one-stage or two-stage or more cold stretching or hot stretching. The total draw ratio is the target fiber (filament or staple)
Although it depends on the required performance of No. 3, it is necessary to stretch the film 2.0 to 3.2 times in order to maintain the tensile strength of 3.0 g / d or more.
【００１９】このようにして得られる本発明の複合繊維
は、前述のように実用に耐え得る一定の耐熱性と優れた
強度特性を備えながら、熱接着性と微生物分解性を有す
るものである。したがって、本発明の繊維は短繊維不織
布やスパンボンド法による長繊維不織布のようなウエブ
を熱接着法で固定する不織布として特に有用であり、そ
れ自体が完全な生分解性を有する。なお、この場合の熱
接着法としては、加熱フラットロール又はエンボスロー
ルによる熱圧着法や熱風を利用したサーマルスルーのよ
うな熱融着法が有効である。The thus-obtained composite fiber of the present invention has thermal adhesiveness and microbial degradability while having a certain level of heat resistance that can withstand practical use and excellent strength characteristics as described above. Therefore, the fiber of the present invention is particularly useful as a non-woven fabric for fixing a web such as a short-fiber non-woven fabric or a long-fiber non-woven fabric by the spunbond method by a heat-bonding method, and has a complete biodegradability itself. In this case, as the heat-bonding method, a heat-bonding method such as a thermocompression bonding method using a heated flat roll or an embossing roll or a thermal through method using hot air is effective.
【００２０】[0020]
【作用】本発明の複合繊維は、芯成分を構成するポリ
（β−ヒドロキシアルカノエート) 又はその共重合体の
融点が、鞘成分を構成するポリ−ε−カプロラクトン及
び／又はポリ−β−プロピオラクトンの融点 (60〜100
℃) よりも高いために、例えばこれらの短繊維不織布を
最も一般的な乾式法である熱接着法で製造する場合、熱
接着温度を鞘成分の融点近傍に設定することにより短繊
維ウエブはその形態を維持したまま短繊維間で熱融着固
定される。これは、本発明の芯鞘複合糸の場合には両成
分の界面での接着力が優れる上に、芯成分を構成する高
融点成分が耐熱的及び力学的強度を支えるために、見掛
け上の耐熱性が著しく向上するためと考えられる。In the conjugate fiber of the present invention, the melting point of poly (β-hydroxyalkanoate) or its copolymer constituting the core component is such that the poly-ε-caprolactone and / or poly-β-propene constituting the sheath component is Melting point of piolactone (60-100
C.), for example, when these short fiber nonwoven fabrics are produced by the heat bonding method, which is the most general dry method, the short fiber web is produced by setting the heat bonding temperature near the melting point of the sheath component. The fibers are fixed by heat fusion while maintaining the shape. This is because, in the case of the core-sheath composite yarn of the present invention, the adhesive strength at the interface between both components is excellent, and the high melting point component constituting the core component supports heat resistance and mechanical strength, and therefore it is apparent. It is considered that the heat resistance is significantly improved.
【００２１】[0021]
【実施例】次に、本発明を実施例によりさらに具体的に
説明する。なお、引張強度はJIS L 1013に準じて測定し
た。また、不織布の引張強力は幅３cm、長さ10cmの試験
片を用い、JIS L 1096に記載のストリップ法に準じて測
定した。EXAMPLES Next, the present invention will be described more specifically by way of examples. The tensile strength was measured according to JIS L 1013. The tensile strength of the non-woven fabric was measured according to the strip method described in JIS L 1096 using a test piece having a width of 3 cm and a length of 10 cm.
【００２２】実施例１ 分子量が約50,000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（共重合モル
比：約90／10）を芯成分に用い、メルトフロレートが４
のポリ−ε−カプロラクトンを鞘成分に用いて、芯鞘複
合比１／１で、直径0.35mmの紡糸孔を30個有する紡糸口
金を使用して、紡糸温度260℃で溶融紡出し、1,200m／m
inの速度で巻き取った。次に、40〜50℃で、全延伸倍率
が2.2倍になるように２段延伸し、引き続き押込ギア式
クリンパー（クリンパー温度：50℃、ニップ圧：3.0 kg
／cm2、押込圧：3.0kg／cm2）に導入して捲縮を与えた
後、油剤付与、乾燥を行い、長さ約51mmにカットして単
糸繊度５デニールのステープル・ファイバーを得た。こ
のステープル・ ファイバーの引張強度は4.2ｇ／ｄであ
った。次に、このステープル・ ファイバーをカードに掛
け、短繊維ウエブを形成した後、70℃の熱風炉中を通過
させ、目付が30ｇ／m2の短繊維不織布を得た。得られた
不織布は、引張強力が2800ｇ／３cmで、極めて均一で、
機械的特性に優れたものであった。この不織布を土壌中
に２カ月間埋入したところ、不織布としての形状をとど
めておらず、極めて良好な微生物分解性を示した。Example 1 Poly-3-hydroxybutyrate having a molecular weight of about 50,000 /
Poly-3-hydroxyvalerate copolymer (copolymerization molar ratio: about 90/10) was used as the core component, and the melt florate was 4
Poly- [epsilon] -caprolactone is used as a sheath component, the core-sheath composite ratio is 1/1, and a spinneret having 30 spinning holes with a diameter of 0.35 mm is used. / M
It was wound up at in speed. Next, two-stage stretching was performed at 40 to 50 ° C so that the total stretching ratio was 2.2 times, and subsequently, a pushing gear type crimper (crimper temperature: 50 ° C, nip pressure: 3.0 kg).
/ Cm 2 , indentation pressure: 3.0 kg / cm 2 ) and crimping it, and then applying an oil agent and drying it and cutting it to a length of about 51 mm to obtain staple fiber with a single yarn fineness of 5 denier. It was The tensile strength of this staple fiber was 4.2 g / d. Next, this staple fiber was hung on a card to form a short fiber web, which was then passed through a hot air oven at 70 ° C. to obtain a short fiber nonwoven fabric having a basis weight of 30 g / m 2 . The resulting nonwoven fabric has a tensile strength of 2800 g / 3 cm and is extremely uniform.
It had excellent mechanical properties. When this non-woven fabric was embedded in soil for 2 months, it did not retain its shape as a non-woven fabric and exhibited extremely good microbial degradability.
【００２３】比較例１ 実施例１で用いたと同じポリ−ε−カプロラクトンを単
独で用いて、実施例１とほぼ同一条件下で製造した短繊
維ウエブを、同様に70℃の熱風炉中を通し、目付が30ｇ
／m2の短繊維不織布を得た。得られた不織布は、引張強
力が1600ｇ／３cmと低く、しかも均一性に劣るものであ
った。Comparative Example 1 A short fiber web produced by using the same poly-ε-caprolactone used in Example 1 alone under substantially the same conditions as in Example 1 was also passed through a hot air oven at 70 ° C. , Weight is 30g
A short-fiber non-woven fabric of / m 2 was obtained. The resulting nonwoven fabric had a low tensile strength of 1600 g / 3 cm and was poor in uniformity.
【００２４】[0024]
【発明の効果】本発明によれば、実用に耐え得る一定の
耐熱性と強度特性を有し、かつ微生物分解性を有する複
合繊維及びそれを用いた熱接着不織布が提供される。本
発明の複合繊維及びそれから製造される熱接着不織布
は、生活用資材、衛生材、廃棄物処理材、ワイピングク
ロス、漁業用資材、農業資材、土木用資材等として好適
であり、使用後微生物が存在する環境（土中又は水中）
に放置しておけば一定期間後には完全に生分解されるた
め、特別な廃棄物処理を必要とせず、公害防止に有用で
ある。Industrial Applicability According to the present invention, there are provided a composite fiber having certain heat resistance and strength characteristics that can be practically used and having biodegradability, and a heat-bonded nonwoven fabric using the same. The composite fiber of the present invention and the heat-bonded non-woven fabric produced therefrom are suitable as household materials, sanitary materials, waste disposal materials, wiping cloths, fishery materials, agricultural materials, civil engineering materials, etc. Existing environment (underground or underwater)
If left undisturbed, it will be completely biodegraded after a certain period of time, so no special waste treatment is required and it is useful for pollution prevention.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 金元 直貴 京都府宇治市宇治小桜23番地 ユニチカ株 式会社中央研究所内 ─────────────────────────────────────────────────── ─── Continued Front Page (72) Inventor Naoki Kanemoto 23 Uji Kozakura, Uji City, Kyoto Prefecture Unitika Ltd. Central Research Laboratory
Claims (3)
又はその共重合体を芯成分とし、ポリ−ε−カプロラク
トン及び／又はポリ−β−プロピオラクトンを鞘成分と
する微生物分解性複合繊維。1. A poly (β-hydroxyalkanoate)
Alternatively, a biodegradable conjugate fiber comprising a copolymer thereof as a core component and poly-ε-caprolactone and / or poly-β-propiolactone as a sheath component.
ト又はその共重合体である請求項１の微生物分解性複合
繊維。2. The biodegradable conjugate fiber according to claim 1, wherein the core component is poly-3-hydroxybutyrate or a copolymer thereof.
性複合繊維を用いて製造された熱接着不織布。3. A heat-bonded non-woven fabric produced by using the microbial degradable conjugate fiber according to claim 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3277247A JPH0593318A (en) | 1991-09-27 | 1991-09-27 | Microorganism degradable conjugate fiber and its nonwoven fabric |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3277247A JPH0593318A (en) | 1991-09-27 | 1991-09-27 | Microorganism degradable conjugate fiber and its nonwoven fabric |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0593318A true JPH0593318A (en) | 1993-04-16 |
Family
ID=17580870
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP3277247A Pending JPH0593318A (en) | 1991-09-27 | 1991-09-27 | Microorganism degradable conjugate fiber and its nonwoven fabric |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0593318A (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1994016135A1 (en) * | 1993-01-07 | 1994-07-21 | Unitika Ltd | Binder fiber and nonwoven fabric produced therefrom |
| US5489470A (en) * | 1994-01-28 | 1996-02-06 | The Procter & Gamble Company | Biodegradable copolymers and plastic articles comprising biodegradable copolymers |
| US5498692A (en) * | 1994-01-28 | 1996-03-12 | The Procter & Gamble Company | Biodegradable copolymers and plastic articles comprising biodegradable copolymers |
| US5502116A (en) * | 1994-01-28 | 1996-03-26 | The Procter & Gamble Company | Biodegradable copolymers and plastic articles comprising biodegradable copolymers of 3-hydroxyhexanoate |
| US5593778A (en) * | 1993-09-09 | 1997-01-14 | Kanebo, Ltd. | Biodegradable copolyester, molded article produced therefrom and process for producing the molded article |
| WO1997002375A1 (en) * | 1995-06-30 | 1997-01-23 | Kimberly-Clark Worldwide, Inc. | Water-degradable multicomponent fibers and nonwovens |
| US5646077A (en) * | 1993-01-07 | 1997-07-08 | Unitika Ltd | Binder fiber and nonwoven fabrics using the fiber |
| US5685756A (en) * | 1994-01-28 | 1997-11-11 | The Procter & Gamble Company | Nonwoven materials comprising biodegradable copolymers |
| US5688582A (en) * | 1995-03-08 | 1997-11-18 | Unitika Ltd. | Biodegradable filament nonwoven fabrics and method of manufacturing the same |
| EP0669358A4 (en) * | 1993-09-09 | 1998-01-28 | Kanebo Ltd | Biodegradable copolyester, molding produced therefrom, and process for producing the molding. |
| US5916678A (en) * | 1995-06-30 | 1999-06-29 | Kimberly-Clark Worldwide, Inc. | Water-degradable multicomponent fibers and nonwovens |
| US5990271A (en) * | 1994-01-28 | 1999-11-23 | The Procter & Gamble Company | Films and absorbent articles comprising a biodegradable polyhydroxyalkanoate comprising 3-hydroxybutyrate and 3-hydroxyhexanoate comonomer units |
| US6143947A (en) * | 1996-01-29 | 2000-11-07 | The Procter & Gamble Company | Fibers, nonwoven fabrics and absorbent articles comprising a biodegradable polyhydroxyalkanoate comprising 3-hydroxybutyrate and 3-hydroxyhexanoate |
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-
1991
- 1991-09-27 JP JP3277247A patent/JPH0593318A/en active Pending
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|---|---|---|---|---|
| US5554442A (en) * | 1993-01-07 | 1996-09-10 | Unitika Ltd. | Binder fiber and nonwoven fabrics using the fiber |
| WO1994016135A1 (en) * | 1993-01-07 | 1994-07-21 | Unitika Ltd | Binder fiber and nonwoven fabric produced therefrom |
| US5646077A (en) * | 1993-01-07 | 1997-07-08 | Unitika Ltd | Binder fiber and nonwoven fabrics using the fiber |
| EP0669358A4 (en) * | 1993-09-09 | 1998-01-28 | Kanebo Ltd | Biodegradable copolyester, molding produced therefrom, and process for producing the molding. |
| US5593778A (en) * | 1993-09-09 | 1997-01-14 | Kanebo, Ltd. | Biodegradable copolyester, molded article produced therefrom and process for producing the molded article |
| US6013590A (en) * | 1994-01-28 | 2000-01-11 | The Procter & Gamble Company | Fibers, nonwoven fabrics, and absorbent articles comprising a biodegradable polyhydroxyalkanoate comprising 3-hydroxybutyrate and 3-hydroxyhexanoate |
| US5990271A (en) * | 1994-01-28 | 1999-11-23 | The Procter & Gamble Company | Films and absorbent articles comprising a biodegradable polyhydroxyalkanoate comprising 3-hydroxybutyrate and 3-hydroxyhexanoate comonomer units |
| US6027787A (en) * | 1994-01-28 | 2000-02-22 | The Procter & Gamble Company | Films and absorbent articles comprising a biodegradable polyhydroxyalkanoate comprising 3-hydroxybutyrate and 3-hydroxyhexanoate comonomer units |
| US5602227A (en) * | 1994-01-28 | 1997-02-11 | The Procter & Gamble Company | Biodegradable copolymers |
| US5618855A (en) * | 1994-01-28 | 1997-04-08 | The Procter & Gamble Company | Biodegradable copolymers and plastic articles comprising biodegradable copolymers |
| US5502116A (en) * | 1994-01-28 | 1996-03-26 | The Procter & Gamble Company | Biodegradable copolymers and plastic articles comprising biodegradable copolymers of 3-hydroxyhexanoate |
| US5685756A (en) * | 1994-01-28 | 1997-11-11 | The Procter & Gamble Company | Nonwoven materials comprising biodegradable copolymers |
| USRE36548E (en) * | 1994-01-28 | 2000-02-01 | The Procter & Gamble Company | Biodegradable copolymers |
| US5498692A (en) * | 1994-01-28 | 1996-03-12 | The Procter & Gamble Company | Biodegradable copolymers and plastic articles comprising biodegradable copolymers |
| US5747584A (en) * | 1994-01-28 | 1998-05-05 | The Procter & Gamble Company | Nonwoven materials comprising biodegradable copolymers |
| US5489470A (en) * | 1994-01-28 | 1996-02-06 | The Procter & Gamble Company | Biodegradable copolymers and plastic articles comprising biodegradable copolymers |
| US5536564A (en) * | 1994-01-28 | 1996-07-16 | The Procter & Gamble Company | Biodegradable copolymers and plastic articles comprising biodegradable copolymers of 3-hydroxyhexanoate |
| US5688582A (en) * | 1995-03-08 | 1997-11-18 | Unitika Ltd. | Biodegradable filament nonwoven fabrics and method of manufacturing the same |
| EP0731198A3 (en) * | 1995-03-08 | 1998-12-02 | Unitika Ltd. | Biodegradable filament nonwoven fabrics and method of manufacturing the same |
| KR100404899B1 (en) * | 1995-03-08 | 2004-01-28 | 유니티카 가부시끼가이샤 | Biodegradable filament nonwoven fabric and its manufacturing method |
| US6415531B1 (en) | 1995-05-23 | 2002-07-09 | Sharp Kabushiki Kaisha | Plane-shaped lighting device and a display using such a device |
| US5916678A (en) * | 1995-06-30 | 1999-06-29 | Kimberly-Clark Worldwide, Inc. | Water-degradable multicomponent fibers and nonwovens |
| WO1997002375A1 (en) * | 1995-06-30 | 1997-01-23 | Kimberly-Clark Worldwide, Inc. | Water-degradable multicomponent fibers and nonwovens |
| US6143947A (en) * | 1996-01-29 | 2000-11-07 | The Procter & Gamble Company | Fibers, nonwoven fabrics and absorbent articles comprising a biodegradable polyhydroxyalkanoate comprising 3-hydroxybutyrate and 3-hydroxyhexanoate |
| WO2025089095A1 (en) * | 2023-10-25 | 2025-05-01 | 株式会社カネカ | Fibers and non-woven fabric |
| WO2025105082A1 (en) * | 2023-11-14 | 2025-05-22 | 株式会社カネカ | Fiber and method for producing same |
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