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WO1991000935A1 - Fibre poreuse et sa fabrication - Google Patents

Fibre poreuse et sa fabrication Download PDF

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Publication number
WO1991000935A1
WO1991000935A1 PCT/JP1990/000890 JP9000890W WO9100935A1 WO 1991000935 A1 WO1991000935 A1 WO 1991000935A1 JP 9000890 W JP9000890 W JP 9000890W WO 9100935 A1 WO9100935 A1 WO 9100935A1
Authority
WO
WIPO (PCT)
Prior art keywords
fiber
porous
unit
hydrophilic copolymer
range
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.)
Ceased
Application number
PCT/JP1990/000890
Other languages
English (en)
Japanese (ja)
Inventor
Toshinobu Koshoji
Hironari Honda
Kiyonobu Okamura
Kunio Misoo
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Mitsubishi Chemical Corp
Original Assignee
Mitsubishi Rayon Co Ltd
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Mitsubishi Rayon Co Ltd filed Critical Mitsubishi Rayon Co Ltd
Publication of WO1991000935A1 publication Critical patent/WO1991000935A1/fr
Anticipated expiration legal-status Critical
Priority to KR1019930700329A priority Critical patent/KR930701265A/ko
Ceased legal-status Critical Current

Links

Classifications

    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D5/00—Formation of filaments, threads, or the like
    • D01D5/24—Formation of filaments, threads, or the like with a hollow structure; Spinnerette packs therefor
    • D01D5/247—Discontinuous hollow structure or microporous structure
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/28—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D01F6/30—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds comprising olefins as the major constituent
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/44—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds
    • D01F6/46—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds of polyolefins

Definitions

  • the present invention relates to a porous polyolefin-based fiber. Background technology
  • a method for making the fibers porous for example, a method in which a blowing agent is blended into a thermoplastic polymer, melt-spun, and the foaming agent is decomposed at the spinning stage to cause foaming to make the fibers porous.
  • a blowing agent is blended into a thermoplastic polymer, melt-spun, and the foaming agent is decomposed at the spinning stage to cause foaming to make the fibers porous.
  • the additives for pore formation inorganic salts, organic low molecular weight compounds, etc.
  • hydrophilic fibers Various materials are used as materials for hydrophilic fibers, but attention has been paid to the development of polyolefin steel fibers, which are superior in terms of strength and the like, to applications that require hydrophilicity.
  • hydrophilization treatment is required to develop polyrefin fibers for applications requiring hydrophilicity.
  • a hydrophilizing agent such as a surfactant
  • the obtained hydrophilic fibers are not liable to fall off due to contact with water. Therefore, there is a problem of losing hydrophilicity.
  • good performance fibers cannot be obtained due to poor affinity between the hydrophilic substance and polyolefin. There's a problem. Disclosure of the invention
  • the inventors of the present invention have conducted intensive studies in view of the above-mentioned situation, and as a result, it has been found that excellent results are obtained by melt-spinning and drawing a blend of a hydrophilic copolymer having specific performance in a polyolefin.
  • the present inventors have found that a porous fiber having a porous structure and permanent hydrophilicity and which can simultaneously satisfy various properties such as lightness, soft feel, and water absorption can be obtained. .
  • the porous fiber of the present invention that can achieve these objects has the following formula: One one
  • R 1 and R 2 independently represent a hydrogen or a methyl group, and n is 1 to 9.
  • This porous fiber is obtained by melt-spinning a blend of a hydrophilic copolymer mainly composed of a monomer unit A and an ethylene unit B represented by the above formula, and a polyolefin Y, and is not drawn.
  • a method comprising the steps of:
  • the porous polyolefin-based fiber of the present invention is entirely surrounded by lamellas and a number of longitudinally arranged fibrils connecting the lamellas from the fiber surface to the fiber center.
  • the space has a communicating pore structure It has a large surface area, is very lightweight, has a soft feel, has a clear white appearance without a sense of transparency, and exhibits excellent mechanical properties despite its high porosity.
  • the porous fiber of the present invention since the undrawn fiber obtained by melt-spinning a blend having a specific composition is made porous, the porous fiber is extracted by the extraction method. It does not contain a solvent such as the obtained porous fiber or an additive for forming pores. Therefore, the porous fiber of the present invention is a sanitary material and has a permanent hydrophilic property, so that it is used as a material for clothing that directly touches the skin, such as underwear, which is required to have excellent sweat absorption properties. Or as a medical fabric material. Further, the porous fiber of the present invention can be used as a material for various industrial materials including wipers and adsorption materials by utilizing its large water content and water absorption in pores. is there. BEST MODE FOR CARRYING OUT THE INVENTION
  • the porous fiber of the present invention comprises a hydrophilic copolymer X having a monomer unit A and an ethylene unit B represented by the above-mentioned formula as main components, and a polyolefin Y, And a number of longitudinal arrangements connecting the lamellas. It has a pore structure in which the space surrounded by the fibrils communicates.
  • polystyrene resin examples include polyethylene, polypropylene, poly (3-methylbutene-11), poly (4-methylpentene-11) and the like. be able to.
  • the polyolefin Y it is preferable to use one having a high degree of crystallinity, and it is preferable to use a crystal of an undrawn fiber obtained by melt-spinning a blend obtained by blending a hydrophilic copolymer X described later with a blend. It is preferable to select a polymer having a degree of crystallinity of 40% or more, preferably 50% or more, and a crystal orientation degree of 50% or more, preferably 60% or more. Yes.
  • n in the above formula representing the unit A represents the average degree of polymerization of the alkylene glycol units in the unit A (average of the number of oxyalkylene groups), and is in the range of 1 to 9.
  • polyalkylene glycol (meta) acrylate as a component for introducing unit A becomes a viscous substance, and ethylene as a component for introducing unit B is obtained. This makes it difficult to make a homogeneous reaction between and, making it impossible to obtain hydrophilic copolymer X.
  • n 1 to 2
  • high reactivity is obtained in the reaction between the component for introducing unit A and the component for introducing unit B.
  • units A differing in the degree of polymerization of the alkylene glycol units of the unit A and the types of R 1 and R 2 may be mixed.
  • oxetylene and oxypropylene may be mixed. It may be mixed in the unit of work.
  • the hydrophilic copolymer X tends to contain a large amount of a low molecular weight substance, and the hydrophilic copolymer X is easily eluted from the porous fiber blended with the low molecular weight substance and the polyolefin Y.
  • the ratio of the unit A is more preferably 70 to 15% by weight, and more preferably 70 to 40% by weight. Especially preferred
  • the molecular weight of the hydrophilic copolymer X is not particularly limited, but it is necessary for the porous fiber to exhibit permanent hydrophilicity. Is preferably a high molecular weight substance, and the intrinsic viscosity [7?] In xylene at 75 ° C. is preferably about 0.07 to 0.40 d £ / g. If [?] Is smaller than this range, the hydrophilic copolymer tends to bleed out during use, while if [ry] is larger than this range, Since the flowability of the hydrophilic copolymer is low, the proportion of the hydrophilic copolymer on the surface of the porous steel including the pore surface tends to be low.
  • the hydrophilic copolymer X basically consists of units A and B, but other units other than these units may be contained as long as the hydrophilic properties of the porous fiber are not impaired. Good.
  • an ethylenically unsaturated carboxylic acid ester an ethylenically unsaturated monomer, an ethylenically unsaturated monomer unit which can be introduced with an ethylenically unsaturated carboxylic acid, or the like.
  • the unit C can be contained in an amount of about 1 to 40 parts by weight, preferably about 1 to 10 parts by weight, based on 100 parts by weight of the total amount of the units A and B.
  • the content of the hydrophilic copolymer X and the polyolefin Y in the porous fiber of the present invention is not particularly limited, and may be arbitrarily selected depending on the required degree of hydrophilicity and ease of production. good.
  • the unit A in the hydrophilic copolymer is The ratio of X and Y can be determined according to the content of unit B and the like.
  • the porous fiber shows sufficient hydrophilicity even if the content of X in the porous fiber is small.
  • the content of the unit A is small, it is necessary to increase the content of X in the porous fiber in order for the porous fiber to exhibit sufficient hydrophilicity.
  • this porous fiber is obtained by a melt spinning or drawing method, if a large amount of the hydrophilic copolymer X containing a large amount of the unit A is blended in the raw material polymer, the unstretched fiber spun out Inversely, the growth of lamellar crystals is hindered.On the contrary, if the hydrophilic copolymer X has a small content of unit A, it is not stretched even if the amount of X in the raw polymer is increased.
  • the blend amounts of X and Y can be determined in consideration of the fact that the growth of lamellar crystals in the fiber is not easily inhibited.
  • the content of the polyolefin Y is preferably about 95 to 50% by weight (No .- / Z. 50, weight ratio). If the content of the polyrefin is less than this range, it is difficult to grow lamellar crystals sufficiently in the undrawn fiber, and it tends to be difficult to obtain a fiber having an excellent porous structure. .
  • the porous fiber of the present invention preferably has a porosity of 30 to 80% and a tensile strength of 0.5 to 8 gZ. d.
  • the tensile elongation is preferably 1 to 300%. If the porosity is less than the above lower limit, the lightness and texture tend to be insufficient, and if the porosity exceeds the upper limit, the strength tends to be insufficient.
  • the strength and elongation are preferably in the above ranges in consideration of clothing use.
  • the above-mentioned hydrophilic copolymer X and polyolefin Y are sufficiently uniformly blended.
  • the blending method include a method of blending these polymers with a blender such as a V-type blender, a method of blending them in a melt extruder and then pelletizing them. No.
  • the blend polymer is melt-spun with a normal spinning machine and wound as an undrawn fiber.
  • the spinning temperature is preferably 20 " ⁇ higher than the melting point of polyolefin Y (hereinafter referred to as Tm) and 80 ° C higher than the melting point. If the fiber is spun at a temperature lower than the lower limit of the temperature range, the obtained undrawn fiber is highly oriented, but the maximum drawing amount when the drawing is made porous in a subsequent drawing step can be increased. On the other hand, spinning at a temperature higher than the upper limit of the above temperature range is not preferable because it is difficult to obtain a material having a sufficiently high porosity. In order to perform stable spinning and increase the crystallinity of the spun undrawn fiber, a slow cooling section with a length of about 1 to 3 m and an ambient temperature of about 50 to 100 ° C is provided immediately below the spinneret. This is preferred.
  • the length of the slow cooling section is less than 1 m or the ambient temperature is less than 50 ° C, thread breakage immediately below the spinneret frequently occurs, and the process stability tends to decrease, which is not preferable. Conversely, if the length of the slow cooling section is longer than 3 m or the ambient temperature is higher than 100 ° C, the cooling of the yarn will be insufficient and substantial draft will occur. However, this is not preferable from the viewpoint of the crystal orientation of the obtained undrawn fiber.
  • the spinning draft employs slightly lower conditions compared to the case of the polyolefin alone system, but is preferably about 50 to 2000, more preferably about 100 to 2000. It is about 1000.
  • the undrawn fiber obtained in this way is heated at a temperature of Tm or less, preferably (Tm ⁇ 10 ° C) to (Tm ⁇ 30 ° C), in order to increase its crystallinity.
  • Heat treatment anneal treatment for one hour or more in a fixed or relaxed state. The longer the processing time, the better, but considering the economy, it is set to about 48 hours or less, and more preferably about 3 to 48 hours.
  • the heat-treated product is made porous by stretching, but a stretching method combining cold stretching and hot stretching is usually employed. That is, first, approximately (Tm ⁇ 220 ° C) to (Tm ⁇ 80 ° C), or more preferably (Tm ⁇ 160 ° C) to (Tm ⁇ 90 ° C). )) And then hot stretched at a temperature in the range of approximately (Tm-60 ° C) to (Tm-5.C).
  • These cold stretching and hot stretching may be multi-stage stretching of two or more stages.
  • Cold drawing is an important step in producing the fiber of the present invention.
  • microcracks are generated in the amorphous portion between the lamellar crystals of the highly oriented crystalline undrawn fiber. It is expanded by the subsequent thermoplastic stretching in the hot stretching step, and the above-mentioned specific porous structure is obtained.
  • the stretching amount in the cold stretching is preferably 5 to 100%, and the hot stretching amount is set so that the total stretching amount of the cold stretching and the hot stretching is 100 to 700%. It is preferable to set If the heat stretching temperature is higher than Tm-5 ° C, the fiber becomes transparent and the desired porous structure cannot be obtained. If the hot stretching temperature is lower than the above lower limit, the lower the temperature, the lower the porosity, which is not preferable. No.
  • one or more stages of heat or wet heat treatment may be heat set in a tensioned or relaxed state. Further, in order to further increase the hydrophilicity of the fiber, the fiber may be treated with heated water or steam at about 50 to 120 ° C as necessary.
  • the crystallinity of the blend polymer was obtained by integrating the omnidirectional diffraction intensities using a wide-angle X-ray diffractometer. I asked for it.
  • Crystallinity Xc (Integrated value of total diffraction intensity-Integral value of diffraction intensity of amorphous portion) Integral value of total diffraction intensity The degree of crystal orientation was determined using a wide-angle X-ray diffractometer (110). ) The half-width of the distribution of the diffraction intensity of the surface in the fiber axis direction was calculated, and calculated by the following formula.
  • the content of the units A and B in the hydrophilic polymer X was determined by measuring the oxygen atoms in the hydrophilic polymer X with an elemental analyzer. It was calculated by quantification.
  • the average degree of polymerization (n) of the alkylene glycol units in the unit A was calculated from the degree of polymerization of the alkylene glycol units in the unit A measured by gel permeation chromatography (GPC). .
  • GPC gel permeation chromatography
  • this pellet was supplied to a spinning machine, and a spinning temperature of 15.5 was established with a spinning cylinder having a length of 2 m immediately below the spinneret, a hole diameter of 1.0 mm ⁇ , and a number of holes of 4 mm. It was spun from a spinneret of No. 0 and wound on a pobin at a spinning draft of 314 at a spinning speed of 250 m / min.
  • the undrawn fiber thus obtained was heat-treated at 115 ° C under a nitrogen atmosphere for 24 hours under a constant length. This unextended The crystallinity of the drawn fiber was 62% and the degree of crystal orientation was 75%.
  • the undrawn fiber is subjected to cold drawing at 25% by 80%, and then, in a 2 m long heating box heated to 115 ° C, the total drawing amount becomes 5200%. Heat stretching was carried out until this time. Furthermore, a relaxation heat set was performed in a 2 m long heating box heated to the same temperature so that the total elongation was 400%.
  • the obtained porous fiber is a slit-shaped space surrounded by lamellas and a number of longitudinally arranged fibrils connecting the lamellas, from the fiber surface to the center.
  • this porous fiber lg was immersed in 200 cc of ion-exchanged water for 1 hour, dehydrated with a centrifugal separator at 1000 rpm for 5 minutes, and the weight gain was measured. The water content was determined to be 135%. Examples 2 and 3
  • Example 1 Consisting of 50% by weight of hydroxyxethyl monomethacrylate unit as unit A and 50% by weight of ethylene unit as unit B, the intrinsic viscosity in xylene at 75 ° C [ 7?] Is 0.19 d £ g and the hydrophilic copolymer X used in Example 1 is Mitsubishi Polyjet JX—20, which is 15:85 (weight ratio, 2) or 2 0: 8 0 (Weight ratio, Example 3) was blended, and a porous fiber was obtained in the same manner as in Example 1.
  • porous fibers had slit-like pores similar to those of Example 1, and had the performance shown in Table 1.
  • Example 4 Weight ratio, Example 4 or 20:80 (weight ratio, Example 5) was blended, and a porous fiber was obtained in the same manner as in Example 1.
  • porous fibers had the same thread and soot pores as those of Example 1, and had the performance shown in Table 1.
  • the average degree of polymerization (n) of polyethylene glycol is 45 wt% of poly (ethylene glycol) monomethacrylate units of 6 and 55 wt% of ethylene units. ?] Is 0.15 dZg and the Mitsubishi copolymer used in Example 1 JX-20 was blended at a ratio of 20:80 (weight ratio), and a porous fiber was obtained in the same manner as in Example 1.
  • porous fibers had the same slit-like pores as those of Example 1 and had the performance shown in Table 1.
  • Example 1 It consists of 35 parts by weight of ethylene glycol monomer having an average degree of polymerization (n) of polyethylene glycol of 6 and 65 parts by weight of ethylene unit.
  • the hydrophilic copolymer X having an intrinsic viscosity [77] of 0.15 d ⁇ g and the Mitsubishi Polytech JX—20 used in Example 1 were mixed in a ratio of 20:80 (weight The blend was blended at a ratio of Example 7) or 25:75 (weight ratio, Example 8), and a porous fiber was obtained in the same manner as in Example 1.
  • porous fibers had slit-like pores similar to those of Example 1, and had the performance shown in Table 1.
  • a porous polyethylene fiber was produced in the same manner as in Example 1 using only Mitsubishi Polyethylene JX-20, which is a high-density polyethylene, as a polymer, and the water content was measured to be 6%.
  • Table 1 Porosity Tensile strength Tensile elongation Water content No U No No No Example 1 3 38 50 5 135 Non 2 3 24 53 6 11 q Non 3 58 5 3 4 48 3 151 Nog 4 • 61 8 3.33 50 5 108 Nono 5 58. 0 3.36 46.7 139 Noso 6 59.8 3.18 48.5 5 115 Nono 7 61.5 3.05 50.2 76 Nono 8 56.5 3.33 46.8 125

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  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Mechanical Engineering (AREA)
  • Artificial Filaments (AREA)

Abstract

Une fibre poreuse possédant une structure de pores qui comprend des espaces communicants enfermés par des lamelles et par un certain nombre de fibrilles disposées longitudinalement qui retient les lamelles partout dans la fibre, laquelle est fabriquée par le mélange d'une polyoléfine avec un copolymère hydrophile principalement constitué d'unités nomonères représentées par la formule ci-dessous et d'unités d'éthylène, par la filature en fusion du mélange, et par l'étirage de la fibre ainsi obtenue: (A), où R1 et R2 représentent chacun indépendamment l'hydrogène ou le méthyle, et n est compris entre 1 et 9. La fibre obtenue possède une hydrophilie permanente et une grande aire de surface, est très légère et moelleuse au toucher, présente une coloration blanche claire sans transparence, et est dotée de propriétés mécaniques excellentes malgré son taux de vides élevé.
PCT/JP1990/000890 1989-07-13 1990-07-11 Fibre poreuse et sa fabrication Ceased WO1991000935A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
KR1019930700329A KR930701265A (ko) 1990-07-11 1992-07-10 다계통 선반용 nc 장치에 있어서의 애니메이션 묘화방법

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP18155789 1989-07-13
JP1/181557 1989-07-13

Publications (1)

Publication Number Publication Date
WO1991000935A1 true WO1991000935A1 (fr) 1991-01-24

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PCT/JP1990/000890 Ceased WO1991000935A1 (fr) 1989-07-13 1990-07-11 Fibre poreuse et sa fabrication

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EP (1) EP0438598A4 (fr)
WO (1) WO1991000935A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5951964A (en) * 1993-06-04 1999-09-14 Diatide, Inc. Technetium-99m labeled peptides for imaging

Families Citing this family (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5677360A (en) * 1991-02-13 1997-10-14 Mitsubishi Rayon Co., Ltd. Hydrophilic polymer alloy, fiber and porous membrane comprising this polymer alloy, and methods for preparing them
WO1992014783A1 (fr) * 1991-02-13 1992-09-03 Mitsubishi Rayon Co., Ltd. Alliage polymere hydrophile, fibre et film poreux produits a partir de cet alliage et procede de production de ceux-ci
FI92337C (fi) * 1993-03-12 1994-10-25 Neste Oy Polyolefiinipohjainen kuitumateriaali
FR2715294B1 (fr) 1994-01-26 1996-03-22 Oreal Composition cosmétique ou dermatologique anhydre contenant l'association d'une huile de silicone et d'une cire d'un homo- ou copolymère d'éthylène .
US5912076A (en) 1996-12-31 1999-06-15 Kimberly-Clark Worldwide, Inc. Blends of polyethylene and peo having inverse phase morphology and method of making the blends
US6255386B1 (en) 1996-12-31 2001-07-03 Kimberly-Clark Worldwide, Inc. Blends of polyolefin and poly(ethylene oxide) and process for making the blends
US6063866A (en) * 1996-12-31 2000-05-16 Kimberly-Clark Worldwide, Inc. Blends of polyolefin and poly(ethylene oxide) and process for making the blends
WO1999034042A1 (fr) 1997-12-31 1999-07-08 Kimberley-Clark Worldwide, Inc. Compositions de fibres jetables dans les toilettes renfermant du polypropylene modifie et du poly(ethylene oxyde) modifie, et procede de fabrication de ces compositions
US6444761B1 (en) 1999-12-28 2002-09-03 Kimberly-Clark Worldwide, Inc. Water-soluble adhesive compositions
US6576576B1 (en) 1999-12-29 2003-06-10 Kimberly-Clark Worldwide, Inc. Multicomponent fibers
US6552124B2 (en) 2000-12-29 2003-04-22 Kimberly-Clark Worldwide, Inc. Method of making a polymer blend composition by reactive extrusion
US7053151B2 (en) 2000-12-29 2006-05-30 Kimberly-Clark Worldwide, Inc. Grafted biodegradable polymer blend compositions
US6500897B2 (en) 2000-12-29 2002-12-31 Kimberly-Clark Worldwide, Inc. Modified biodegradable compositions and a reactive-extrusion process to make the same
US6579934B1 (en) 2000-12-29 2003-06-17 Kimberly-Clark Worldwide, Inc. Reactive extrusion process for making modifiied biodegradable compositions
US6890989B2 (en) 2001-03-12 2005-05-10 Kimberly-Clark Worldwide, Inc. Water-responsive biodegradable polymer compositions and method of making same

Citations (3)

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JPS5120610B1 (fr) * 1971-01-14 1976-06-26
JPS6183305A (ja) * 1984-09-25 1986-04-26 Mitsui Petrochem Ind Ltd 極細繊維束の製造方法
JPH02133607A (ja) * 1988-11-14 1990-05-22 Mitsubishi Rayon Co Ltd 多孔質ポリオレフィン繊維

Patent Citations (3)

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Publication number Priority date Publication date Assignee Title
JPS5120610B1 (fr) * 1971-01-14 1976-06-26
JPS6183305A (ja) * 1984-09-25 1986-04-26 Mitsui Petrochem Ind Ltd 極細繊維束の製造方法
JPH02133607A (ja) * 1988-11-14 1990-05-22 Mitsubishi Rayon Co Ltd 多孔質ポリオレフィン繊維

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5951964A (en) * 1993-06-04 1999-09-14 Diatide, Inc. Technetium-99m labeled peptides for imaging

Also Published As

Publication number Publication date
EP0438598A4 (en) 1992-06-10
EP0438598A1 (fr) 1991-07-31

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