EP0574507A1 - Fibres de polyamide aromatique a capacite elevee de traitement, leur production et leur utilisation. - Google Patents

Fibres de polyamide aromatique a capacite elevee de traitement, leur production et leur utilisation.

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Publication number
EP0574507A1
EP0574507A1 EP19920907819 EP92907819A EP0574507A1 EP 0574507 A1 EP0574507 A1 EP 0574507A1 EP 19920907819 EP19920907819 EP 19920907819 EP 92907819 A EP92907819 A EP 92907819A EP 0574507 A1 EP0574507 A1 EP 0574507A1
Authority
EP
European Patent Office
Prior art keywords
acid
weight
fibers
surface treatment
alcohol
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
Application number
EP19920907819
Other languages
German (de)
English (en)
Other versions
EP0574507B1 (fr
Inventor
Serge Rebouillat
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.)
EIDP Inc
Original Assignee
EI Du Pont de Nemours and Co
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Filing date
Publication date
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Application filed by EI Du Pont de Nemours and Co filed Critical EI Du Pont de Nemours and Co
Publication of EP0574507A1 publication Critical patent/EP0574507A1/fr
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Classifications

    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/322—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing nitrogen
    • D06M13/372—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing nitrogen containing etherified or esterified hydroxy groups ; Polyethers of low molecular weight
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/10—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing oxygen
    • D06M13/165—Ethers
    • D06M13/17—Polyoxyalkyleneglycol ethers
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/10—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing oxygen
    • D06M13/224—Esters of carboxylic acids; Esters of carbonic acid
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M7/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made of other substances with subsequent freeing of the treated goods from the treating medium, e.g. swelling, e.g. polyolefins
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M2200/00—Functionality of the treatment composition and/or properties imparted to the textile material
    • D06M2200/40—Reduced friction resistance, lubricant properties; Sizing compositions

Definitions

  • the present invention relates to highly processable aromatic polyamide fibers, their production and use.
  • finishes useful for treating industrial fibers such as polyamide and aramid fibers
  • finishes include a lubricant, comprising esters composed of an aliphatic, saturated carboxylic acid and a polyhydric or aliphatic unbranched alcohol.
  • These finishes also contain an emulsifier or emulsifying system, an anti-oxidant to increase the stability of the composition, polysiloxanes as a further thermostable lubricant, o and a sulfonated natural oil as an antistatic agent.
  • these finishes may contain biostats, further emulsifiers, and lubricants.
  • the finishes according to the above reference are not suitable for the purposes of the present invention in terms of surface frictional properties, scourability, the protection from depositing due to abrasion, fibrillation 5 and antistatic properties of the resulting treated fibers.
  • the application of a particular combination of surface treatment agents on the surface of previously dried aramid fibers using a finishing process already known; or the application of those agents on never-drawn never-dried aramid fibers yields a new surface treated fiber which exhibits excellent processability characteristics in its use as a reinforcing element for rubber applications or as a yarn for fabric woven structures.
  • the end use performance of final products, using the fibers, is consequently significantly improved.
  • the present invention accordingly relates to highly processable aramid fibers of high modulus, improved surface frictional properties, improved scourability, low abrasion polymer depositing, low fibrillation and improved longterm antistatic properties, having a coating of a lubricant, an emulsifying system, an antistatic agent, and other components, derived from a surface treatment agent which consists of
  • an esteroil lubricant consisting of an ester, composed of (I) an alcohol component which is a branched, primary or secondary, saturated monohydric alcohol of the general formula
  • R 1 represents Ci-Ci ⁇ -alkyl
  • R3 represents C -Ci9-alkenyl, C4-CiQ-alka- 5 dienyl, C4-Ci9-alkatrienyl, phenyl, naphthyl,
  • an antistatic agent consisting of alkali salts of C4-C12- alkyl sulfonates, C4-Ci2-alkyl phosphates or C4-C20-alky- carboxylic acids,
  • the coating preferably consists of 50 to 60% by weight, most preferably 55 to 60% by weight of the esteroil (a), 25 to 40% by weight, most preferably 29 to 35% by weight of the emulsifying system (b), 5 to 10% by weight, most preferably 5 to 7% by weight of the antistatic agent (c), 0.3 to 1% by weight, most preferably 0.3 to 0.5% by weight of the corrosion inhibitor (d) and, if desired, optionally additives (e).
  • the aramid fibers of this invention are further characterized by a specific breaking strength of 2.65 to 33.5 cN/dtex (3 to 38 g/den), a specific modulus of 8.83 to 2207 cN/dtex (10 to 2500 g/den), a fiber to metal dynamic friction coefficient on a 1100 dtex aramid yarn of lower than 0.55, preferably below 0.50 at 200 m/min, a fiber to metal boimdary friction coefficient on a 1100 dtex aramid yarn of lower than 0.10, preferably below 0.05 at 0.016 cm/s, an amount of deposit due to abrasion of lower than 0.5 mg/kg of yarn, a residual finish level of lower than 15% by weight of the initial finish level after washing.
  • the fiber of this invention provides an improved blend of properties in terms of fume emission measured by weight losses, washability of the fiber and cohesiveness of the fiber compared with fibers using other finishes.
  • fibers are meant continuous filaments as well as a single yarn or cord, staple fibers, fiber tows (for example from stretch breaking processes), yarns or flat textile skeins, staple crimped fibers, pulps, industrial woven, twisted, knitted, braided, spiralled or wrapped textiles from aramids with a fiber type structure.
  • Aramids are such polymers that are partially, preponderantly or exclusively composed of aromatic rings, which are connected through carbamide bridges or optionally, in addition also through other bridging structures.
  • the structure of such aromatic polyamides can be elucidated by the following general formula of repeating units:
  • a ⁇ and A2 are the same or different and signify aromatic and/or polyaromatic and/or heteroaromatic rings, that can also be substituted.
  • Ai and A2 may, independently from each other, be selected from 1,4-phenylene, 1,3-phenyIene, 1,2-phenylene, 4,4'-biphenylene, 2,6-naphthylene, 1,5-naphthylene,
  • 1,4-naphthylene, phenoxyphenyl-4,4'-diylene, phenoxyphenyl-3,4'-diylene, 2,5- pyridylene and 2,6-quinolylene which may or may not be substituted by one or more substituents which may comprise halogen, C ⁇ -C4-alkyl, phenyl, carboalkoxyl, C1-C4- alkoxyl, acyloxy, nitro, dialkylamino, thioalkyl, carboxyl and sulfonyl.
  • the -CONH-group may also be replaced by a carbonyl-hydrazide (-CONHNH-) group, azo-or azoxy-group.
  • Fibers derived from wholly aromatic polyamides are preferred.
  • aramids are poly-m-phenylene-isophthalamide and poly-p-phenylene- terephthalamide.
  • poly-m-phenylene- isophthalamide fibers according to US 3,287,324 and poly-p-phenylene- terephthalamide fibers according to US 3,869,429 and DE 22 19703.
  • Additives can be used with the aramid and, in fact, it has been found that up to as much as 10 percent by weight of other polymeric material can be blended with the aramid or that copolymers can be used having as much as 10 percent by weight of other diamine substituted for the diamine of the aramid or as much as 10 percent by weight of other diacid chloride substituted for the diacid chloride of the aramid.
  • Additional suitable aromatic polyamides are of the following structure
  • X represents O, S, SO2, NR, N2, CR2, CO
  • R represents H, C ⁇ -C4-alkyl
  • Arj and Ar2 which may be same or different are selected from 1,2-phenylene, 1,3- phenylene and 1,4-phenylene and in which at least one hydrogen atom may be substituted with halogen and/or C ⁇ -C4-alkyl.
  • the finish formulation of this invention comprises a lubricant, an emulsifying system, an antistatic agent and a corrosion inhibitor, and if desired, water and/or other additives.
  • the lubricant is an esteroil which is characterized as stated above.
  • Examples for the alcohol compound (I) of the ester can be 2-methyl-l-propanol, 2- butanol, 2-pentanol, 2-methyl-l-butanol, 3-methyl-3-l-butanol, 3-methyl-2-butanol, 2-methyl-l-pentanol, 4-methyl-l-pentanol, 4-methyl-2-pentanol, 2rpentanol, 3- heptanol, 2-octanol, 2-ethyl-l-hexanol, 3,5-dimethyl-l-hexanol, 5-nonanol, 2-6- dimethyl-4-heptanol, iso-hexadecyl alcohol or iso-tridecyl alcohol.
  • Examples for the carboxylic acid component (II) can be lauroleic acid, myristoleic acid, palmitoleic acid, oleic acid, gadoleic acid, erucic acid, ricinoleic acid, tallow acid, linoleic acid, linolenic acid, fumaric acid, maleic acid, cinnamic acid, naphthaline carboxylic acid, benzoic acid, terephthalic acid, isophthalic acid, trimellitic acid or pyromellitic acid.
  • the kinematic viscosity of the esteroil preferably is in the range of 200 to 300 mm 2 /s (20°C).
  • the emulsifying system of this invention is as defined above.
  • unsaturated fatty acids are lauroleic acid, myristoleic acid, palmitoleic acid, gadoleic acid, erucic acid or ricinoleic acid, preferably oleic acid (with 3-15 moles ethylene oxide).
  • unsaturated fatty alcohol are elaidyl alcohol, erucyl alcohol, brassidyl alcohol, preferably oleyl alcohol and/or tallow alcohol (with 3-10 moles of EO).
  • Further examples are Cg- or C9-alkylphenolethoxylates, preferably octylphenol-or nonylphenolethoxylates (5-5 moles of EO).
  • the antistatic compounds are alkali salts, preferably sodium salts of alkyl sulfonates (e.g. lauiyl or oleyl sulfonate), alkyl phosphates like C4-Ci2- lkyl phosphates (mono/diester mixture) and salts of fatty acids, e.g. oleic acid.
  • alkyl sulfonates e.g. lauiyl or oleyl sulfonate
  • alkyl phosphates like C4-Ci2- lkyl phosphates (mono/diester mixture)
  • salts of fatty acids e.g. oleic acid.
  • the sodium chloride content should be below 0.1%. It is also possible to use alkylsulfates, however, they are not preferred because they hydrolyze easily and therefore loose their antistatic efficiency.
  • Useful corrosion inhibitors are diethanolamine salts of C4-C12- alkylphosphate-esters (mono/di) or amine salts of fatty acids or benzoic acid.
  • the formulation may optionally contain water for stabilization reasons even before it is diluted with water in order to obtain the concentration at which it is applied to the fibers.
  • Additives can optionally be incorporated in the formulation if specific properties or process conditions are required, for example adhesion, specific cross- linkage, UV-protection, antioxidation, pigmentation or Theological adjustment. These additives may further comprise fungicides, bacteriocides and biocides.
  • a formulation for the treatment of aramid fibers can be prepared by mixing all components at an elevated temperature, preferably at a temperature between 30° and 40°C, in order to obtain a homogeneous and clear oil.
  • a mixture consisting of 550 g of isobutyl oleate, 350 g of emulsifying system which consists of 200 g nonylphenol ethoxylate (8 EO) and 150 g of oleic acid ethoxylate (10 EO), 70 g of sodium decylsulfonate and 5 g of the diethanolamine salt of benzoic acid can be prepared.
  • emulsifying system which consists of 200 g nonylphenol ethoxylate (8 EO) and 150 g of oleic acid ethoxylate (10 EO)
  • 70 g of sodium decylsulfonate and 5 g of the diethanolamine salt of benzoic acid
  • the pH value can be adjusted to be within 6 and 8, preferably 7, using diethanolamine or acetic acid.
  • the finish formulation of this invention is further characterized by a viscosity of 150 to 500 mm 2 /s, preferably of 150 to 300 mm 2 /s (at 20°C), a weight- loss of less than 25%, preferably less than 15%, after 2 h at 200°C, a surface tension of a 1% emulsion of less than 35 mN/m, preferably less than 32 mN/m at 20 °C. 5
  • the invention further relates to a process for the production of a highly processable aromatic polyamide fiber coated on the surface with a surface treatment agent.
  • Coating of aramid fibers with the surface treatment agent of this invention can take place in various ways and, more specifically, for example, 0 according to the following processes (a) and (b).
  • the application of the surface treatment agent is made on never-dried never-drawn aramid fiber; and according to process (b) the application of the surface treatment agent is done on previously dried aramid fiber, in each case using any known coating device.
  • the finish formulation is 5 used neat or in a diluted aqueous form, which is in a concentration of as low as 1% by weight.
  • the finish formulation is applied in a concentration of about 30% by weight in water (this means 30 parts by weight finish formulation + 70 parts by weight water) on a wet aramid fiber.
  • the emulsion o treated fiber is then dried during the fiber stretching drying step at a temperature between 150 and 190°C, preferably at around 170°C for few seconds (5-10 s) while the yarn speed is around 630 m/min (workable range 120-1200 m/min).
  • yarns and cords of aramid fibers are passed through a dip of the finish formulation in a dipping unit to coat them and 5 then are dried in an air heated chamber at 80 to 190°C, preferably at 110 to 130°C with a predetermined tension of 6 N for an untwisted 1670 dtex yarn.
  • the most preferred temperature for this step is about 120°C.
  • the dip concentration for the finish formualtion which may be from 1% to 100% by weight in water, the speed is adjusted to be from 15 to 100 m/min.
  • a -finish formulation 0 of 100% is meant that the finish is neat.
  • finish levels for both processes, (a) and (b), are in the range of 0.05 to 2% by weight, preferably 0.2 to 1.0% by weight.
  • processes (a) and (b) can be conducted as a multi-step process in which the fiber may be several times immersed in a surface treatment 5 agent and in turn dried.
  • the treatment agent can be applied on the never-dried wet fiber, then the fiber can be dried and thereafter the surface treatment agent can be applied once more or even several times more with or without intermediate drying.
  • Fibers of this invention can be used in the reinforcement of hoses, belts, ropes and cables including optical cables, mbber goods and composite structures (e.g. sporting goods, medical supplies, building and acoustic material, transport and protective equipment for civil and military applications ).
  • mbber goods and composite structures e.g. sporting goods, medical supplies, building and acoustic material, transport and protective equipment for civil and military applications ).
  • aramid fiber in a yam of 1100 dtex and coated by the finish of this invention was compared with commercially-available aramid yam of the same dtex coated by a standard finish.
  • the aramid fiber of this invention shows superiority, in terms of friction, especially dynamic friction F/M (200 m/min), deposit measured in mg/kg of yarn, and fibrillation compared to the control aramid fiber (Comparison) which is commercially available.
  • the scourability is a very important factor since the residual finish level after a washing-step (measured in %) impacts any subsequent finishing operation. Scourability values mentioned in the Table below were obtained on an industrial scale using fabrics made of the yam of this invention and compared with a control yam which was a commercial product of the same denier treated with a standard finish. The values were confirmed in the laboratory by washing the yarns two times with soft water at 50°C using 100 ml of water for 10 g of yam.
  • the Rothschild friction meter R-1182 has been used according to the standard procedure known in the art. The deposit due to abrasion was measured on a "Staff-Tester G 555"
  • the fibrillation index was determined on a "G 566" apparatus (Zweigle, West Germany).
  • Friction Fiber/Fiber (0.016 cm/s)
  • Fiber/Metal (0.016 cm/s) (128 cm/s) (200 m/min) 2. Deposit (mg/kg)
  • the fabrics were made of 1111 dtex (1000 denier) yarns.
  • the weaving operation of ballistic fabrics leads to strength losses usually quantified by extracting the yarn out of the fabric and measuring the tenacity according to the standard procedures known in the art.
  • the following Table shows that the product of this invention yields a significant advantage since, in a heavy fabric construction (typically 12 ends per cm), the strength loss is reduced by half (7 vs. 14%).
  • the ballistic performance (V50: see test procedure) is also improved by 8% at the greige fabric level and 5 to 8% at the finished level (meaning after final fabric treatment).
  • the ballistic test method for determining V50 was carried out according to the NATO standardization agreement STANAG 2920.
  • the V50 ballistic limit velocity for a material or armour is defined as that velocity for which the probability of penetration of the chosen projectiles is exactly 0.5, using the Up and Down firing method and calculation described below.
  • the first round shall be loaded with the amount of propellant calculated to give the projectile a velocity equivalent to the estimated V50 ballistic limit of the armour. If the first round fired produces a complete penetration, the second round shall be loaded with a fixed decrement of propellant calculated to produce a velocity about 30 m/s lower than the first. If the first round fired results in a partial penetration, the second round shall be loaded with a fixed increment of propellant calculated to produce a velocity about 30 m/s higher than the first round. Upon achieving the first set of penetration reversals, the propellant charge should be adjusted with the fixed amount to yield an increment or decrement of velocity of about 15 m/s. Firing will then continue in accordance with a given procedure to obtain an estimate of the V50 (BLP) [Ballistic limit Protection],
  • V50 calculation After a number of projectiles have been fired the V50 is calculated as the mean of the velocities recorded for the fair impact the fair impacts consisting of the three highest partial velocities for partial penetration and the three lowest velocities for complete penetration provided that all six velocities fall within a bracket of 40 m/s.
  • knitting processability evaluation was carried out under the following conditions: ELHA Circular Knitting Machine (Model RRU), test duration 4 hours, machine speed 670 rpm, knitting speed 1 5 m/min ; knitting construction 3 stitches /cm .
  • Example 6 In this example, several qualities of yam of this invention were tested and compared with those qualities as exhibited by Comparison yam.
  • Weight loss is measured by the percentage of finish material lost after exposing the fibers at 230°C for 8 hours.
  • the finish percentage is determined by solvent extraction before and after the heat exposure.
  • the percentage of residue after scouring is also determined by solvent extraction of the residual finish remaining on the fiber after washing (scouring) the fiber according to washing procedures known and applied in the industry. The percentage is calculated versus the initial finish level determined prior to the scouring step.
  • the fiber to metal (F/M) friction coefficient is measured at 150 m/min using the Rothschild equipment and method as described previously.
  • All yarns were 1000 denier, 670 filament and were coated in the dried state using a neat finish formulation at a rate of 750 m/minute to a level of 0.8%.
  • the finish of A included a 70/30 mixture of benzene tricarboxylic acid and benzene dicarboxylic acid as the carboxylic acid component for the esteroil.
  • the finish of B included a 70/30 mixture of C-18/C-16 alkenyl monocarboxylic acid component for the esteroil.
  • the finish of the Comparison was C-12/C-15 mineral oil-based as disclosed in Research Disclosure No. 195, disclosure 19520, July, 1980.

Abstract

L'invention concerne des fibres d'aramide comportant une couche d'un lubrifiant d'ester et d'huile, un système émulsifiant constitué par des dérivés éthoxylés d'acides gras non saturés et/ou des alcools gras non saturés et/ou des alkylamines propoxylées par éthoxy ainsi qu'un agent antistatique; et leur procédé de production.
EP92907819A 1991-03-02 1992-03-02 Fibres de polyamide aromatique a capacite elevee de traitement, leur production et leur utilisation Expired - Lifetime EP0574507B1 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
DE4106682A DE4106682C2 (de) 1991-03-02 1991-03-02 Aromatische Hochleistungs-Polyamid-Fasern, ihre Herstellung und Verwendung
DE4106682 1991-03-02
PCT/US1992/001891 WO1992015747A1 (fr) 1991-03-02 1992-03-02 Fibres de polyamide aromatique a capacite elevee de traitement, leur production et leur utilisation
CN92103391A CN1049462C (zh) 1991-03-02 1992-04-03 可加工性优良的芳族聚酰胺纤维及其生产和用途

Publications (2)

Publication Number Publication Date
EP0574507A1 true EP0574507A1 (fr) 1993-12-22
EP0574507B1 EP0574507B1 (fr) 1994-08-10

Family

ID=25742744

Family Applications (1)

Application Number Title Priority Date Filing Date
EP92907819A Expired - Lifetime EP0574507B1 (fr) 1991-03-02 1992-03-02 Fibres de polyamide aromatique a capacite elevee de traitement, leur production et leur utilisation

Country Status (8)

Country Link
EP (1) EP0574507B1 (fr)
JP (1) JP3383860B2 (fr)
CN (1) CN1049462C (fr)
AU (1) AU660455B2 (fr)
BR (1) BR9205704A (fr)
DE (2) DE4106682C2 (fr)
ES (1) ES2057991T3 (fr)
WO (1) WO1992015747A1 (fr)

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Publication number Priority date Publication date Assignee Title
US5269952A (en) * 1992-12-21 1993-12-14 E. I. Du Pont De Nemours And Company Antistatic finish for dyeable surfactant-containing poly(m-phenylene isophthalamide) fibers
DE60003629T2 (de) 1999-07-12 2004-06-03 Société de Technologie Michelin Reifen, dessen seitenwände einen glasierten film enthalten
US6706931B2 (en) * 2000-12-21 2004-03-16 Shell Oil Company Branched primary alcohol compositions and derivatives thereof
JP4747255B2 (ja) * 2000-12-27 2011-08-17 Ｊｎｃ株式会社 帯電性を有するトウおよびそれを用いた積層体
EP1435407A1 (fr) 2003-01-02 2004-07-07 Teijin Twaron B.V. Fil d'aramide ayant un apprêt conducteur
CN1318684C (zh) * 2004-07-09 2007-05-30 竹本油脂(苏州)有限公司 兽毛纤维的纺纱用处理剂
JP4480176B2 (ja) * 2006-12-27 2010-06-16 竹本油脂株式会社 合成繊維用処理剤の水性液及び合成繊維の処理方法
JP5604141B2 (ja) * 2010-03-11 2014-10-08 Ｊｘ日鉱日石エネルギー株式会社 油剤組成物及び極微量油剤供給式切削・研削加工方法
JP5260621B2 (ja) * 2010-12-15 2013-08-14 花王株式会社 繊維用処理剤
WO2017136264A1 (fr) * 2016-02-03 2017-08-10 Elevance Renewable Sciences, Inc. Acides gras insaturés alcoxylés et leurs utilisations
CN109486181A (zh) * 2018-11-22 2019-03-19 江苏利德尔新材料科技有限公司 一种抗静电高阻燃mc尼龙复合材料的制备方法

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US3287324A (en) * 1965-05-07 1966-11-22 Du Pont Poly-meta-phenylene isophthalamides
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DE3929376C1 (fr) * 1989-09-05 1991-04-18 E.I. Du Pont De Nemours And Co., Wilmington, Del., Us

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Also Published As

Publication number Publication date
EP0574507B1 (fr) 1994-08-10
JPH06505312A (ja) 1994-06-16
DE4106682C2 (de) 1995-08-10
DE69200321D1 (de) 1994-09-15
DE69200321T2 (de) 1995-02-09
JP3383860B2 (ja) 2003-03-10
ES2057991T3 (es) 1994-10-16
BR9205704A (pt) 1994-08-02
AU660455B2 (en) 1995-06-29
AU1460892A (en) 1992-10-06
CN1076977A (zh) 1993-10-06
WO1992015747A1 (fr) 1992-09-17
CN1049462C (zh) 2000-02-16
DE4106682A1 (de) 1992-10-08

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