CN1049462C - Highly processable aromatic polyamide fibers, their production and use - Google Patents

Highly processable aromatic polyamide fibers, their production and use Download PDF

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Publication number
CN1049462C
CN1049462C CN92103391A CN92103391A CN1049462C CN 1049462 C CN1049462 C CN 1049462C CN 92103391 A CN92103391 A CN 92103391A CN 92103391 A CN92103391 A CN 92103391A CN 1049462 C CN1049462 C CN 1049462C
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Prior art keywords
acid
fiber
alcohol
alkyl
weight
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CN1076977A (en
Inventor
S·勒布拉特
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EIDP Inc
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EI Du Pont de Nemours and Co
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Priority to DE4106682A priority Critical patent/DE4106682C2/en
Priority to EP92907819A priority patent/EP0574507B1/en
Priority to US07/844,271 priority patent/US5270113A/en
Priority to PCT/US1992/001891 priority patent/WO1992015747A1/en
Priority to JP50744992A priority patent/JP3383860B2/en
Priority to DE69200321T priority patent/DE69200321T2/en
Priority to ES92907819T priority patent/ES2057991T3/en
Priority to BR9205704A priority patent/BR9205704A/en
Priority to AU14608/92A priority patent/AU660455B2/en
Application filed by EI Du Pont de Nemours and Co filed Critical EI Du Pont de Nemours and Co
Priority to CN92103391A priority patent/CN1049462C/en
Publication of CN1076977A publication Critical patent/CN1076977A/en
Publication of CN1049462C publication Critical patent/CN1049462C/en
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    • 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

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  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
  • Artificial Filaments (AREA)

Abstract

The present invention relates to a polyarylamide fibre with a coating layer and a processing method thereof. The coating layer contains a lubricant, an emulsion system and an antistatic agent.

Description

The aramid fibre of highly processable and production thereof and purposes
The present invention relates to give aramid fibre and the production and the purposes of excellent processability.
Be stated from＜Research Disclosure (NO.195, in July, 1980) in No. 19520 open source information on, disclose out some finishing agents that can be used to handle industrial fibers such as polyamide and aramid fiber, this finishing agent comprises lubricant, and said lubricant comprises the ester that is made of aliphatic saturated carboxylic acid and polyhydroxy-alcohol or aliphatic nonbranched alcohol.These finishing agents also contain emulsifying agent or emulsification system, raising composition stable with antioxidant, as the polysiloxanes of another kind of heat endurance lubricant with as the sulfonation natural oil of antistatic agent.In addition, these finishing agents also can contain biostatic agent and other emulsifying agents and lubricant.
But, the finishing agent of putting down in writing in the above-mentioned document, but at the mantle friction character scrubbing character of the fiber of the processing that obtains, prevent that corruption from touching and be not suitable for the object of the invention aspect the deposition, fibrillation effect and the static electricity resistance that cause.
Some high strength have been proposed, high modulus fibre strengthens elastomeric material and plastic material.
The commercially available fiber rigidity height of the overwhelming majority, mainly because of excessive friction between long filament cause the suface friction of fibrillation poor, poor with the surface affinity of most traditional elastomeric matrices, thermoplastic matrix and the heat-curable matrix of the enhancing of using.
These shortcomings and defective cause the physical property of intensity and modulus and so on to reduce, thereby to have stimulated the active demand of people for the fiber of some highly processables, this fiber must be to handle and do not produce machine with knitting or knit operation easily to amass attached.
According to the present invention, utilize known covering with paint method a kind of specific surface treatment composition of coating on the surface of the prior dry aramid fiber of crossing, perhaps on the unstretched and dry aramid fiber of crossing, be coated with this finishing agent, a kind of surface-treated new fiber of output, this fiber with rubber coating with strengthening article form or demonstrating good machinability characteristic during with the yarn shape of fiber weave structure or use.Use said fiber final products the product serviceability thereby significantly improve.
Therefore, the present invention relates to a kind of aramid fiber of highly processable, but this fiber has high-modulus, improved mantle friction performance and scrubbing character, the long-pending attached effect of the abrasion of polymer is little, the fibrillation effect is little, and has the long-term antistatic behaviour of improvement, and has the coating of being drawn by surface conditioning agent, wherein contain lubricant, emulsifier system, antistatic additive and other composition, the composition of said finishing agent is:
(a) the ester oil lubricant of forming by a kind of ester of 30～70wt%, its composition
Be:
(I) pure composition: the saturated mono hydroxyl uncle or the secondary alcohol of branching, its general formula:
Figure C9210339100102
Wherein
R 1Represent C 1-C 16Alkyl
R 2Represent H, C 1-C 16Alkyl (when K=1) and
R 2Represent C 1-C 16Alkyl (when K=0)
h＝0～5
K=0 or 1
j＝0～4
M=0～16, and
Wherein the total number of carbon atoms is less than 25, and
(II) carboxylic acid composition: unrighted acid, its general formula:
R 3-(COOH) s，s＝1～6
Wherein
R 3Represent C 4～C 19Alkenyl, C 4～C 19Alkadienyl, C 4
～C 19Alkatriene base, phenyl, naphthyl, 2-phenyl vinyl, or
Unsaturated dicarboxylic acid with following general formula:
HOOC-(CH＝CH) n-COOH
Wherein n is 1 or 2, and said ester composition solidification point is lower than 5 (preferably being lower than 0) ℃, and dynamic viscosity is (20 ℃) 100～350mm 2/ second, iodine number is between 30～140 (preferably 30～80);
(b) emulsification system of 20～50 weight %, said emulsification system by the aliphatic acid of undersaturated ethoxylation and (or) fatty alcohol of undersaturated ethoxylation and (or) alkylamine (general formula is as follows) of ethoxylation forms,
R 4-X-(EO) p(PO) q-OH
Wherein
R 4Represent C 5-C 20Alkenyl, phenyl, naphthyl or C 8Or C 9
Alkyl phenyl
X representative-COO-,-NH-or-O-
EO represents an ethylene oxide unit
PO represents a propylene oxide units
P=2～15 and
q＝0～10；
(C) antistatic additive of 5～15 weight % is by C 4-C 12Alkyl sulfonic ester, C 4-C 12Alkyl phosphate or C 4-C 20The alkali metal salt of alkyl carboxylic acid is formed:
(d) corrosion inhibitor of 0.2～2 weight %, and
(e) the selective additives composition makes said coating amount on the said fiber account for 0.05～2.0 (preferred 0.2～1.0) weight % of said fiber.
The composition of said coating preferred (most preferably) is: the ester oil (a) of 50～60 (55～60) weight %, the emulsification system (b) of 25～40 (29～35) weight %, the antistatic additive (C) of 5～10 (5～7) weight %, the corrosion inhibitor (d) of 0.3～1 (0.3～0.5) weight % and the selective additives (e) that adds in case of necessity.
Polyarylamide of the present invention has following further feature: than fracture strength is 2.65-33.5 li of newton/dtex (3-38 restrains the dawn),
Specific modulus is 8.83～2207 lis of newton/dtexs (the 10-2500 gram/dawn)
The coefficient of kinetic friction of fiber and metal (on 1100 dtex polyarylamide yarns, under 200 meters/minute conditions) is less than 0.55, preferably less than 0.50,
Fiber and intermetallic interfacial friction factor (on 1100 dtex polyarylamide yarns, under 0.016 cel condition) be less than 0.10, preferably less than 0.05,
The long-pending attached amount that causes because of abrasion is less than the 0.5mg/kg yarn,
Remnants covering with paint amount after the washing is less than 15 weight % of initial covering with paint amount.
Compare with the fiber that uses other finishing agent, fiber of the present invention has the combination property of improvement at aspects such as the washability of scatter and disappear with the sootiness of the loss in weight tolerance property, fiber and adherences.
Within the scope of the invention, said " fiber " textile raw material of being meant continuous filament yarn and single thread or rope, staple fibre, fibre bundle (for example obtaining), yarn or common weaving reeled yarn, cutting off crimped fibre, paper pulp and have industrial woven, the twisting of making by polyarylamide of fibre structure, knitting, braiding, curl or pack by pull-cut process.
Said polyarylamide is a kind of like this polymer, and they are part, the overwhelming majority or all are made up of aromatic ring that these aromatic rings link to each other or optionally link to each other by other bridge construction in addition by the phosphoamide bridge.Utilize following repetitive general formula:
(CO-NH-A 1-NH-CO-A 2-CO-) nThe structure of this aromatic polyamides can be described, in the formula: A 1And A 2Identical or different, be aromatic ring, many aromatic rings or hetero-aromatic ring, and these aromatic rings can also be substituted.A 1And A 2Usually can be selected from independently of each other: 1,4-phenylene, 1,3-phenylene, 1,2-phenylene, 4,4 '-biphenylene, 2,6-naphthylene, 1,5-naphthylene, 1,4-naphthylene, phenoxy group benzene-4,4 '-subunit, phenoxy group benzene-3,4 '-subunit, 2, the inferior pyridine radicals and 2 of 5-, the inferior quinolyl of 6-, these groups also can be replaced or not replace by one or more following substituting groups; Said substituting group can comprise: halogen, C 1-C 4Alkyl, phenyl, carbonylic alkoxy, C 1-C 4Alkoxyl, acyloxy, nitro, dialkyl amino, alkylthio, carboxyl and sulfonyl.-CONH-group also can (CONHNH-) base, azo group or azoxy replace by carboxylic hydrazide.
The preferred fiber that all obtains by aromatic polyamides.The example of polyarylamide is benzenedicarboxamide and a polyparaphenylene terephthalamide between poly-metaphenylene.
US3, benzenedicarboxamide and US3 between the poly-metaphenylene of record in 287,324,869,429 and DE2219703 in the polyparaphenylene terephthalamide particularly suitable introduced.
Additive can use and in fact discovery with said polyarylamide: nearly other polymer of 10 weight % can mix with said polyarylamide, perhaps can use and contain nearly 10 other diamines of weight % (diamines that replaces said polyarylamide) or the nearly copolymer of 10 other diacid chlorides of weight % (diacid chloride that replaces said polyarylamide).
Other aromatic polyamides that is suitable for has following array structure:
(NH-Ar 1-X-Ar 2-NH-CO-Ar 1-X-Ar 2-CO-) nWherein: X represents O, S, SO 2, NR, N 2, CR 2, CO, R representative
H, C 1-C 4Alkyl, and
Ar 1And Ar 2Can be identical or different, and be selected from 1,2-phenylene, 1,3-phenylene and 1, the 4-phenylene, at least one hydrogen can be by halogen in these phenyl
Plain and (or) C 1-C 4Alkyl replaces.
The decorative composition that is coated with of the present invention contains lubricant, emulsification system, antistatic additive and corrosion inhibitor, and water in case of necessity and (or) other additive.
Said lubricant is the ester oil with above-mentioned feature.The alcoholic compound of said ester oil (I) example, can be 2-methyl isophthalic acid-propyl alcohol, 2-butanols, 2-amylalcohol, 2-methyl-1-butene alcohol, 3-methyl isophthalic acid-butanols, 3-methyl-2-butanols, 2-methyl-1-pentene alcohol, 4-methyl-1-pentene alcohol, 4-methyl-2-amylalcohol, 2-amylalcohol, 3-enanthol, sec-n-octyl alcohol, 2-ethyl-1-hexanol, 3,5-dimethyl-1-hexanol, 5-nonyl alcohol, 2,6-2,6-dimethyl-4-heptanol, different 16 carbon alcohol or different 13 carbon alcohol.Carboxylic acid composition's (II) example can be lauroleic acid, 9-tetradecenoic acid, palmitoleic acid, oleic acid, cis 9-eicosenoic acid, erucic acid, castor oil acid, tallow fatty acid, linoleic acid, linolenic acid, fumaric acid, maleic acid, cinnamic acid, naphthoic acid, benzoic acid, M-phthalic acid, terephthalic acid (TPA), trimellitic acid or 1,2,4, the 5-benzenetetracarboxylic acid.
The dynamic viscosity of said ester oil is preferably at 200～300mm 2In/second (20 ℃) scope.
Emulsifier system definition of the present invention as above.The example of unrighted acid is lauroleic acid, 9-tetradecenoic acid, cis 9-eicosenoic acid, palmitoleic acid, erucic acid or castor oil acid, preferred oleic acid (containing the 3-15 moles of ethylene oxide).The example of unsaturated fatty alcohol is trans 9-oleyl alcohol, erucyl alcohol, Brazilian enol, preferred oil pure and mild (or) lipidol (containing the 3-10 moles of ethylene oxide).Other example is C 8-or C 9-alkylphenol b-oxide, preferred octyl phenol-or nonyl phenol b-oxide (containing 5.5 moles of ethylene oxide).
Said antistatic agent compound is alkyl (as dodecyl or oil base) sulfonic acid, C 4-C 12The alkali metal of alkyl phosphoric acid (mixture of monoesters and dibasic acid esters) and so on alkyl phosphoric acid (preferred sodium) salt, and the salt of aliphatic acid (as oleic acid).Sodium chloride content should be lower than 0.1%.Also can use alkyl sulfate, but preferred it because their easy hydrolysis, thereby lose its antistatic usefulness.
Operable corrosion inhibitor is C 4-C 12The diethanolamine salt of alkyl phosphate (list or dibasic acid esters) or aliphatic acid or benzoic amine salt.
Said composition is can selectivity moisture to be beneficial to that it is stable, even dilute with water it so that can be moisture before obtaining the required concentration of coated fiber.
Need additive optionally to be added among the said composition under the situation of specific character or process conditions, for example handle like this under the occasions such as adhesion strength, the degree of cross linking, antiultraviolet, anti-oxidant, painted or this sex change adjusting.These additives can also contain fungicide, bactericide and pesticide.
A kind of processing aramid fiber can be prepared as follows with composition: under the temperature that improves, preferably mix whole compositions under 30～40 ℃ of temperature, so that make a kind of grease of evenly and clearly infusing.The mixture that for example can prepare a kind of following composition: 550 gram tebelons, 350 gram emulsification systems (by 200 gram nonyl phenol b-oxides (containing 8EO) and 150 gram oleic acid b-oxides (containing 10EO)), 70 gram sodium sulfonates and 5 gram benzoic acid diethanolamine salts.In case of necessity, in this mixture, add about 25 gram water so that eliminate turbidity.The oil of infusing clearly in order to obtain a kind of stablizing also must add entry.When needing, can the pH value be adjusted to 6～8, preferably be adjusted to 7 with diethanol amine or acetate.
The further feature that the present invention is coated with decorative composition is: viscosity is 150～500mm 2/ second (preferred 150～300mm 2/ second (20 ℃), weightless (200 ℃ following 2 hours after) are less than 25% (preferably less than 15), 20 ℃ down the surface tension of 1% emulsions less than 35 (preferably less than 32) mN/m.
The invention still further relates to the production method that scribbles aramid fibre surface conditioning agent, that processability is good on the surface.
Cover with paint, lacquer, colour wash, etc. aramid fiber with surface conditioning agent of the present invention, can adopt the whole bag of tricks, more specifically say, for example can adopt following method (a) and (b).
Method (a) is never to be coated with said surface conditioning agent on the dry and aramid fiber that stretched, and method (b) is to be coated with said surface conditioning agent in advance on the dry aramid fiber of crossing, and two kinds of methods all adopt known coating apparatus.The said decorative composition that is coated with uses with the stoste form or with the dilution aqua form that concentration is low to moderate 1 weight %.
The preferred version of method (a) is the said decorative composition (this is equivalent to 30 parts of weight and is coated with decorative composition+70 part water) that is coated with that is applied in the about 30 weight % of concentration in the water on wet aramid fiber.Then 150～190 under (preferred about 170) ℃ temperature, stretch in the drying steps dry through fiber several seconds (5-10 second) that said emulsion was handled at fiber.About 630 bundle/minute (accessible scope is 120～1200 meters/minute) of speed that keep yarn simultaneously.
The preferred version of method (b) is: the yarn of aramid fiber or rope are passed through in the dipping unit, the said decorative composition that is coated with of dipping, in addition dry in the air chamber of heating down in 80～190 (preferred 110～130) ℃ then, dry under 6 newton's predetermined tension for 1670 untwisted dtex yams.The most preferably temperature of this step is approximately 120 ℃.Speed is adjusted to 15～100 meters/minute, decides on the said dipping concentration that is coated with decorative composition (concentration in the water can from 1 weight % to 100 weight %).So-called 100% be coated with decorative composition, be meant said finishing agent stoste.
Method (a) and covering with paint amount (b) are 0.05～2 (preferred 0.2～1.0) weight %.
In case of necessity, can adopt multistep processes implementation method (a) and (b), though said fiber in surface conditioning agent submergence several times, drying successively then.For example, said finishing agent is coated on the never dry wet fiber of crossing, fiber drying then can be used said surface conditioning agent once or several drying steps in the middle of can being with or without again therebetween then.
Fiber of the present invention can be used to strengthen flexible pipe, band, rope and cable (comprising optical cable), rubber articles and composite (as sports goods, medical running stores, construction material and acoustical material, civilian or military transportation and protective equipment).
Embodiment 1
The 1100 dtex yams type aramid fibers that scribble finishing agent of the present invention and the commercially available polyarylamide yarn of the identical dtex that scribbles the standard finishing agent have been compared in this example.
Aramid fiber of the present invention is compared with aramid fiber (contrast) with commercially available contrast, at frictional property, dynamic friction F/M (200 meters/minute) especially is much all superior with aspects such as the long-pending attached amount of mg/ kilogram yarn tolerance and fibrillation effects.
Therefore when antistatic behaviour was evaluated, excellent antistatic started from-6KV usually, and this that fiber of the present invention is recorded-2.5KV value sees it is outstanding from electrostatics.
Washing performance (washing (-)off properties) is a very important factor, because residual covering with paint dosage (in %) influence covering with paint is subsequently operated after the washing step.The scourability numerical value of being mentioned in the following table obtains with commercial scale, comprising using the fiber made by yarn of the present invention and with the commercially available yarn of same Denier in contrast data after the processing of standard finishing agent.These data were examined through laboratory test, and verification mechanism is with 50 ℃ of soft water washing sample yarns twice, per 10 gram yarn water 100ml.
Coefficient of friction is measured by laxative remedy: a volume yarn is in tensioning apparatus threading between a deflector roll and two deformeters on the work beam that is driven by a variable speed motor by one.Said two deformeters write down T respectively 1And T 2, the tension force of input and output.Be calculated as follows out coefficient of friction:
T 1/ T 2=e * p (α, f) in the formula, α is an angle of friction, f be coefficient of friction (fiber and fiber, fiber and metal or fiber and pottery, depend on use be through the polishing chromium pin or ceramic pin).Use R-1182 type Rothschild frictiograph according to standard operation formality known in the art.
" Staff-Tester G a 555 " type test instrument (the long-pending attached amount that causes because of abrasion Zweigle) is measured by West Germany, with this Instrument measuring fiber and fibre frictoin cause the mill amount of touching of fibrous material.
(West Germany has measured the fibrillation index on Zweigle) at " G566 " type equipment.
The physical property comparison sheet
(1100 dtex fiber) edition with parallel text invention 1. frictions
Fiber and fiber (0.016cm/s) 0.22 0.215
(128cm/s) 0.28 0.265
Fiber and metal (0.016cm/s) 0.12 0.045
(128cm/s) 0.30 0.265
(200cm/s) long-pending attached amount (mg/kg) the 10 0.53. fibrillation indexes 21 2-54. scourabilities of 0.70 0.552. 46% 9%
(residual covering with paint dosage)
Embodiment 2
This example has been tested the fabric that is made into yarn of the present invention and the ballistic performance of the control fabric that the commercially available yarn covered with paint, lacquer, colour wash, etc. with the standard finishing agent is made into.
Said fabric is made with 1111 dtexs (1000 dawn) yarn.
In the high-tenacity fiber field, the weaving process of ballistic fabric can cause loss of strength usually, and the amount of this loss of strength is determined with conventional method known in the art usually, promptly extracts yarn out and measure toughness from said fabric.Following table demonstrates product of the present invention and has remarkable advantage, and promptly under heavily fabric (typical case be 12 warp thread/centimetre) situation, said loss of strength reduces half (7% pair 14%).Ballistic performance (V 50: see test method) also be improved, improve 8% and 5-8% respectively for embryo cloth and the cloth through covering with paint, lacquer, colour wash, etc. (referring to that fabric is after final the processing).
For light-weight fabric, the ballistic performance of lightweight embryo cloth also improves 4.5%.
Strength Changes and ballistic performance
Fabric grade Loss of strength Bullet-proof improvement rate (%)
The present invention's contrast V of the present invention 50Contrast
Heavily fabric (prior art) is 3. ballistic performance+5～8% (covering with paint cloth) light-weight fabric prior art of embryo cloth 5-9% 14-18%2. ballistic performance+8% (embryo cloth) 1.) 1. embryo cloth 0-2% 0-2%2. ballistic performance+5% (embryo cloth)
Shellproof test
STANAG2920 measures V according to the NATO standardization agreement 50Shellproof test method.
Material or armoring shellproof limit velocity V 50Be defined as such speed, utilizing the probability that penetrates of plus-minus ammunition gunning and following computing method selected bullet under this speed is 0.5 just.
Plus-minus ammunition gunning (The Up and Down firingmethod):
First powder volume that bullet is packed into, the speed that bullet is produced equal the shellproof limit V of estimated plate armour 50If first bullet of shooting all penetrates plate armour, the gunpowder of packing in second bullet and quantitatively reducing then.Make it about 30 meter per seconds of reduction of first of velocity ratio.If first bullet that penetrates only part passes plate armour, second gunpowder that bullet is packed into and quantitatively increased then makes it high about 30 meter per seconds of first of velocity ratio.After first round penetration test is finished, should quantitatively regulate explosive payload, make the speed of bullet after each adjusting increase or reduce about 15 meter per seconds.Continue shooting according to given method of operating then, so that the V that obtains expecting 50(BLP, Ballistic Limit Protection).
V 50Calculate
Calculate V after shooting many bullets 50, it is the mean value of speed that clear impact is noted, said clear impact is made up of three partial velocities the highest of partial penetration bullet and three minimum speeds penetrating bullet fully, condition be these six speed all fall into ± 40 meter per second scopes in.
Embodiment 3
This example has been carried out knitting machinability evaluation under following routine condition: ELHA swinging knitting machine (RRU type), and 4 hours test periods, 670 rev/mins of machine speeds, 15 meters/minute of knitting speed, knitted structure 3 knitting technology weaves/centimetre.
The serviceability yarn type contrast edition with parallel text inventive method of different yarn types
(a) and (b)
The long-pending addendum of the no knit stitches outward appearance heterogeneity homogeneous homogeneous of the high nothing of 0T/m 120T/m 0T/m fibrillation effect is gathered few no spreadability is not had low optimum factor homogeneous
What as above table was found out is such, compares with control yarn, uses yarn of the present invention can access best productivity levels and maximum use value.The situation of prior art product is to use twisting.The result clearly illustrates that: use the advantage of yarn of the present invention to be to avoid the twisting operation.
Embodiment 4
In this example the flexible pipe made from yarn of the present invention has been done fatigue test, tested the waveform that has adopted irregular by the Ford standard, pressure is the 1-3.5 crust, and frequency is 0.5Hz.
For control yarn, generally reached for 50,000 weeks before the fracture, be enough to by this test.But obtained the result in 80,000 weeks for five hose tests that contain yarn of the present invention.This shows that yarn of the present invention has significant superiority aspect fatigue durability.
Embodiment 5
This example has compared rope made from yarn of the present invention and the difference of rope on strength efficiency made from control yarn.
Compare with commercially available polyarylamide base-material structure, the rope made from yarn of the present invention improves on strength efficiency and reaches 30%.If a kind of rope is made with several strands of yarns, the intensity that should equal per share yarn on the strength theory of so this rope multiply by the number of share of stock of used yarn, but in fact situation is not like this.And finishing agent of the present invention helps to overcome this shortcoming.
In single test chamber test, the yarn rope brute force that has recorded a kind of parallel construction is 524 newton, and this rope is that 1100 dtexs (1000 threads) the polyarylamide yarn sold by three stock markets (twist with the fingers 140T/m eventually, every meter add twisting count) is made.In contrast to this, measured the brute force of the parallel warp rope structure of being made by the yarn of handling through finishing agent of the present invention (the covering with paint amount is 0.8%) of three strand of 1100 dtex, the amount of twist that records at last is that the brute force of the yarn of 140T/m is 592 newton, raising amount suitable 30%.
Embodiment 6
Tested several quality index of yarn of the present invention in this example, and done contrast with these quality index of control yarn.
Experimental condition:
Under 230 ℃, fiber placed and measured the percentage (weightlessness) that coating material loses after 8 hours.Finishing agent percentage is measured with the lytic agent method of extraction before and after placing with heat.
Known according to the industry and adopt washing (coming unstuck) method of operating, after the said fiber of washing, the remaining finishing agent that solvent extraction retains on said fiber, the percentage of residue after also mensuration is come unstuck in this way.This percentage be come unstuck relatively the initial covering with paint dosage that records before the step calculate.
The coefficient of friction that utilizes the Rothschild equipment introduced previously and method under 150 meters/minute condition, to measure said fiber and intermetallic (F/M).
All yarns were for 1000 dawn, contained 670 threads, and covered with paint, lacquer, colour wash, etc. with 750 meters/minute speed with a kind of decorative composition stoste that is coated with under drying regime, and the covering with paint amount is 0.8%.
Said finishing agent A contains the carboxylic acid composition of 70: 30 mixtures of benzenetricarboxylic acid and phthalic acid as said ester oil.Finishing agent B contains C 18Alkenyl formic acid and C 1670: 30 mixtures of alkenyl formic acid are as the alkenyl formic acid composition of ester oil.
Contrast with finishing agent is＜Research Disclosure〉NO.The C that discloses in No. 19520 open source information (in July, 1980) in 195 12/ C 15Mineral oil.
Find that by this example be coated with in the middle of the decorative composition of the present invention, the carboxylic acid composition of the ester oil of use has an above carboxyl, n=2～6 wherein, this weightless much less when being coated with the decorative composition heating.Weight loss on heating is more little, means to use under improving temperature and be fuming when operating few more.The remaining F/M friction in the back of coming unstuck of fiber finishing agent
Finishing agent coefficient A the present invention 58 0.50 (not being fuming) B the present invention 11 14 0.47C of weight loss on heating contrast 23 45 0.65

Claims (16)

1. have the aramid fiber of the coating that is produced by a kind of surface conditioning agent, said coating contains lubricant, emulsification system, antistatic additive and other composition, and said surface conditioning agent is made up of following ingredients:
(a) the ester oil lubricant formed by a kind of ester of 30～70 weight %, said ester generates by composition (I) with (II),
(I) pure composition: the saturated monohydric primary alcohol or the secondary alcohol of branching, its general formula is:
Figure C9210339100021
Wherein
R 1Represent C 1-C 16Alkyl
R 2Represent H, C 1-C 16Alkyl, (when K=1) and C 1-
C 16Alkyl (when K=0)
h＝0～5
j＝0～4
K=0 or 1
M=0～16, and
Wherein the total number of carbon atoms is less than 25; (II) carboxylic acid composition: unrighted acid, its general formula:
R 3-(COOH) sS=1-6 wherein
R 3Represent C 4-C 9Alkenyl, C 4-C 19Alkadienyl, C 4-C 19Alkatriene base, phenyl, naphthyl, 2-phenyl vinyl, or have the unsaturated dicarboxylic acid of following general formula:
HOOC-(CH＝CH) n-COOH
N=1 or 2 wherein, and
Said ester solidification point is lower than+and 5 ℃, dynamic viscosity (20 ℃) is 100～350mm 2/ second and iodine number are between 30～140;
(b) 20～50 weight % emulsification systems, by undersaturated ethoxylated fatty acid and (or) undersaturated ethoxylized fatty alcohol and (or) ethoxylated alkylamine (general formula is as follows) forms;
R 4-X-(EO) p(PO) q-OH
Wherein
R 4Represent C 5～C 20Alkenyl, phenyl, naphthyl or C 8-or C 9Alkyl phenyl;
X representative-COO-,-NH-or-O-
EO represents an ethylene oxide unit
PO represents a propylene oxide units
P=2～15 Hes
q＝0～10；
(C) 5～15 weight % antistatic additive are by C 4-C 12The C of alkyl sulfonic ester 4-C 12Alkyl phosphate or C 4-C 20The alkali metal salt of alkyl carboxylic acid is formed;
(d) corrosion inhibitor of 0.2-2 weight %, and
(e) to make the said coating amount on the said fiber be 0.05～2.0 weight % to the selective additives composition.
2. according to the said fiber of claim 1, the pure composition (I) that it is characterized in that said (a) is 2-methyl isophthalic acid-propyl alcohol, 2-butanols, 2-amylalcohol, 2-methyl-1-butene alcohol, 3-methyl isophthalic acid-butanols, 3-methyl-2-butanols, 2-methyl-1-pentene alcohol, 4-methyl-1-pentene alcohol, 4-methyl-2-amylalcohol, 2-amylalcohol, 3-enanthol, sec-n-octyl alcohol, 2-ethyl-1-hexanol, 3,5-dimethyl-1-hexanol, 5-nonyl alcohol, 2,6-2,6-dimethyl-4-heptanol, different 16 carbon alcohol or different 13 carbon alcohol.
3. according to the said fiber of claim 1, the carboxylic acid composition (II) who it is characterized in that said (a) is lauroleic acid, 9-tetradecenoic acid, palmitoleic acid, oleic acid, cis 9-eicosenoic acid, erucic acid, castor oil acid, tallow fatty acid, linoleic acid, linolenic acid, fumaric acid, maleic acid, cinnamic acid, naphthoic acid, benzoic acid, M-phthalic acid, terephthalic acid (TPA), trimellitic acid or 1,2,4, the 5-benzenetetracarboxylic acid.
4. according to the described fiber of claim 1, it is characterized in that said emulsification system contain octyl phenol b-oxide (5-15 mole EO) and (or) nonyl phenol b-oxide (5-15 mole EO) and (or) dodecenoic acid, 9-tetradecenoic acid, palmitoleic acid, cis 9-eicosenoic acid, erucic acid, castor oil acid or the oleic acid (3-15 mole EO) of ethoxylation and (or) b-oxide (3-10 mole EO) of trans 9-oleyl alcohol, erucyl alcohol, Brazilian enol or oleyl alcohol and (or) tallow alcohol b-oxide (3-10 mole EO).
5. according to the described fiber of claim 1, it is characterized in that said surface conditioning agent consists of (% meter by weight):
50-60(a)，
25-40(b)，
5-10(c)，
0.3-1 (d) and
Selective additives composition (e).
6. according to the described fiber of claim 1, it is characterized in that the repetitive general formula of said polyarylamide is:
(NH-A 1-NH-CO-A 2-CO-) n A wherein 1And A 2Identical or different, representative replace or unsubstituted aromatic ring and (or) many aromatic rings and (or) hetero-aromatic ring.
7. according to the described fiber of claim 6, it is characterized in that A 1And A 2Be selected from independently of each other: 1,4-phenylene, 1,3-phenylene, 1,2-phenylene, 4,4 '-biphenylene, 2,6-naphthylene, 1,5-naphthylene, 1,4-naphthylene, phenoxy group benzene-4,4 '-two bases, phenoxy group benzene-3,4 '-two bases, 2, the inferior pyridine radicals and 2 of 5-, the inferior quinolyl of 6-and can be replaced or not replace by one or more substituting groups, said substituting group comprises halogen, C 1-C 4Alkyl, phenyl, carbonylic alkoxy, C 1-C 4Alkoxyl, acyloxy, nitro, dialkyl amido, alkylthio, carboxyl and sulfonyl; Wherein said amide groups also can be replaced by carbonyl diazanyl, azo group or azoxy.
8. according to the described fiber of claim 6, it is characterized in that said aromatic polyamides is a kind of like this copolyamide, wherein total amount A 1And A 2In preferably at least 80 moles of % be can replace or unsubstituted 1,4-phenylene and phenoxy group benzene-3,4 '-subunit, and phenoxy group benzene-3,4 '-subunit content is 10-40 mole %.
9. according to the described fiber of claim 6, it is characterized in that said polyamide fiber is made up of poly-(benzenedicarboxamide between metaphenylene).
10. according to the described fiber of claim 6, it is characterized in that said polyamide fiber is made up of poly-(to phenylene terephthalate amine).
11., it is characterized in that said polyamide fiber optionally contains the unit that is derived by 3-or 4-aminobenzoic acid according to the described fiber of claim 6.
12. a manufacturing has the method for the aramid fiber of surface conditioning agent coating, comprising following each step: coating concentration is the said surface conditioning agent aqueous systems of 1-100 weight % on said fiber, dry said fiber under temperature between 150～190 ℃, and can optionally reuse said surface conditioning agent, it is characterized in that said surface conditioning agent consists of:
(a) the ester oil lubricant formed by a kind of ester of 30-70 weight %, said ester forms by (I) with (II):
(I) pure composition is saturated monohydric primary alcohol of branching or secondary alcohol, and general formula is:
Figure C9210339100062
Wherein
R 1Represent C 1-C 16Alkyl,
R 2Represent H, C 1-C 16Alkyl, (during K=1) and C 1-
C 16Alkyl (during K=0),
h＝0～5
j＝0～4
K=0 or 1
M=0～16, and
Wherein the total number of carbon atoms is less than 25, and (II) carboxylic acid composition, is a kind of unrighted acid, and general formula is:
R 3-(COOH) s，s＝1-6
Wherein
R 3Represent C 4-C 19Alkenyl, C 4-C 19Alkadienyl, C 4-C 19Alkatriene base, phenyl, naphthyl, 2-phenyl vinyl, or the unsaturated dicarboxylic acid of following general formula:
HOOC-(CH＝CH) n-COOH
N=1 or 2 wherein,
And said ester solidification point be lower than+5 ℃, dynamic viscosity (20 ℃) is 100～350mm 2/ second, iodine number is 30～140;
(b) 20～50 weight % emulsification systems, this emulsification system by undersaturated ethoxylated fatty acid and (or) undersaturated ethoxylized fatty alcohol and (or) ethoxylated alkylamine forms, its general formula is:
R 4-X-(EO) p(PO) q-OH
Wherein
R 4Represent C 5-C 20Alkenyl, phenyl, naphthyl or C 8Or C 9
-alkyl phenyl.
X representative-COO-,-NH-or-O-,
EO represents ethylene oxide unit,
PO represents propylene oxide units,
P=2-15 and
q＝0-10，
(c) 5-15 weight % antistatic additive is by C 4-C 12Alkyl sulfonic ester, C 4-C 12Alkyl phosphate or C 4-C 20The alkali metal salt of alkyl carboxylic acid is formed,
(d) 0.2-2 weight % corrosion inhibitor, and
(e) selective additives composition.
13. the described method of claim 12 is characterized in that the concentration of said surface conditioning agent in water is 30 weight %.
14. the described method of claim 12 is characterized in that said surface treatment agent concentration is 100 weight %, i.e. stostes.
15. the described method of claim 12 is characterized in that said surface conditioning agent is applied on the never dry aramid fiber of crossing.
16. the described method of claim 12 is characterized in that said surface treatment is coated on the prior dry aramid fiber of crossing.
CN92103391A 1989-09-05 1992-04-03 Highly processable aromatic polyamide fibers, their production and use Expired - Fee Related CN1049462C (en)

Priority Applications (10)

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DE4106682A DE4106682C2 (en) 1991-03-02 1991-03-02 Aromatic high-performance polyamide fibers, their production and use
AU14608/92A AU660455B2 (en) 1991-03-02 1992-03-02 Highly processable aromatic polyamide fibers, their production and use
PCT/US1992/001891 WO1992015747A1 (en) 1991-03-02 1992-03-02 Highly processable aromatic polyamide fibers, their production and use
JP50744992A JP3383860B2 (en) 1991-03-02 1992-03-02 Aromatic polyamide fibers with high processability, their production and use
DE69200321T DE69200321T2 (en) 1991-03-02 1992-03-02 EASILY PROCESSABLE AROMATIC POLYAMIDE FIBERS, THEIR PRODUCTION AND USE.
ES92907819T ES2057991T3 (en) 1991-03-02 1992-03-02 HIGHLY PROCESSABLE AROMATIC POLYAMIDE FIBERS, THEIR PRODUCTION AND USE.
EP92907819A EP0574507B1 (en) 1991-03-02 1992-03-02 Highly processable aromatic polyamide fibers, their production and use
US07/844,271 US5270113A (en) 1989-09-05 1992-03-02 Highly processable aromatic polyamide fibers, their production and use
BR9205704A BR9205704A (en) 1991-03-02 1992-03-02 Highly processable aromatic polyamide fibers, their production and use
CN92103391A CN1049462C (en) 1991-03-02 1992-04-03 Highly processable aromatic polyamide fibers, their production and use

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JP4796724B2 (en) * 1999-07-12 2011-10-19 ソシエテ ド テクノロジー ミシュラン Sidewall tire casing capable of having a glossy film
JP4747255B2 (en) * 2000-12-27 2011-08-17 Ｊｎｃ株式会社 Tow having charging property and laminate using the same
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JP4480176B2 (en) * 2006-12-27 2010-06-16 竹本油脂株式会社 Synthetic fiber treatment liquid and synthetic fiber treatment method
JP5604141B2 (en) 2010-03-11 2014-10-08 Ｊｘ日鉱日石エネルギー株式会社 Oil composition and ultra-trace oil supply type cutting / grinding method
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JP2019507218A (en) * 2016-02-03 2019-03-14 エレヴァンス リニューアブル サイエンシズ インコーポレイテッドＥｌｅｖａｎｃｅ Ｒｅｎｅｗａｂｌｅ Ｓｃｉｅｎｃｅｓ， Ｉｎｃ． Alkoxylated unsaturated fatty acids and their use
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