CN1092254C - Filled thermoplastic cut-resistant fiber - Google Patents

Filled thermoplastic cut-resistant fiber Download PDF

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Publication number
CN1092254C
CN1092254C CN96195351A CN96195351A CN1092254C CN 1092254 C CN1092254 C CN 1092254C CN 96195351 A CN96195351 A CN 96195351A CN 96195351 A CN96195351 A CN 96195351A CN 1092254 C CN1092254 C CN 1092254C
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fiber
filler
particle size
cut
volume
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CN1190444A (en
Inventor
R·B·桑德
G·E·吉尔博格－拉夫司
W·F·科里尔
J·富林特
L·拉尼夫
S·W·桑普森
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CNA Holdings LLC
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Hoechst Celanese Corp
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    • D—TEXTILES; PAPER
    • D02—YARNS; MECHANICAL FINISHING OF YARNS OR ROPES; WARPING OR BEAMING
    • D02G—CRIMPING OR CURLING FIBRES, FILAMENTS, THREADS, OR YARNS; YARNS OR THREADS
    • D02G3/00—Yarns or threads, e.g. fancy yarns; Processes or apparatus for the production thereof, not otherwise provided for
    • D02G3/44—Yarns or threads characterised by the purpose for which they are designed
    • D02G3/442—Cut or abrasion resistant yarns or threads
    • A—HUMAN NECESSITIES
    • A41—WEARING APPAREL
    • A41D—OUTERWEAR; PROTECTIVE GARMENTS; ACCESSORIES
    • A41D31/00—Materials specially adapted for outerwear
    • A41D31/04—Materials specially adapted for outerwear characterised by special function or use
    • A41D31/24—Resistant to mechanical stress, e.g. pierce-proof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • 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
    • D01F1/10—Other agents for modifying properties
    • 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
    • D01F6/58—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products
    • D01F6/60—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products from polyamides
    • 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
    • D01F6/58—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products
    • D01F6/62—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products from polyesters

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  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Manufacturing & Machinery (AREA)
  • Health & Medical Sciences (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Medicinal Chemistry (AREA)
  • Mechanical Engineering (AREA)
  • Artificial Filaments (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Sealing Material Composition (AREA)

Abstract

A fiber having increased cut resistance is made from an isotropic polymer and a hard filler having an average particle size in the range of about 0.25 to about 10 microns and having a Mohs Hardness Value greater than about 3. The filler is included in an amount of at least about 0.1 % by weight. The preferred isotropic polymer is poly(ethylene terephthalate). The preferred filler is calcined alumina.

Description

High cut-resistant fiber and method for making thereof that the isotropism melt processable polymers of filling is made
Relevant application
The application is commonly assigned May 16 1994 08/243344 applying date of U.S. Patent application, and still in examination, and two parts divided an application.
Scope of the present invention
The present invention relates to fiber by the thermoplastic polymer system that contains hard filler with improved cut-resistance.
Background of the present invention
The fiber that always has improved anti-sharp knife edges cutting for a long time in exploration.It is very favourable adopting the anti-gloves that cut in meat-packing industry and automotive field.As United States Patent (USP) 4004295,4384449 and 4470251 and European patent 458343 pointed, made gloves with cut-resistance by the yarn that comprises the ductile metal silk or by the yarn that the fiber of high-tensile strength is spun into.
Thereby have by the gloves that the yarn that comprises the ductile metal silk is made and to cause the tired shortcoming that causes productivity ratio to descend and increase injured possibility of hand.And, to wear and tear for a long time and fold with gloves, both hands can be cut and abrade to the tired and fracture of wire possibility also.In addition, when washed gloves were at high temperature dry, wire can play thermolysis, can reduce the TENSILE STRENGTH of yarn or fiber like this, had therefore reduced the protective effect of gloves and had shortened service life of gloves.
The more conventional semi-crystalline polymer of cut-resistance of height-oriented fiber with high-modulus and high-tensile strength is good.The example of these height-oriented polymer comprises polyarylamide, TLCP and extended chain polyethylene.The also restricted shortcoming that their are used of these polymer: can lose various performances (polyethylene), anti-bleaching poor (polyarylamide) when in drying box, being heated, feel is uncomfortable and cost is high.
Flexibility is good, not only comfort and washing but also the uncomplicated anti-protective clothing that cuts are arranged is desirable.Therefore, need a kind of cut-resistant fiber that after daily washing, still can keep flexibility.This fiber can help being used to make protective clothing, particularly makes the highly soft anti-gloves that cut.
The thermoplastic polymer that will be mixed with particulate matter is made fiber, but with regard to improving the fiber cut-resistance, except that the thermic liquid crystal polymer, can't improve the cut-resistance of fiber significantly.For example, small amount of fines shape titanium dioxide has been used for polyester fiber as delustering agent.Also have and a small amount of cataloid is used for polyester fiber improves its gloss.Existing magnetic material is mixed makes magnetic fibre in the fiber.Example comprises: change thing mutually as the cobalt/rare earth elemental metals that is used for thermoplastic fibre that Japanese patent application 55/098909 (1980) is announced; Change thing or strontium ferrite mutually and as people's such as Poland Patent 251452 and K.Turek J.Magn.Magn.Mater. (1990) as the cobalt/rare earth elemental metals of announcing among the Japanese patent application 3-130413 (1991) that is used for skin-core fibre, 83 (1-3), the described magnetisable material that is used for thermoplastic polymer of pp.279-280.
Summary of the present invention
By sneaking into hard filler (preferably can be dispersed in all fibres), the isotropic polymer of melt-processable can be spun into fiber and yarn with more anti-sharp knife edges cutting.The Moh's scale number of hard filler is greater than 3, and consumption is 0.1-5 (volume) %.Particle mean size is between 0.25 micron-10 microns.The fiber height that the cut-resistance of this fiber is made by the same polymer of not adding hard filler.When measuring by Ashland anti-cutting performance (Ashland Cut Protection Performance) test, cut-resistance improves 20% at least.
It is also open that a kind of manufacturing has the new method of the synthetic fiber of more anti-sharp knife edges cutting or yarn.This method comprises the isotropic polymer for preparing melt-processable and the Moh's scale number homogeneous mixture greater than 3 hard filler, with melt spinning process polymer spun is made fiber or yarn then, the cut-resistance that this fiber or yarn are measured with Ashland anti-cutting performance test improves 20% at least, preferably improves 35% at least.
Can adopt at present any method of fiber and yarn being made fabric, comprise and weaving, above-mentioned fiber and yarn be made the fabric of cut-resistance with improvement with knitting.Also this fiber and yarn can be made the bondedfibre fabric with improved cut-resistance.This kind fabric all is new with making the anti-fabric that cuts the method for fabric and make thus.
Detailed description of the present invention
As mentioned above, hard filler is mixed in the fiber, can produce the soft cut-resistant fiber that is used to make protective clothing.This fiber is spinned by isotropic polymer.Term " isotropic " is meant and is not liquid crystal.Preferably, polymer can melt-processed, that is to say, this polymer can fusion in a certain temperature range, and the melt phase compound can be spun into fiber and polymer tangible decomposition can not take place under this temperature.The method for optimizing of making fiber is a melt spinning process.
Preferred isotropic polymer is half-crystalline polymer.Half-the crystalline polymer that highly is suitable for comprises poly-(terephthalic acid (TPA) alkylene ester), poly-(alkylene naphthalate), poly-((arylene sulfide)), aliphatic series and aliphatic-aromatic polyamide, comprises the polyester of the monomeric unit of being derived by cyclohexanedimethanol and terephthalic acid (TPA) and comprise polyethylene and polyacrylic polyolefin.The example of half concrete-crystalline polymer comprises poly-(ethylene glycol terephthalate), poly-(mutual-phenenyl two acid bromide two alcohol ester), poly-((ethylene naphthalate)), poly-(phenylene sulfide), poly-(terephthalic acid (TPA) 1, the 4-cyclohexanedimethanoester ester), wherein 1, the 4-cyclohexanedimethanol is the mixture of cis and transisomer, nylon 6, nylon 66, polyethylene and polypropylene.These polymer all are the polymer of well-known suitable manufacturing fiber.Partly preferred-crystalline polymer is poly-(ethylene glycol terephthalate).
Can not also can fill hard particles with the polymer of melt,, normally carry out dry spinning as solvent with acetone as cellulose acetate ester; Or polyarylamide, as the polymer of terephthalic acid (TPA) and p-phenylenediamine (PPD), carry out dry-jet wet spinning with concentrated sulfuric acid solution.In order to make fiberfill fibers, can in the spinning process of these polymer, mix hard particles.Unbodied, amorphous polymer (as the copolymer (polyarylate) of isophthalic acid, terephthalic acids and bisphenol-A) also can be through filling particulate and being used for the present invention by melt spinning process.
An importance of the present invention is to find and can make soft cut-resistant fiber by a kind of suitable polymers that is filled with the hard material that can give the fiber cut-resistance.This hard material can be metal such as metal element or metal alloy, perhaps can be nonmetal.Usually, Moh's scale number be 3 or higher any filler all can use.The Moh's scale number of the filler of particularly suitable is higher than 4, preferably is higher than 5.Iron, steel, tungsten and nickel are metal and metal alloy illustrative example, and the tungsten of Moh's scale number 6.5-7.5 is preferred.Nonmetallic materials also are suitable for.Nonmetallic materials comprise (but not limited) metal oxide (as aluminium oxide and silica), metal carbides (as carborundum, tungsten carbide), metal nitride, metal sulfide, metal silicate, metal silicide, metal sulfate, metal phosphate and metal boride.Other ceramic material also can adopt.Aluminium oxide and special burnt aluminium oxide are most preferred.Usually titanium dioxide is less preferred.
Under the condition that keeps fibrous mechanical property, be the cut-resistance that obtains, the size of particulate and Size Distribution are important parameters.Usually, hard filler should be a particulate form, and powdery generally suits.The effect of flat particulate (sheet) and elongated particulate (needle-like) also is good.Average particle size particle size is usually at 0.25 micron to 10 microns.Preferred average particle size particle size is at the 1-6 micron.3 microns of most preferred average particle size particle size.Concerning flat particulate (being sheet) or elongated particulate, particle size is meant along the length of particulate major axis (average diameter of the length of elongated particulate or sheet particulate flat horizontal surface).Particulate preferably should be logarithm normal distribution.For making textile fabric (the dawn scope of counting that is fiber is 1.5-15 filament denier dpf), particulate should after filtration or sieve, to remove the particulate greater than 6 microns.
The usage percentage of hard filler is very low.The selection of consumption is to improve cut-resistance can not make tensile property that obvious decline is arranged again, fiber or wished by the raising at least 20% (measuring by Ashland anti-cutting performance test method) of the cut-resistance of this fibrous fabric.With compare by the fiber of the same polymer system that does not contain filler, preferred fiber cut-resistance improves 35% at least, most preferably improves 50% at least.The decline of tensile fiber performance (intensity and modulus) preferably can not surpass 50%, more preferably can not surpass 25%.Most preferably, tensile property does not have obvious variation (being to be reduced to 10% under the tensile property).
By weight, the consumption of filler should at least 0.1%.The upper limit of amount of filler mainly is to be determined by the influence to tensile property, not too wishes but common consumption is higher than 20 (weight) %.By volume, particulate consumption concentration 0.1-5 (volume) %, more preferably 0.5%-3 (volume) %, most preferably 2.1 (volume) %.For embodiment preferred (calcined alumina in polyethylene terephthalate), preferable amount is 0.3-14% by weight, 1.4%-8.5% more preferably, most preferably 6%.
According to the present invention, fiberfill fibers is made by potting resin.Can adopt any standard method that filler is added in the resin to produce potting resin.For example, concerning the isotropic polymer of melt-processable, can be in extruder with the polymer of hard filler and fusion under the condition that is distributed in the resin with making uniform filling, produce potting resin easily as in double screw extruder, mixing.Filler also can add in the polymer manufacture process, or adds when polymer feeds the extruder of fiber spinning equipment, and in this case, blend and spinning step are almost carried out simultaneously.
Because filler is evenly distributed in the polymer melt, therefore, except elongated and flat particulate had to a certain degree orientation under the dipole-dipole force effect of spinning process, filler particles also was equally distributed in all fibres.The phenomenon of some particulate to the fiber surface migration also may take place.Therefore, be " uniformly " though the distribution of particulate in fiber is aforesaid, " uniformly " speech is interpreted as also comprising the inhomogeneities that the homogeneous polymer blend is taken place during processing (as melt spinning).This fiber still belongs to the scope of the invention.Can make the fiber of any fiber number according to the present invention.For the manufacturing of yarn and fabric, the dawn number of fiber usually between the 1-50 filament denier, preferably between the 1.5-15 filament denier, 4 filament deniers most preferably.Also can make the anti-monofilament that cuts by adding hard filler.Usually, the diameter of monofilament is the 0.05-2 millimeter.Fiber is made by conventional spinning technique.As previously mentioned, preferable methods is a melt spinning process, but also can adopt wet spinning process and dry spinning method.
More than be the explanation to fiber, the noun fiber not only comprises conventional filament, and comprises the yarn that is spun into by many this fibers.Generally, yarn is used for making clothes, fabric etc.
By conventional method (as knitting or weave) and conventional equipment, adopt fiberfill fibers of the present invention to can be made into the anti-fabric that cuts.Also can be made into bondedfibre fabric.This fabric is compared with the identical fabric of the fiber manufacturing that is spinned by the same polymer that does not contain filler, and its cut-resistance has had raising.The cut-resistance of this fabric (pressing Ashland anti-cutting performance test method measures) improves at least 20%, and preferred cut-resistance improves at least 35%, and most preferred cut-resistance improves at least 50%.
So, can make the cut-resistance clothes by above-mentioned cut-resistance fabric.For example, can make the safety gloves of anti-cutting that is exclusively used in food-processing industry by this fabric.This gloves are highly soft, the easy cleaning, and anti-chlorine bleach and the heating of anti-drying box.Cut-resistant fiber of the present invention also can be used to make the medical protection gloves.Other purposes of fabric and monofilament comprises as the side shield screen of truck and WATERPROOF FABRIC, soft baggages, industrial covering jewelry, spray part, fuel tank, folding packaging bag, cargo aircraft overlap with curtain, rotary hose and anti-apron, the saw chaps etc. of cutting used during mental package.
Embodiment 1
The following describes poly-(ethylene glycol terephthalate) of blending tungsten powder filler.The Moh's scale number of tungsten is about 6.5-7.5.Inherent viscosity (measuring in orthomonochlorphenol) is by Hoechst Celanese Corporation (PET) for about 0.95 tyre cord level poly-(ethylene glycol terephthalate), Somerville, the pellet that New Jersey provides.This polymer and 10 (weight) % tungsten powder is mixed and made into masterbatch in double screw extruder.The average particle size particle size of tungsten is about 1 micron.Polymeric aggregate and tungsten powder before mixing all through super-dry.Masterbatch is mixed in double screw extruder with the PET that adds and contains the mixture that tungsten powder is 1 (weight) % and 4 (weight) %.Allow molten mixture pass through filter assemblies earlier, by spinnerets mixture is carried out melt spinning then.Then long filament is drawn from 90 ℃ hot feeding roller, is stretched then through the hot-die cover, carries out 2% loose operations at 225 ℃ at last.The long filament plying is supplied performance test.Test data is compiled in table 1.Be not filtered off when filtering in order to ensure filler, the fiber of a tungstenic 10% carried out the analysis of tungsten.The analysis result of fiber shows, contains the tungsten of about 8.9 (weight) % in the fiber.
Tensile property adopts ASTM methods of test D-3822 to measure intensity, percentage elongation and modulus.
Cut-resistance at first is made into fiber needle the anti-fabric that cuts test usefulness.The surface density of yarn is measured (OSY in table 1 and the table 2) with ounce per square yard in the fabric.Press the cut-resistance of Ashland anti-cutting performance (" CPP ") test method determination fabric then.Test is at TRI/Environmental, and Inc. (9063 Bee Cave Road, Anstin, Texas 78733-6201) carries out.During test, the fabric sample is placed on the nonreentrant surface of an axle.Carry out a series of tests, this test is to be pulled through fabric with a slasher that is added with variable loading, cut fully up to fabric, and when the measurement blade cuts this fabric fully, the distance that this blade moves on fabric.When slasher cuts fabric fully that is exactly the position that axle and slasher electrically contact.To cut the function construction of fabric required separation distance as the slasher loading.The cutting distance is set between 0.3 inch (0.7 centimetre) to 1.8 inches (4.6 centimetres), determination data and mapping.The curve map of drawing is approximately a straight line.Go up point-rendering or calculate desirable straight line by scheming, and can be from figure curve or calculate blade by regression analysis and when fabric moves 1 inch, cut the required loading of fabric.Blade moves 1 inch interpolate value of cutting the required loading of fabric and lists in table 1 and the table 2 with " CPP " on fabric, CPP is the abbreviation of anti-cutting performance (CutProtection Performance).At last, for the fabric sample of more different surface densities, come the fabric of different surface densities is compensated divided by the surface density (OSY) of fabric with the CPP value.This numerical value is listed in table 1 and the table 2 with CPP/OSY.
Embodiment 2
In these experiments, the PET fiber sample is filled with alumina powder, and this alumina powder is that commercially available trade mark is MICROPOLISH The polish abrasive of II.Adopt average particle size particle size be respectively about 0.05 micron with about 1.0 microns two kinds different alumina powders.These two kinds of alumina powders are by Buehler, and Ltd. (Illinois 60044 for Waukegan Road, Lake Bluff) provides the decondensation powdery aluminum.0.05 micrometer alumina is that the r-aluminium oxide and the Moh's scale number of cubic crystal structure is 8.1.0 micrometer alumina is that the alpha-aluminium oxide and the Moh's scale number of hexagonal system structure is 9.By the method identical two kinds of alumina powders are mixed with PET respectively, obtain the salic filling PET sample of about 0.21%, 0.86%, 1.9% and 2.1% (weight) that is with embodiment 4.The performance of fiber and cut-resistance are to measure by the method identical with embodiment 1.Determination data is listed in the table 2.
Table 1 and table 2 data show, the cut-resistance of the different sample of loading all has raising in these experiments, at least about 10-20%.Have in the data two groups about the filler incorporation in the fiber in about 0.07% data to about 0.7% (by volume).The performance of its fiber does not have tangible decline to occur with the variation of the particle size of loading and particulate.
Embodiment 3
To the tungsten particulate with several varying particle sizes (0.6-1.6 micron) is that filler, packing density are that the PET of 0.4-1.2 (volume) % carries out a series of experiments.With filling the PET spinning resultant yarn of tungsten, then yarn is knitted into the fabric that is for experiment.Adopt following improved step to measure cut-resistance with Ashland anti-cutting performance test method.Come the actual effect of testing with the fabric of different densities is proofreaied and correct divided by the surface density of fabric with the CPP value.Data are listed in the table 3.
Anti-cutting performance (CPP)
Narrated Ashland CPP test at the end of experiment 1, but this experiment adopts the standard sample of a known CPP value to come the correcting determination result as benchmark.The calibration standard sample be 0.062 inch on NS-5550 type (0.157 centimetre) neoprene (available from FAIRPRENE, 85Mill Plain Road, Fairfield, CT06430), the CPP value of this rubber be 400 the gram.Measure the CPP value of this standard sample respectively in the beginning of a series of tests with when finishing, and calculate the standard sample CPP value correction that to measure to the 400 average normalization factors that restrain.Then, this normalization factor is used to proofread and correct the determination data of a series of tests.When calculating CPP value, also can utilize the logarithm that cuts the fabric required separation distance graph of a relation, because both are better linearity and concern these to loading on the slasher.
Embodiment 4
Adopting sintered alumina is that fiberfill is carried out a series of tests.The step of these experiments is identical with step among the embodiment 1-3, but the particle size range broad of particulate (0.5-3 micron), and concentration range (0.8-3.2 (volume) %) is wide than embodiment 2.
(N.J.07604), this aluminium oxide is the sheet crystal formation to the sintered alumina that is used for testing, and is called Alumina #1 for 621 Route 46, Hasbrouck available from Agsco Corporation.
Press the described step measurements CPP value of latter end of embodiment 3.Calculate the CPP/OSY value then as stated above.These data are all listed in the table 4.
By institute's column data in the table as can be seen, the influence of listed all parameters during the CPP/OSY value is shown (being the filament denier of particle size, particle concentration, surface density and fiber).During high areal density (OSY), the CPP/OSY value significantly descends.Therefore the most handy have the fabric do test of similar face density to compare.
Yet, be that 2.4 (volume) % (6.8 weight %), particle size are 2 microns, surface density (the CPP/OSY value of the fabric of 2.8 monofilament dawn spinning is greater than about 100 less than the textile fabric of about 10 ounce per square yard by fraction of particle as can be seen by table 4 data.(the sample sequence number is 22-24 and 30).The CPP/OSY value of the fabric of spinning is greater than about 100.(the sample sequence number is 22-24 and 30).The average CPP/OSY value about 53 of the PET fiber sample that this value is close than unfilled, fibre number and surface density (in the table 1 three in the same old way) improves more than 50%.The average CPP/OSY value (70) of the PET sample that all tungsten are filled in the table 3 and the average CPP/OSY value (75) of all alumina filled PET samples of table 4 all are higher than the mean value in the same old way significantly.
The specific embodiments of the invention described above is just to explanation of the present invention, and those skilled in the art can be made amendment to it, and this is self-evident.Therefore can not think that the present invention is only limited to embodiment disclosed herein.
Table 1, tungsten are filled the cut-resistance of PET
No. % tungsten bulking value Particle size (micron) dpf T/E/M 1 CPP 2 OSY 3 CPP/OSY
Contrast 1 - - - 3.1 6.8/6.7/124 421 7.1 59
Contrast 2 - - - 5.0 - 384 6.8 56
Contrast 3 - - - 5.0 - 589 13.0 45
1-1 1％ 0.07％ 1 micron 6.0 6.3/9.0/128 540 9.1 59
1-2 1％ 0.07％ 1 micron 5.6 - 565 7.3 77
1-3 4％ 0.29％ 1 micron 6.0 7.2/11.6/109 643 7.0 92
1-4 4％ 0.29％ 1 micron 5.9 7.0/12.5/100 620 7.3 85
1-5 10％ 0.72％ 1 micron 11.6 6.3/10.0/123 697 7.5 93
1-6 10％ 0.72％ 1 micron 7.4 4.1/22.9/75 759 8.5 90
1-7 10％ 0.72％ 1 micron 6.0 - 670 7.6 89
1Intensity (gram/dawn), percentage elongation (%), modulus (gram/dawn) are measured by ASTM methods of test D-3822.
2The anti-cutting performance is pressed Ashland CPP determination of test method.
3Oz/yd 2
The cut-resistance of the alumina filled PET of table 2
No. % alumina weight volume Particle size (micron) dpf T/E/M 1 CPP 2 OSY 3 CPP/OSY
2-1 0.21％ 0.07％ 1 micron 11.4 6.7/10.3/112 547 7.2 76
2-2 0.21％ 0.07％ 1 micron 5.6 7.4/12.4/104 463 7.5 62
2-3 0.86％ 0.30％ 0.05 micron 5.6 7.4/14.0/110 501 7.3 69
2-4 0.86％ 0.30％ 0.05 micron 5.7 6.9/12.8/110 497 6.7 73
2-5 1.9％ 0.67％ 1 micron 11.8 5.8/12.0/108 683 8.2 83
2-6 1.9％ 0.67％ 1 micron 5.6 7.4/10.9/108 478 6.7 71
2-7 2.1％ 0.74％ 0.05 micron 5.4 6.6/11.6/117 496 6.7 74
2-8 2.1％ 0.74％ 0.05 micron 5.9 5.4/12.8/100 431 6.2 69
1Intensity (gram/dawn), percentage elongation (%), modulus (gram/dawn) are measured by ASTM methods of test D-3822.
2The anti-cutting performance is pressed Ashland CPP determination of test method.
3Oz/yd 2
Table 3 tungsten is filled the cut-resistance of PET
Sample Particle size (micron) Concentration (volume %) DPF Intensity (gpd) Percentage elongation (%) Modulus (gpd) The OSY oz/yd 2 CPP CPP/OSY
1 0.6 0.4 10 7.3 9 112 8 562 70
2 0.8 1.2 10 5.5 13 102 9.5 557 59
3 1.4 0.4 10 6 14 96 8.2 714 87
4 1.6 1.2 10 5.9 11 100 8.2 821 100
5 1 0.8 10 8 708 89
6 0.8 0.8 10 5.7 8 109 7 724 103
7 0.6 0.8 10 5.9 13 118 6.8 621 91
8 0.8 0.8 10 5.7 8 109 7 596 85
9 0.6 0.8 10 6.3 13 103 7.9 703 * 89
10 1.5 0.8 12 6.7 9 102 7.6 644 85
11 0.6 0.8 2.4 13.6 656 48
12 1 0.8 7.2 8 108 7.5 503 67
13 0.6 0.8 2.4 28 1226 44
14 0.6 0.8 2.4 19 964 51
15 0.6 0.8 2.4 26 1225 47
16 0.6 0.8 10 20 900 45
17 0.6 0.8 2.4 12 628 52
18 0.6 0.8 1.4 16 685 43
19 0.6 0.8 1.4 7 580 80
Particle size is in micron.
Concentration is the concentration of hard particles, in volume % among the PET.
DPF is a fiber Denier, in dpf (filament denier).
Fibre strength, percentage elongation and modulus are the tensile properties of fiber, measure by ASTM methods of test D-3822.
OSY is the surface density of knit goods, with oz/yd 2Meter.
CPP is the CPP value by Ashland CPP determination of test method.
CPP/OSY is the ratio of CPP value and surface density (OSY).
*Pressing embodiment 1 described method measures.
The cut-resistance of the alumina filled PET of table 4
Sample Particle size (micron) Concentration (volume %) DPF Intensity (gpd) Percentage elongation (%) Modulus (gpd) The OSY oz/yd 2 CPP CPP/OSY
1 0.6 2.4 3 22 1285 58
2 0.6 0.8 10 6.6 15 109 10 990 * 99
3 0.6 1.6 10 5.2 17 100 12 912 76
4 0.6 2.4 10 5.8 9 107 10 823 82
5 0.6 3.2 10 4.8 14 93 10 852 85
6 0.6 2.4 3 19 1074 57
7 0.6 2.4 3 9 487 54
8 3 2.4 3.6 5 23 16 1234 77
9 3 2.4 3.6 5 23 11 981 89
10 0.5 2.4 1.4 4.9 22 15 810 54
11 0.5 2.4 1.4 4.9 22 13 623 48
12 3 2.4 3.1 3.4 19 18 1555 86
13 0.5 2.4 5.5 23 1197 52
14 0.5 2.4 5.5 21 1082 52
15 0.6 2.4 6.4 23 1242 54
16 0.6 2.4 5.5 19 1505 79
17 0.5 2.4 6.7 8 597 75
18 0.6 2.4 4 13 818 63
19 3 2.4 3.1 15 1370 91
20 3 2.4 3.1 15 1283 86
21 2 2.4 2.8 5 15 80 18 1562 87
22 2 2.4 2.8 5 15 80 9 905 101
23 2 2.4 2.8 5 15 80 5 611 122
24 2 2.4 2.8 5 15 80 5 615 123
25 2 2.4 2.8 5 15 80 11 785 71
26 2 2.4 2.8 5 15 80 17 1593 94
27 2 2.4 2.8 5 15 80 17 1506 89
28 2 2.4 2.8 5 15 80 36 1022 28
29 2 2.4 2.8 5 15 80 18 1573 87
30 2 2.4 2.8 5 15 80 9 956 106
31 3 1.2 10 23 1414 62
32 0.6 2.4 6.4 18 1084 60
33 0.6 2.4 6.4 21 996 47
34 3 2.4 4.2 14 1079 77
35 3 2.4 4.2 11 883 80
36 1 2.4 12.9 73 943 129
Particle size is in micron.
Concentration is the concentration of hard particles, in volume % among the PET.
DPF is a fiber Denier, in dpf (filament denier).
Fibre strength, percentage elongation and modulus are the tensile properties of fiber, measure by ASTM methods of test D-3822.
OSY is the surface density of knit goods, with oz/yd 2Meter.
CPP is the CPP value by Ashland CPP determination of test method.
CPP/OSY is the ratio of CPP value and surface density (OSY).
*Pressing embodiment 1 described method measures.

Claims (37)

1. a polymer that comprises the isotropism melt-processable and be distributed in the cut-resistant fiber of the hard filler in the described fiber, the Moh's scale number of described filler is greater than 3; The average particle size particle size of described filler is between 0.25 micron to 10 microns; The consumption of described filler is 0.1-5 volume %; The dawn number of described fiber is between 1-50dpf, and the cut-resistance that described fiber is measured by Ashland anti-cutting performance test improves at least 20% than the same fiber that does not contain described filler.
2. according to a kind of cut-resistant fiber of claim 1, the Moh's scale number of wherein said hard filler is greater than 5.
3. according to a kind of cut-resistant fiber of claim 1, the average particle size particle size of wherein said hard filler is between the 1-6 micron.
4. according to a kind of cut-resistant fiber of claim 1, the average particle size particle size of wherein said hard filler is 3 microns.
5. according to a kind of cut-resistant fiber of claim 3, wherein said hard filler is to be selected from metal oxide, comprises aluminium oxide and silica, metal carbides, metal nitride, metal sulfide, metal silicate, metal silicide, metal sulfate, metal phosphate, metal boride and their mixture a kind of nonmetal, but described hard filler is not a titanium dioxide.
6. according to a kind of cut-resistant fiber of claim 5, the content of wherein said hard filler is 0.5%-3%, by volume.
7. according to a kind of cut-resistant fiber of claim 5, the content of wherein said hard filler is 2.1 volume %.
8. according to a kind of cut-resistant fiber of claim 6, wherein said hard filler is a calcined alumina.
9. according to a kind of cut-resistant fiber of claim 3, wherein said hard filler is a kind of metal or metal alloy.
10. according to a kind of cut-resistant fiber of claim 9, the content of wherein said hard filler is 0.5-3 volume %.
11. according to a kind of cut-resistant fiber of claim 9, the content of wherein said hard filler is 2.1 volume %.
12. according to a kind of cut-resistant fiber of claim 10, wherein said hard filler chosen from Fe, steel, nickel, tungsten and their mixture.
13. according to a kind of cut-resistant fiber of claim 1, wherein said polymer isotropic, melt-processable is selected from the polyester and the polyolefin of poly-(terephthalic acid (TPA) alkylene ester), poly-(alkylene naphthalate), poly-((arylene sulfide)), aliphatic polyamide, aliphatic-aromatic polyamide, cyclohexanedimethanol and terephthalic acid (TPA).
14. a kind of cut-resistant fiber according to claim 1, wherein said polymer isotropic, melt-processable is selected from poly-(ethylene glycol terephthalate), poly-(mutual-phenenyl two acid bromide two alcohol ester), poly-((ethylene naphthalate)), poly-(phenylene sulfide), poly-(terephthalic acid (TPA)-1,4 cyclohexane dimethanol ester), nylon 6, nylon 66, polyethylene and polypropylene.
15. according to each a kind of cut-resistant fiber in the claim 1,6,8 and 12, wherein said polymer isotropic, melt-processable is poly-(ethylene glycol terephthalate).
16. according to a kind of cut-resistant fiber of claim 7, wherein said hard filler is that the polymer of calcined alumina and described isotropic melt-processable is poly-(ethylene glycol terephthalate).
17. a cut-resistant fiber that comprises the polymer of isotropism melt-processable and be distributed in the hard filler in the described fiber, the Moh's scale number of described filler is greater than 3; The average particle size particle size of described filler is at 0.25 micron-6 microns, and its maximum particle size is 6 microns; The consumption of described filler is 0.1-5 volume %; The dawn number of described fiber is between 1-15dpf.
18. a cut-resistant fiber that comprises poly-(ethylene glycol terephthalate) polymer and be distributed in the calcined oxide Al filler in the described fiber, the average particle size particle size scope of described fiber is 0.5 micron to 3 microns; The content of described filler is 0.80-3.2 volume %; The dawn number of described fiber is between 1-15dpf.
19. according to the cut-resistant fiber of claim 18, the average particle size particle size of wherein said filler is 2 microns, the consumption of described filler is 2.4 volume %.
20. a cut-resistant fiber that comprises poly-(ethylene glycol terephthalate) polymer and be distributed in the tungsten filler in the described fiber, the average particle size particle size scope of described filler is 0.6 micron to 1.6 microns; The consumption of described filler is 0.4～1.2 volume %; The dawn number of described fiber is at 1-15dpf.
21. according to the cut-resistant fiber of claim 20, the average particle size particle size scope of wherein said filler is 0.8 micron to 1.6 microns; The consumption of described filler is 0.8-1.2 volume %.
Have a kind of method of high cut-resistance fiber or yarn 22. make, this method comprises the steps:
(a) preparation mixture, this mixture contains 0.1-5 volume %'s
(1) Moh's scale number greater than 3, particle size is at a kind of hard filler of 0.25 micron to 10 microns, with
(2) be selected from the polymer of poly-(ethylene glycol terephthalate), poly-(mutual-phenenyl two acid bromide two alcohol ester), poly-((ethylene naphthalate)), poly-(phenylene sulfide), poly-(terephthalic acid (TPA) 1,4 cyclohexane dimethanol ester), nylon 6, nylon 66, polyethylene and polyacrylic a kind of isotropism, melt-processable; And
(b) described mixture is spun into fiber or yarn, the dawn number of fiber is between 1-50dpf in wherein said fiber or the described yarn, and the cut-resistance that described fiber is measured with Ashland anti-cutting performance test improves at least 20% than the same fiber that does not contain described filler.
23. according to the method for claim 22, the average particle size particle size scope of wherein said filler is 0.25 micron to 6 microns, its maximum particle size is 6 microns; The consumption of described filler is 0.1-5 volume %; With the dawn number of described fiber be 1-15dpf.
24. according to the method for claim 22, wherein said polymer is poly-(ethylene glycol terephthalate) polymer; Described filler is that consumption is 0.80-3.2 volume %, and the average particle size particle size scope is 0.5 micron to 3 microns a calcined oxide Al filler, and the dawn number of described fiber is 1-15dpf.
25. according to the method for claim 24, the average particle size particle size of wherein said filler is 2 microns, consumption is 2.4 volume %.
26. according to the method for claim 22, wherein said polymer is poly-(ethylene glycol terephthalate); Described filler is that the average particle size particle size scope is that 0.6 micron to 1.6 microns and consumption are the tungsten filler of 0.4-1.2 volume %; And the dawn number of described fiber is 1-15dpf.
27. according to the method for claim 26, it is 0.8-1.2 volume % with amount ranges that the average particle size particle size scope of wherein said filler is 0.8 micron to 1.6 microns.
28. make a kind of method of the fabric with high cut-resistance, this method comprises the steps:
A) according to the method for claim 22 make fiber or yarn and
B) described fiber or yarn are made into fabric.
29. a cut-resistant fiber that comprises polymer that can not melt-processed and be distributed in the hard filler in the described fiber, the Mohs' hardness of described filler is greater than 3; The average particle size particle size scope of described filler is 0.25 micron to 10 microns; The consumption of described filler is 0.1-5 volume %; The cut-resistance that described fiber is measured with Ashland anti-cutting performance test improves at least 20% than the same fiber that does not contain described filler.
30. according to the cut-resistant fiber of claim 29, wherein said polymer that can not melt-processed is a polyarylamide.
31. according to the cut-resistant fiber of claim 30, wherein said polyarylamide is the polymer of p-phenylenediamine (PPD) and terephthalic acid (TPA).
32. the anti-yarn that cuts that comprises the fiber of a large amount of claims 1, the dawn number of wherein said fiber is between 1.5-15dpf.
33. according to the cut-resistant fiber of claim 20, the average particle size particle size of wherein said filler is 1.6 microns, consumption is 1.2 volume %.
34. according to the cut-resistant fiber of claim 20, the average particle size particle size of wherein said filler is 0.8 micron, consumption is 0.8 volume %.
35. according to the method for claim 26, the average particle size particle size of wherein said filler is 1.6 microns, consumption is 1.2 volume %.
36. according to the method for claim 26, the average particle size particle size of wherein said filler is 0.8 micron, consumption is 0.8 volume %.
37. according to the cut-resistant fiber of claim 1, the cut-resistance that wherein said fiber is measured with Ashland anti-cutting performance test improves at least 35% than the same fiber that does not contain described filler.
38. according to the cut-resistant fiber of claim 1, the cut-resistance that wherein said fiber is measured with Ashland anti-cutting performance test improves at least 50% than the same fiber that does not contain described filler.
CN96195351A 1995-06-07 1996-05-31 Filled thermoplastic cut-resistant fiber Expired - Fee Related CN1092254C (en)

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Families Citing this family (10)

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US5851668A (en) * 1992-11-24 1998-12-22 Hoechst Celanese Corp Cut-resistant fiber containing a hard filler
DE19605511A1 (en) * 1996-02-15 1997-08-21 Hoechst Trevira Gmbh & Co Kg Cut-resistant aramid fibers, yarns containing these aramid fibers and their use
KR101129067B1 (en) * 2008-09-18 2012-03-23 코오롱인더스트리 주식회사 Aramid Fiber and bulletproof fabric using the same
KR101682429B1 (en) * 2009-08-19 2016-12-05 쇼와 글로브 가부시키가이샤 Work glove
DE102012001623A1 (en) * 2012-01-30 2013-08-01 Hahl Filaments GmbH Producing abrasive bristle, comprises melting a plastic material, mixing granules made of abrasive particles, extruding into a filament, processing and cutting filament, where plastic material is a high-temperature-resistant polymer
CN106149140A (en) * 2012-12-20 2016-11-23 帝斯曼知识产权资产管理有限公司 Polyethylene yarn and manufacture method thereof
CN107574519A (en) * 2017-09-29 2018-01-12 汇鸿(南通)安全用品有限公司 A kind of anti-encapsulated yarn of cutting
WO2020065842A1 (en) * 2018-09-27 2020-04-02 東洋紡株式会社 Polyethylene fiber and product employing same
CN112779623B (en) * 2020-09-17 2022-03-15 安丹达工业技术(上海)有限公司 Composition for cutting-resistant fiber, application and preparation method
CN113897696A (en) * 2021-11-03 2022-01-07 福建永荣锦江股份有限公司 Preparation method of anti-cutting polyamide 6 fiber

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0238444A (en) * 1988-07-28 1990-02-07 Toray Ind Inc Thermoplastic polyester composition
EP0599231A1 (en) * 1992-11-24 1994-06-01 Hoechst Celanese Corporation Filled fiber
CN1148874A (en) * 1994-05-16 1997-04-30 赫希斯特人造丝公司 Filled cut-resistant fiber

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0261430B1 (en) * 1986-08-27 1999-11-24 Teijin Limited Biaxially oriented polyester film

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0238444A (en) * 1988-07-28 1990-02-07 Toray Ind Inc Thermoplastic polyester composition
EP0599231A1 (en) * 1992-11-24 1994-06-01 Hoechst Celanese Corporation Filled fiber
CN1148874A (en) * 1994-05-16 1997-04-30 赫希斯特人造丝公司 Filled cut-resistant fiber

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