EP0110223B1 - Filler containing acrylic fibres, their preparation and use - Google Patents

Filler containing acrylic fibres, their preparation and use Download PDF

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Publication number
EP0110223B1
EP0110223B1 EP83111351A EP83111351A EP0110223B1 EP 0110223 B1 EP0110223 B1 EP 0110223B1 EP 83111351 A EP83111351 A EP 83111351A EP 83111351 A EP83111351 A EP 83111351A EP 0110223 B1 EP0110223 B1 EP 0110223B1
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Prior art keywords
filler
meth
weight
acrylonitrile
fibres
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EP83111351A
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German (de)
French (fr)
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EP0110223A2 (en
EP0110223A3 (en
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Carlhans Dr. Süling
Bernd Dr. Willenberg
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Bayer AG
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Bayer AG
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Priority claimed from DE19823244028 external-priority patent/DE3244028A1/en
Priority claimed from DE19833321528 external-priority patent/DE3321528A1/en
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Publication of EP0110223A3 publication Critical patent/EP0110223A3/en
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Classifications

    • 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
    • D01F1/00—General methods for the manufacture of artificial filaments or the like
    • D01F1/02—Addition of substances to the spinning solution or to the melt
    • D01F1/07—Addition of substances to the spinning solution or to the melt for making fire- or flame-proof filaments
    • 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
    • D01F6/02—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D01F6/18—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds from polymers of unsaturated nitriles, e.g. polyacrylonitrile, polyvinylidene cyanide

Definitions

  • the invention relates to halogen-free, dry-spun acrylic fibers that contain high proportions of mineral fillers, a process for their production and their use.
  • Halogen-free, wet-spun acrylonitrile fibers do not have the property of low flammability (example of the Japanese patent publication 53 052 733 with LOI values of 13.0 and 14.6).
  • wet-spun, filler-containing polyacrylonitrile fibers obtained from 70 to 99% by weight of acrylonitrile and customary comonomers, such as (meth) acrylic acid ester or (meth) allyl sulfonate, the 1 to 30% by weight on total solids, on inorganic materials from the series of oxides, silicates, carbides, sulfates, chlorides and fluorides, show less tendency to pilling.
  • the invention therefore relates to filler-containing, halogen-free acrylic fibers made of acrylonitrile polymers with at least 50% by weight of acrylonitrile, preferably at least 85% by weight of acrylonitrile, which as filler contains a water-insoluble metal oxide, hydroxide, carbonate, silicate or sulfate with a medium Particle diameter of 1 to 1000 nm, preferably 5 to 500 nm, in an amount of 15 to 50 wt .-%, based on total solids, characterized in that they are dry-spun.
  • a water-insoluble metal oxide, hydroxide, carbonate, silicate or sulfate with a medium Particle diameter of 1 to 1000 nm, preferably 5 to 500 nm, in an amount of 15 to 50 wt .-%, based on total solids, characterized in that they are dry-spun.
  • Preferred acrylonitrile polymers are acrylonitrile homopolymer and copolymers with (meth) acrylic acid, (meth) acrylic acid ester, itaconic acid, (meth) acrylamides, (meth) allyl sulfonate, styrene sulfonate or N, N-dialkylaminoalkyl (meth) acrylamide.
  • Preferred fillers are silicon dioxide, aluminum hydroxide and aluminum oxide, in particular aluminum hydroxide.
  • the fibers according to the invention have LOS values of 21 to 24.
  • LOI Limiting Oxygen Index
  • Acrylnitrilcopolymeriste containing 5 - 10 4 to 2 - 10 contain 2 eq acid groups / g of polymer.
  • the filler-containing fibers are obtained by introducing the filler and the fiber raw material into the spinning solvent, preferably adding an emulsifier for better dispersion of the filler, and heating the reaction mixture to temperatures between 70 and 150 ° C., preferably between 70 and 130 ° C., where the fiber raw material dissolves and the spinning solution spins into threads under the usual conditions of dry spinning.
  • Preferred comonomers are (meth) acrylic acid, (meth) acrylic acid methyl and ethyl esters and methallyl sulfonate.
  • Comonomer-free polymers so-called acrylonitrile unipolymerisates, are also preferred.
  • Solvents for the spinning process are preferably dimethylformamide and dimethylacetamide.
  • Anionic emulsifiers such as lauryl sulfate or sulfosuccinic acid esters, cationic emulsifiers such as quaternary ammonium compounds or nonionic emulsifiers such as oxalkylated alkylphenols and corresponding block copolymers are suitable as emulsifiers and dispersants.
  • the filler-containing fibers are flame retardant and can be used to manufacture textile materials such as woven, knitted, crocheted or non-woven fabrics. They are also suitable as reinforcing fibers in abrasives, friction materials and building materials.
  • DMF dimethylformamide
  • aluminum hydroxide with an average particle diameter ⁇ 400 nm
  • 10.54 kg of an acrylonitrile copolymer containing 93.6% by weight of acrylonitrile, 5.7% by weight of methyl acrylate and 0.7 wt .-% sodium methallylsulfonate entered with stirring at room temperature, dissolved at 80 ° C and filtered.
  • the spinning solution thus obtained had a viscosity of 111 Pa.s.
  • the spinning solution was spun dry, the shaft temperature being 160 ° C., the temperature of the spinning air being 180 ° C. With a take-off speed of 250 m / min, an individual titer of 10 dtex resulted.
  • the spinning belt was stretched four times, washed with shrinkage approval, prepared and dried.
  • a fleece with a basis weight of 200 g / m 2 was produced from the filament yarn thus obtained and the LOI value was determined on it.
  • Example 4 The procedure was as in Example 4, but a copolymer consisting of 94% by weight of acrylonitrile and 6% by weight of methacrylic acid was used as the acrylonitrile copolymer.
  • Example 4 The procedure was as in Example 4, but the filler used was silicon dioxide with an average particle diameter of ⁇ 50 nm.
  • Example 4 The procedure was as in Example 4, but aluminum oxide with an average particle diameter of ⁇ 20 nm was used as the filler.

Description

Die Erfindung betrifft halogenfreie, trockengesponnene Acrylfasern, die hohe Anteile an mineralischen Füllstoffen enthalten, ein verfahren zu ihrer Herstellung und ihre Verwendung.The invention relates to halogen-free, dry-spun acrylic fibers that contain high proportions of mineral fillers, a process for their production and their use.

Es ist bekannt, schwer entflammbare Acrylfasern aus 90 bis 65 Gew.-% eines Acrylpolymers und 10 bis 35 Gew.-% Aluminiumhydroxyd mit kleinem Teilchendurchmesser herzustellen, wobei das Acrylpolymer aus 40 bis 90 Gew.-% Acrylnitril, 10 bis 60 Gew.-% eines Halogen enthaltenden Monomers und weniger als 50 % anderer ungesättigter Monomerer besteht (Japanische Patentpublikation 53 052 733). Nachteilig für diese produkte wie für alle Halogen enthaltenden Acrylfasern ist, daß im Brandfalle, der auch bei Schwerentflammbarkeit nicht ausgeschlossen werden kann, Halogenwasserstoff entsteht, der zwar den Zutritt von Sauerstoff an den Brandherd verhindert oder vermindert, durch dessen Einwirkung aber ein dem eigentlichen Brandschaden vergleichbarer Schaden entstehen kann.It is known to produce flame-retardant acrylic fibers from 90 to 65% by weight of an acrylic polymer and 10 to 35% by weight aluminum hydroxide with a small particle diameter, the acrylic polymer being made from 40 to 90% by weight acrylonitrile, 10 to 60% by weight. % of a halogen-containing monomer and less than 50% of other unsaturated monomers (Japanese Patent Publication 53 052 733). A disadvantage of these products, as for all halogen-containing acrylic fibers, is that in the event of a fire, which cannot be ruled out even in the case of flame retardancy, hydrogen halide is formed, which prevents or reduces the access of oxygen to the source of the fire, but by its action is comparable to the actual fire damage Damage can occur.

Halogenfreie, naßgesponnene Acrylnitrilfasern haben nicht die Eigenschaft der Schwerentflammbarkeit (Beispiel der japanischen Patentpublikation 53 052 733 mit LOI-Werten von 13,0 und 14,6).Halogen-free, wet-spun acrylonitrile fibers do not have the property of low flammability (example of the Japanese patent publication 53 052 733 with LOI values of 13.0 and 14.6).

Weiterhin ist aus der Japanischen Patentpublikation 55-99383 bekannt, daß naßgesponnene, füllstoffhaltige Polyacrylnitrilfasern aus 70 bis 99 Gew.-% Acrylnitril und üblichen Comonomeren, wie (Meth)acrylsäureester oder (Meth)allylsulfonat, die 1 bis 30 Gew.-%, bezogen auf Gesamtfeststoff, an anorganischen Materialien aus der Reihe der Oxide, Silikate, Carbide, Sulfate, Chloride und Fluoride enthalten, geringere Neigung zum Pilling zeigen.Furthermore, it is known from Japanese Patent Publication 55-99383 that wet-spun, filler-containing polyacrylonitrile fibers obtained from 70 to 99% by weight of acrylonitrile and customary comonomers, such as (meth) acrylic acid ester or (meth) allyl sulfonate, the 1 to 30% by weight on total solids, on inorganic materials from the series of oxides, silicates, carbides, sulfates, chlorides and fluorides, show less tendency to pilling.

Es wurde nun überraschenderweise gefunden, daß trockengesponnene, halogenfreie Acrylfasern, gefüllt mit bestimmten anorganischen Füllstoffen von bestimmter Teilchengröße und in bestimmter Konzentration, deutlich schwerer entflammbar sind als entsprechende naßgesponnene Fasern.It has now surprisingly been found that dry-spun, halogen-free acrylic fibers, filled with certain inorganic fillers of a certain particle size and in a certain concentration, are significantly less flammable than corresponding wet-spun fibers.

Gegenstand der Erfindung sind daher füllstoffhaltige, halogenfreie Acrylfasern aus Acrylnitrilpolymerisaten mit mindestens 50 Gew.-% Acrylnitril, vorzugsweise mindestens 85 Gew.-% Acrylnitril, die als Füllstoff ein wasserunlösliches Metalloxid, -hydroxid, -carbonat, -silikat oder -sulfat mit einem mittleren Teilchendurchmesser von 1 bis 1000 nm, vorzugsweise 5 bis 500 nm, in einer Menge von 15 bis 50 Gew.-%, bezogen auf Gesamtfeststoff, enthalten, dadurch gekennzeichnet, daß sie trockengesponnen sind.The invention therefore relates to filler-containing, halogen-free acrylic fibers made of acrylonitrile polymers with at least 50% by weight of acrylonitrile, preferably at least 85% by weight of acrylonitrile, which as filler contains a water-insoluble metal oxide, hydroxide, carbonate, silicate or sulfate with a medium Particle diameter of 1 to 1000 nm, preferably 5 to 500 nm, in an amount of 15 to 50 wt .-%, based on total solids, characterized in that they are dry-spun.

Bevorzugte Acrylnitrilpolymerisate sind Acrylnitrilhomopolymerisat und Copolymerisate mit (Meth)acrylsäure, (Meth)acrylsäureester, Itaconsäure, (Meth)acrylamide, (Meth)allylsulfonat, Styrolsulfonat oder N,N-Dialkylaminoalkyl (meth)-acrylamid.Preferred acrylonitrile polymers are acrylonitrile homopolymer and copolymers with (meth) acrylic acid, (meth) acrylic acid ester, itaconic acid, (meth) acrylamides, (meth) allyl sulfonate, styrene sulfonate or N, N-dialkylaminoalkyl (meth) acrylamide.

Bevorzugte Füllstoffe sind Siliciumdioxid, Aluminiumhydroxid und Aluminiumoxid, insbesondere Aluminiumhydroxid.Preferred fillers are silicon dioxide, aluminum hydroxide and aluminum oxide, in particular aluminum hydroxide.

Die erfindungsgemäßen Fasern weisen LOS-Werte von 21 bis 24 auf.The fibers according to the invention have LOS values of 21 to 24.

Als Prüfmethode filr die Entflammbarkeit und das Brennverhalten von textilen Flächengebilden wurde die Messung nach dem Limiting Oxygen Index (LOI) durchgeführt. Hierbei wird das Volumenverhältnis von Sauerstoff zur Summe aus Sauerstoff und Stickstoff in jenem Gemisch bestimmt, bei dem das Textil nach der Entzündung gerade noch von oben nach unten weiter brennt. Es gilt:As a test method for the flammability and the burning behavior of textile fabrics, the measurement was carried out according to the Limiting Oxygen Index (LOI). The volume ratio of oxygen to the sum of oxygen and nitrogen in the mixture in which the textile just burns from top to bottom after ignition is determined. The following applies:

Figure imgb0001
Da Probenanordnung und Flächengewicht die Ergebnisse beeinflussen, wurden nur Vliese von ca. 200 g/m2 Flächengewicht getestet, die in eine Probenhalterung geklemmt wurden. Die LOI-Wert gibt demnach die zur Verbrennung notwendige Sauerstoffkonzentration an. Je höher diese Konzentration ist, um so schwerer brennbar sind die Fäden.
Figure imgb0001
 Since the sample arrangement and basis weight influence the results, only nonwovens with a basis weight of approx. 200 g / m 2 that were clamped in a sample holder were tested. The LOI value therefore indicates the oxygen concentration required for combustion. The higher this concentration, the more difficult the threads are to burn.

Vorzugsweise verwendet man Acrylnitrilcopolymeriste, die 5 - 10-4 bis 2 - 10-2 val saure Gruppen/g Polymer enthalten.Are preferably used Acrylnitrilcopolymeriste containing 5 - 10 4 to 2 - 10 contain 2 eq acid groups / g of polymer.

Die füllstoffhaltigen Fasern werden erhalten, indem man den Füllstoff und den Faserrohstoff in das Spinnlösungsmittel einträgt, vorzugsweise einen Emulgator zur besseren Dispergierung des Füllstoffes zusetzt, die Reaktionsmischung auf Temperaturen zwischen 70 und 150°C, vorzugsweise zwischen 70 und 130°C, erwärmt, wobei sich der Faserrohstoff löst, und die Spinnlösung unter den üblichen Bedingungen des Trockenspinnens zu Fäden verspinnt.The filler-containing fibers are obtained by introducing the filler and the fiber raw material into the spinning solvent, preferably adding an emulsifier for better dispersion of the filler, and heating the reaction mixture to temperatures between 70 and 150 ° C., preferably between 70 and 130 ° C., where the fiber raw material dissolves and the spinning solution spins into threads under the usual conditions of dry spinning.

Bevorzugte Comonomere sind (Meth)acrylsäure, (Meth)acrylsäure-methyl- und -ethyl-ester und Methallylsulfonat. Bevorzugt sind auch comonomerfreie Polymerisate, sogenannte Acrylnitrilunipolymerisate. Lösungsmittel für das Spinnverfahren sind vorzugsweise Dimethylformamid und Dimethylacetamid.Preferred comonomers are (meth) acrylic acid, (meth) acrylic acid methyl and ethyl esters and methallyl sulfonate. Comonomer-free polymers, so-called acrylonitrile unipolymerisates, are also preferred. Solvents for the spinning process are preferably dimethylformamide and dimethylacetamide.

Als Emulgier- und Dispergiermittel kommen anionische Emulgatoren, wie Laurylsulfat oder Sulfobernsteinsäureester, kationische Emulgatoren, wie quartäre Ammoniumverbindungen oder nichtionische Emulgatoren, wie oxalkylierte Alkylphenole sowie entsprechende Blockcopolymerisate in Betracht.Anionic emulsifiers such as lauryl sulfate or sulfosuccinic acid esters, cationic emulsifiers such as quaternary ammonium compounds or nonionic emulsifiers such as oxalkylated alkylphenols and corresponding block copolymers are suitable as emulsifiers and dispersants.

Die füllstoffhaltigen Fasern sind schwer entflammbar und lassen sich zur Herstellung textiler Materialien, wie Gewebe, Gewirke, Gestricke oder Vliese verwenden. Sie eignen sich ferner als Verstärkungsfasern in Reibmitteln, Friktionsmaterialien und Baustoffen.The filler-containing fibers are flame retardant and can be used to manufacture textile materials such as woven, knitted, crocheted or non-woven fabrics. They are also suitable as reinforcing fibers in abrasives, friction materials and building materials.

Beispiel 1example 1

In 30,00 kg Dimethylformamid (DMF) wurden 2,11 kg Aluminiumhydroxid einem mittleren Teilchendurchmesser <400 nm und 10,54 kg eines Acrylnitril-Copolymerisates, enthaltend 93,6 Gew.-% Acrylnitril, 5,7 Gew.-% Acrylsäuremethylester und 0,7 Gew.-% Natriummethallylsulfonat unter Rühren bei Raumtemperatur eingetragen, bei 80°C gelöst und filtriert. Die so erhaltene Spinnlösung hatte eine Viskosität von 111 Pa.s. Die Spinnlösung wurde trockenversponnen, dabei betrug die Schachttemperatur 160°C die Temperatur der Spinnluft 180°C Bei einer Abzugsgeschwindigkeit von 250 m/min ergab sich ein Einzeltiter von 10 dtex. Das Spinnband wurde vierfach verstreckt, unter Schrumpfzulassung gewaschen, präpariert und getrocknet.In 30.00 kg of dimethylformamide (DMF) were 2.11 kg of aluminum hydroxide with an average particle diameter < 400 nm and 10.54 kg of an acrylonitrile copolymer containing 93.6% by weight of acrylonitrile, 5.7% by weight of methyl acrylate and 0.7 wt .-% sodium methallylsulfonate entered with stirring at room temperature, dissolved at 80 ° C and filtered. The spinning solution thus obtained had a viscosity of 111 Pa.s. The spinning solution was spun dry, the shaft temperature being 160 ° C., the temperature of the spinning air being 180 ° C. With a take-off speed of 250 m / min, an individual titer of 10 dtex resulted. The spinning belt was stretched four times, washed with shrinkage approval, prepared and dried.

Der Einzeltiter betrug jetzt 3,3 dtex, die feinheitsbezogene Festigkeit und die Bruchdehnung sind in Tabelle 1 aufgeführt.The individual titer was now 3.3 dtex, the fineness-related strength and the elongation at break are listed in Table 1.

Aus dem so erhaltenen Filamentgarn wurde ein Vlies mit einem Flächengewicht von 200 g/m2 hergestellt, an dem der LOI-Wert bestimmt wurde.A fleece with a basis weight of 200 g / m 2 was produced from the filament yarn thus obtained and the LOI value was determined on it.

Die Ergebnisse sind in Tabelle 1 aufgeführt.The results are shown in Table 1.

Beispiele 2 - 5Examples 2-5

Bei sonst identischer Verfahrensweise wie in Beispiel 1 wurden lediglich die eingesetzten Mengen an Aluminiumhydroxid auf 3,16, 4,22, 5,27 bzw. 10,54 kg erhöht entsprechend einem Füllstoffgehalt von 23,1, 28,6, 33,6 bzw. 50,0 Gew.-% bezogen auf die gesamte Faser. Die Ergebnisse sind in Tabelle 1 aufgeführt.If the procedure was otherwise identical to that in Example 1, only the amounts of aluminum hydroxide used were increased to 3.16, 4.22, 5.27 or 10.54 kg, corresponding to a filler content of 23.1, 28.6, 33.6 or 50.0% by weight, based on the total fiber. The results are shown in Table 1.

Beispiel 6Example 6

Es wurde wie in Beispiel 4 verfahren, als Acrylnitrilcopolymerisat wurde jedoch ein Copolymerisat bestehend aus 94 Gew.-% Acrylnitril und 6 Gew.-% Methacrylsäure eingesetzt.The procedure was as in Example 4, but a copolymer consisting of 94% by weight of acrylonitrile and 6% by weight of methacrylic acid was used as the acrylonitrile copolymer.

Die Ergebnisse sind in Tabelle 1 aufgeführt.The results are shown in Table 1.

Beispiel 7Example 7

Es wurde wie in Beispiel 4 verfahren, als Füllstoff wurde jedoch Siliziumdioxid mit einem mittleren Teilchendurchmesser von < 50 nm eingesetzt.The procedure was as in Example 4, but the filler used was silicon dioxide with an average particle diameter of <50 nm.

Die Ergebnisse sind in Tabelle 1 aufgeführt.The results are shown in Table 1.

Beispiel 8Example 8

Es wurde wie in Beispiel 4 verfahren, als Füllstoff wurde jedoch Aluminiumoxid mit einem mittleren Teilchendurchmesser < 20 nm eingesetzt.The procedure was as in Example 4, but aluminum oxide with an average particle diameter of <20 nm was used as the filler.

Die Ergebnisse sind in Tabelle 1 aufgeführt.

Figure imgb0002
The results are shown in Table 1.
Figure imgb0002

Claims (7)

1. Filler-containing acrylic fibres or acrylonitrile polymers containing at least 50 % by weight of acrylonitrile which contain as filler a water-insoluble metal oxide, hydroxide carbonate, silicate or sulphate having an average particle diameter of from 1 to 1000 nm in a quantity of from 15 to 50 % by weight, based on total solids, characterised in that they are dry-spun.
2. Filler-containing acrylic fibres according to Claim 1 of acrylonitrile polymers containing at least 85 % by weight of acrylonitrile and up to 15 % by weight of (meth)acrylic acid, (meth)acrylic acid alkyl ester, itaconic acid, (meth)acrylamide, (meth)allylsulphonate, styrene sulphonate or N,N-dialkylaminoalkyl (meth)-acrylamide as comonomer and aluminium hydroxide as filler.
3. Fibres according to Claim 1, the average particle diameter of the filler being 5 to 500 nm.
4. Fibres according to Claim 1, the raw fibre material containing from 5.104 to 2.10-2 vals of acid groups per g of polymer.
5. Process for producing the filler-containing fibres according to Claim 1, characterised in that the filler and raw fibre material are introduced into the spinning solution, the reaction mixture is heated to temperatures between 70 and 150° C, during which prrocess the raw fibre material dissolves, and the spinning solution is dry-spun.
6. Process according to Claim 4, characterised in that an emulsifier is added to the spinning solution.
7. Process of fibres according to Claim 1 for the production cf textile materials and as reinforcing fibres.
EP83111351A 1982-11-27 1983-11-14 Filler containing acrylic fibres, their preparation and use Expired EP0110223B1 (en)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
DE19823244028 DE3244028A1 (en) 1982-11-27 1982-11-27 Filler-containing acrylic fibres, their production and their use
DE3244028 1982-11-27
DE3321528 1983-06-15
DE19833321528 DE3321528A1 (en) 1983-06-15 1983-06-15 Filler-containing acrylic fibres, production thereof and use thereof

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EP0110223A2 EP0110223A2 (en) 1984-06-13
EP0110223A3 EP0110223A3 (en) 1986-07-02
EP0110223B1 true EP0110223B1 (en) 1988-06-08

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Publication number Priority date Publication date Assignee Title
DE3443680A1 (en) * 1984-11-30 1986-06-05 Bayer Ag, 5090 Leverkusen FILLER-CONTAINING ACRYLIC AND MODACRYL FIBERS AND A METHOD FOR THEIR PRODUCTION
US20120215148A1 (en) * 2010-09-14 2012-08-23 Yvonne Ewert Highly functional spunbonded fabric made from particle-containing fibres and method for producing same
US10501876B2 (en) 2010-09-14 2019-12-10 Thueringisches Institut Fuer Textil-Und Kunststoff-Forschung E.V. Highly functional spunbonded fabric made from particle-containing fibres and method for producing same

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JPS51147547A (en) * 1975-06-12 1976-12-17 Toyobo Co Ltd Process for preparing viscous liquid containing fire-proofing inorgani c oxides
JPS5473923A (en) * 1977-11-24 1979-06-13 Mitsubishi Rayon Co Ltd Fibers having dry-touch feeling and their production

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