EP1496331B1 - Composite hybride de protection - Google Patents

Composite hybride de protection Download PDF

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Publication number
EP1496331B1
EP1496331B1 EP04024471A EP04024471A EP1496331B1 EP 1496331 B1 EP1496331 B1 EP 1496331B1 EP 04024471 A EP04024471 A EP 04024471A EP 04024471 A EP04024471 A EP 04024471A EP 1496331 B1 EP1496331 B1 EP 1496331B1
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EP
European Patent Office
Prior art keywords
layers
fabric
woven
fibers
tightly
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.)
Expired - Lifetime
Application number
EP04024471A
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German (de)
English (en)
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EP1496331A1 (fr
Inventor
Minshon J. Chiou
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
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EI Du Pont de Nemours and Co
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Publication date
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Priority claimed from US09/217,360 external-priority patent/US6162746A/en
Application filed by EI Du Pont de Nemours and Co filed Critical EI Du Pont de Nemours and Co
Publication of EP1496331A1 publication Critical patent/EP1496331A1/fr
Application granted granted Critical
Publication of EP1496331B1 publication Critical patent/EP1496331B1/fr
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Classifications

    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F41—WEAPONS
    • F41H—ARMOUR; ARMOURED TURRETS; ARMOURED OR ARMED VEHICLES; MEANS OF ATTACK OR DEFENCE, e.g. CAMOUFLAGE, IN GENERAL
    • F41H5/00—Armour; Armour plates
    • F41H5/02—Plate construction
    • F41H5/04—Plate construction composed of more than one layer
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F41—WEAPONS
    • F41H—ARMOUR; ARMOURED TURRETS; ARMOURED OR ARMED VEHICLES; MEANS OF ATTACK OR DEFENCE, e.g. CAMOUFLAGE, IN GENERAL
    • F41H5/00—Armour; Armour plates
    • F41H5/02—Plate construction
    • F41H5/04—Plate construction composed of more than one layer
    • F41H5/0471—Layered armour containing fibre- or fabric-reinforced layers
    • F41H5/0485—Layered armour containing fibre- or fabric-reinforced layers all the layers being only fibre- or fabric-reinforced layers

Definitions

  • This invention relates to protective composites in the field of knife and ice pick stab resistance which composites provide, on one hand, greater protection for a given weight; and, on the other hand, equivalent protection in a lighter weight, in comparison with other protective composites currently available.
  • the composite of this invention is flexible.
  • European Patent Application No. 670,466 published September 6, 1995, describes a ballistic and stab-resistant system wherein the knife stab resistance is imparted by embedding chainmail in a polymer resin.
  • UK Patent No. GB 2 198 628 discloses the use of polybenzothiazole fibres in textile armour for protection against projectile fragments comprising a plurality of textile layers.
  • the present invention provides a protective composite structure with a plurality of primarily knife resistant layers of woven fabric comprising polybenzoxale (PBO) or polybenzothiazole (PBT) fibers, and a plurality of primarily ice pick resistant layers of tightly-woven penetration resistant fabric having a tightness factor of at least 0.75.
  • PBO polybenzoxale
  • PBT polybenzothiazole
  • the Fig. shows an expanded perspective view of a composite of this invention.
  • Knitch protection is required in garments worn by guards, police officers, and the like; and ballistic protection is, also, a desirable quality in such garments.
  • Such garments must be as flexible as possible to ensure comfort sufficient that the garment will be readily worn.
  • the kernel of the present invention resides in use of a particular combination of two different layers of materials to afford the desired protection results, each of the different layers do exhibit a primary utility in the combination.
  • the materials of this hybrid composite which are primarily effective for the knife stab resistance are polybenzoxazole or polybenzothiazole in fiber form in woven layers.
  • Polybenzoxazole and polybenzothiazole are generally, as described in the aforementioned WO 93/20400 , incorporated herein by reference. Polybenzoxazole and polybenzothiazole are preferably made up of mers of the following structures:
  • aromatic groups shown joined to the nitrogen atoms may be heterocyclic, they are preferably carbocyclic; and while they may be fused or unfused polycyclic systems, they are preferably single six-membered rings.
  • group shown in the main chain of the bis-azoles is the preferred para-phenylene group, that group may be replaced by any divalent organic group which doesn't interfere with preparation of the polymer, or no group at all. For example, that group may be aliphatic up to twelve carbon atoms, tolylene, biphenylene, bis-phenylene ether, and the like.
  • the polybenzoxazole and polybenzothiazole used to make fibers of this invention should have at least 25 and preferably at least 100 mer units. Preparation of the polymers and spinning of those polymers is disclosed in the aforementioned International Publication WO 93/20400 .
  • polybenzoxazole and polybenzothiazole fibers are woven in any, generally-used, fabric configuration such as plain weave, crowfoot weave, basket weave, satin weave, and the like. Plain weave is preferred.
  • fibers and yarns of any linear density will be effective to increase knife stab resistance in the present invention.
  • the preferred linear density for individual fibers should be 0.3 to 17 dtex, and 0.5 to 3.5 dtex is most preferred.
  • Yarns in the range of 100 to 3300 dtex are preferred with 220 to 1700 dtex being most preferred.
  • Yarns with a linear density of greater than 3300 dtex are generally more difficult to produce and use efficiently and yarns with a linear density of less than 100 dtex are difficult to weave without damage to the yarn.
  • the materials of this hybrid composite which are primarily effective for the ice pick stab resistance can be, among other things, polyamide and polyolefin; and can, also, be polybenzoxazole and polybenzothiazole.
  • aramid is preferred.
  • aramid is meant a polyamide wherein at least 85% of the amide (-CO-NH-) linkages are attached directly to two aromatic rings. Suitable aramid fibers are described in Man-Made Fibers - Science and Technology, Volume 2, Section titled Fiber-Forming Aromatic Polyamides, page 297, W. Black et al., Interscience Publishers, 1968 . Aramid fibers are, also, disclosed in U.S. Patents 4,172,938 ; 3,869,429 ; 3,819,587 ; 3,673,143 ; 3,354,127 ; and 3,094,511 .
  • Additives can be used with the aramid and 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 of other diamine substituted for the diamine of the aramid or as much as 10 percent of other diacid chloride substituted for the diacid chloride or the aramid.
  • the preferred aramid is a para-aramid and poly(p-phenylene terephthalamide) (PPD-T) is the preferred para-aramid.
  • PPD-T poly(p-phenylene terephthalamide)
  • PPD-T is meant the homopolymer resulting from mole-for-mole polymerization of p-phenylene diamine and terephthaloyl chloride and, also, copolymers resulting from incorporation of small amounts of other diamines with the p-phenylene diamine and of small amounts of other diacid chlorides with the terephthaloyl chloride.
  • PPD-T means copolymers resulting from incorporation of other aromatic diamines and other aromatic diacid chlorides such as, for example, 2,6-naphthaloyl chloride or chloro- or dichloroterephthaloyl chloride or 3,4'-diaminodiphenylether.
  • polyethylene is meant a predominantly linear polyethylene material of preferably more than one million molecular weight that may contain minor amounts of chain branching or comonomers not exceeding 5 modifying units per 100 main chain carbon atoms, and that may also contain admixed therewith not more than about 50 weight percent of one or more polymeric additives such as alkene-1-polymers, in particular low density polyethylene, propylene, and the like, or low molecular weight additives such as anti-oxidants, lubricants, ultra-violet screening agents, colorants and the like which are commonly incorporated. Such is commonly known as extended chain polyethylene (ECPE).
  • ECPE extended chain polyethylene
  • polypropylene is a predominantly linear polypropylene material of preferably more than one million molecular weight.
  • High molecular weight linear polyolefin fibers are commercially available. Preparation of polyolefin fibers is discussed in US 4,457,985 .
  • flexible articles with ice pick penetration resistance are made using layers of fabric woven from yarn material with high tenacity and toughness; and the degree of ice pick penetration resistance is, among other things, a function of the linear density of the yarn and tightness of the weave. The lower the linear density of the yarn and the tighter the weave, the greater the ice pick penetration resistance.
  • Cover factor is a calculated value relating to the geometry of the weave and indicating the percentage of the gross surface area of a fabric which is covered by yarns of the fabric. The equation used to calculate cover factor is as follows (from Weaving: Conversion of Yarns to Fabric, Lord and Mohamed, published by Merrow (1982), pages 141-143 ):
  • the maximum cover factor which is possible for a plain weave fabric is 0.75; and a plain weave fabric with an actual cover factor of 0.68 will, therefore, have a fabric tightness factor of 0.91.
  • the preferred weave for practice of this invention is plain weave.
  • the particular combination of this invention utilizing special penetration resistant materials, exhibits an ice pick and knife penetration resistance which is much greater than would be expected from the sum of the penetration resistance of the individual elements of the combination.
  • the individual elements in the combination of this invention have a particular element-to-element relationship.
  • the primarily knife penetration resistant layers of polybenzoxazole or polybenzothiazole fabric may be located anywhere in the composite of this invention. Generally, more than one layer of these fabrics will be required to afford the desired knife stab protection.
  • Each layer of polybenzoxazole and polybenzothiazole generally has an areal density of 75 to 450 grams per square meter and, generally, 1 to 15 layers are used. The areal density of the layers depends greatly on the form of the network and on the kind and linear density of the fibers. Generally, however, the polybenzoxazole and polybenzothiazole fibers constitute from 10 to 90, and preferably 15 to 50, weight percent of the total composite.
  • the primarily ice pick stab resistant fabric layers are made from tightly-woven yarns of high strength fibers wherein the yarns generally have a linear density of less than 500 dtex and, preferably, the individual fibers in those yarns have a linear density of 0.2 to 2.5 dtex and more preferably 0.7 to 1.7 dtex.
  • These layers can be made from polyamides, polyolefins, polybenzoxazoles, polybenzothiazole, or other fibers usually used for penetration resistance.
  • the preferred material for these layers is para-aramid yarns.
  • the preferred linear density for the yarns is 100 to 500 dtex and those yarns are preferably woven to a fabric tightness factor of 0.75 to 1.00 or, perhaps, higher, and, more preferably greater than 0.95. It is most preferred that the tightly woven fabric layers have a relationship between the yarn linear density (dtex) and the fabric tightness factor as follows:
  • Yarns used in any of the fabric layers of this invention should exhibit a tenacity of greater than 20 grams per dtex and as much as 50 grams per dtex or more; an elongation to break of at least 2.0% and as much as 6% or more; and a modulus of at least 270 grams per dtex and as much as 2000 grams per dtex or more.
  • a combination of the two elements of this invention is made by placing the two together, in face to face relation, with other layer materials therebetween or not, as desired.
  • Other layer materials which may be placed among the two elements include, for example, water proofing materials, anti-trauma materials, and the like.
  • Improved ice pick and knife penetration resistance can be obtained using the two elements in accordance with this invention.
  • the layers which form the sections of this composite can be joined such as by being sewn together or they can be stacked together and held, for example, in a fabric envelope.
  • the layers which constitute each section are usually placed together and the composite can, thereby, be seen as a structure having distinct sections of layers.
  • the high knife penetration resistance of this invention is provided by the polybenzoxazole or polybenzothiazole fabric layers.
  • the polybenzoxazole or polybenzothiazole fabric layers can be located anywhere in the article.
  • the high ice pick penetration resistance of this invention is provided by the tightly woven fabric layers.
  • the Fig. shows the protective composite 10 of this invention with a section 11 of layers 12 of woven polybenzoxazole or polybenzothiazole, and a section 13 of layers 14 of tightly-woven layers.
  • the layers 12 and 14 can be intermixed in any sequence such that sections 11 and 13 are not distinct.
  • Linear Density The linear density of a yarn is determined by weighing a known length of the yarn. "dtex" is defined as the weight, in grams, of 10,000 meters of the yarn.
  • the measured dtex of a yarn sample, test conditions, and sample identification are fed into a computer before the start of a test; the computer records the load-elongation curve of the yarn as it is broken and then calculates the properties.
  • the yarns to be tested are conditioned at 25°C, 55% relative humidity for a minimum of 14 hours and the tensile tests are conducted at those conditions.
  • Tenacity (breaking tenacity), elongation to break, and modulus are determined by breaking test yarns on an Instron tester (Instron Engineering Corp., Canton, Mass.).
  • Tenacity, elongation, and initial modulus are determined using yarn gage lengths of 25.4 cm and an elongation rate of 50% strain/minute. The modulus is calculated from the slope of the stress-strain curve at 1% strain and is equal to the stress in grams at 1% strain (absolute) times 100, divided by the test yarn linear density.
  • Knife penetration resistance is determined on a sample to be tested using a boning knife (made by Russell Harrington Cutlery, Inc., Southbridge, Massachusetts, U.S.A.) with a single edged blade 15 cm (6 inches) long and about 2 cm (0.8 inch) wide, tapering toward the tip and having a Rockwell hardness of C-55.
  • the tests are conducted in accordance with HPW test TP-0400.03 (28 November 1994) from H. P. White Lab., Inc.
  • the test samples, placed on a 10% gelatin backing, are impacted with the knife, weighted to 4.55 kilograms (10 pounds) and dropped from various heights until penetration of the sample of greater than 6mm under test conditions is accomplished.
  • Ice pick penetration is determined using the same procedure as set out above except that the boning knife is replaced with an ice pick 18 centimeters (7 inches) long and 0.64 centimeters (0.25 inch) in shaft diameter having a Rockwell hardness of C-42. Results are reported as penetration energy (joules) by multiplying kilogram-meters, from the energy at the penetrating height, by 9.81.
  • Ballistics Performance Ballistic tests of the multi-layer panels are conducted to determine the ballistic limit (V50) in accordance with MIL-STD-662e, except in the selection of projectiles, as follows: A panel to be tested is placed against a backing material of Roma Plastina No. 1 clay in a sample mount to hold the panel taut and perpendicular to the path of test projectiles.
  • the projectiles are 9mm full metal jacket hand-gun bullets weighing 124 grains, and are propelled from a test barrel capable of firing the projectiles at different velocities. The first firing for each panel is for a projectile velocity estimated to be the likely ballistics limit (V50).
  • the next firing is for a projectile velocity of about 15.5 meters (50 feet) per second less in order to obtain a partial penetration of the panel.
  • the next firing is for a velocity of about 15.2 meters (50 feet) per second more in order to obtain a complete penetration.
  • subsequent velocity increases or decreases of about 15.2 meters (50 feet) per second are used until enough firings are made to determine the ballistics limit (V50) for that panel.
  • the ballistics limit (V50) is calculated by finding the arithmetic mean of an equal number of at least three of the highest partial penetration impact velocities and the lowest complete penetration impact velocities, provided that there is a difference of not more than 38.1 meters (125 feet) per second between the highest and lowest individual impact velocities.
  • the composite structures provide much higher penetration energy results than would be expected from a simple sum of the individual section elements of the combination. It is, also, noted that the penetration resistance is remarkably higher when the polybenzoxazole section is located on the top (exposed to the knife stab).
  • the composite structures provide much higher penetration energy results than would be expected from a simple sum of the individual elements of the combination. It is, also, noted that the penetration energy results are poor for the comparison composite wherein the tightly-woven layers are nearer the inner face than ballistic layers.

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  • Engineering & Computer Science (AREA)
  • General Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
  • Laminated Bodies (AREA)
  • Woven Fabrics (AREA)
  • Professional, Industrial, Or Sporting Protective Garments (AREA)
  • Reinforced Plastic Materials (AREA)

Claims (9)

  1. Article résistant à la pénétration d'un couteau ou d'un piolet (10), comprenant
    a. une pluralité (11) de couches essentiellement résistantes au couteau (12) en tissu comprenant des fibres de polybenzoxazole ou de polybenzothiazole et
    b. une pluralité (13) de couches essentiellement résistantes au piolet (14) en tissu à tissage serré résistant à la pénétration ayant une densité de tissage d'au moins 0,75.
  2. Article selon la revendication 1, dans lequel ledit tissu à tissage serré résistant à la pénétration inclut des fibres polyamide.
  3. Article selon la revendication 2, dans lequel lesdites fibres polyamide sont des fibres paraaramides.
  4. Article selon la revendication 1, dans lequel la pluralité (13) de couches en tissu à tissage serré et résistant à la pénétration (14) inclut du fil d'aramide ayant une densité linéaire de moins de 500 dtex et caractérisée en ce que le tissu à tissage serré résistant à la pénétration a un facteur de densité de tissage d'au moins 0,95.
  5. Article selon l'une quelconque des revendications 1 à 4, dans lequel ledit tissu à tissage serré et résistant à la pénétration inclut des fibres de polyolefines.
  6. Article selon la revendication 5, dans lequel lesdites fibres de polyolefines sont du polyéthylène.
  7. Article selon l'une quelconque des revendications 1 à 6, dans lequel ledit tissu à tissage serré résistant à la pénétration inclut des fibres de polybenzoxazole ou de polybenzothiazole.
  8. Article selon la revendication 1, dans lequel la pluralité (13) de couches en tissu à tissage serré et résistant à la pénétration (14) inclut un fil polybenzoxazole ou polybenzothiazole ayant une densité linéaire de moins de 500 dtex et caractérisé en ce que le tissu à tissage serré et résistant à la pénétration a un facteur de densité de tissage d'au moins 0,95.
  9. Article selon la revendication 1, dans lequel les fibres de polybenzoxazole ou polybenzothiazole sont dans un fil avec une densité linéaire de 100 à 3300 dtex et les fibres ont une densité linéaire de 0,3 à 17 dtex.
EP04024471A 1998-12-21 1999-08-10 Composite hybride de protection Expired - Lifetime EP1496331B1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
US217360 1994-03-24
US09/217,360 US6162746A (en) 1998-09-29 1998-12-21 Hybrid protective composite
EP99942041A EP1141649B2 (fr) 1998-12-21 1999-08-10 Composite hybride protecteur

Related Parent Applications (1)

Application Number Title Priority Date Filing Date
EP99942041A Division EP1141649B2 (fr) 1998-12-21 1999-08-10 Composite hybride protecteur

Publications (2)

Publication Number Publication Date
EP1496331A1 EP1496331A1 (fr) 2005-01-12
EP1496331B1 true EP1496331B1 (fr) 2008-11-05

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Application Number Title Priority Date Filing Date
EP04024471A Expired - Lifetime EP1496331B1 (fr) 1998-12-21 1999-08-10 Composite hybride de protection
EP99942041A Expired - Lifetime EP1141649B2 (fr) 1998-12-21 1999-08-10 Composite hybride protecteur

Family Applications After (1)

Application Number Title Priority Date Filing Date
EP99942041A Expired - Lifetime EP1141649B2 (fr) 1998-12-21 1999-08-10 Composite hybride protecteur

Country Status (13)

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EP (2) EP1496331B1 (fr)
JP (1) JP3794924B2 (fr)
KR (1) KR100471335B1 (fr)
CN (1) CN1118677C (fr)
AU (1) AU755697B2 (fr)
BR (1) BR9917018B1 (fr)
CA (1) CA2346980C (fr)
DE (2) DE69927712T3 (fr)
HK (1) HK1040279A1 (fr)
IL (1) IL142522A0 (fr)
RU (1) RU2217682C2 (fr)
TW (1) TWI227197B (fr)
WO (1) WO2000037876A1 (fr)

Families Citing this family (13)

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Publication number Priority date Publication date Assignee Title
EP1219915A1 (fr) * 2000-12-19 2002-07-03 Dsm N.V. Gilet ballistique
EP1219916B1 (fr) * 2000-12-19 2006-08-09 DSM IP Assets B.V. Gilet pare-balles
US6610617B2 (en) 2001-04-12 2003-08-26 E. I. Du Pont De Nemours And Company Ballistic resistant article
EP1384041B1 (fr) * 2001-05-03 2013-07-10 Barrday, Inc. Tissu quasi unidirectionnel pour applications pare-balle
US6737368B2 (en) * 2001-12-19 2004-05-18 E. I. Du Pont De Nemours And Company Multiple threat penetration resistant articles
CN101310159A (zh) * 2005-08-10 2008-11-19 纳幕尔杜邦公司 可挠曲耐穿透物品
JP5050399B2 (ja) * 2006-04-28 2012-10-17 東洋紡績株式会社 防弾チョッキ
US7994075B1 (en) * 2008-02-26 2011-08-09 Honeywell International, Inc. Low weight and high durability soft body armor composite using topical wax coatings
US8236711B1 (en) 2008-06-12 2012-08-07 Milliken & Company Flexible spike and knife resistant composite
CN104943289B (zh) * 2014-03-28 2018-04-24 杜邦公司 纤维增强的复合层合体和由其制成的制品
BE1023672B1 (nl) 2016-05-19 2017-06-12 Seyntex N.V. Flexibele, licht-gewicht antiballistische bescherming
RU2707781C1 (ru) * 2018-12-18 2019-11-29 Акционерное Общество "Научно-производственное предприятие "Термостойкий текстиль" (АО НПП "Термотекс") Гибридный композиционный материал для оболочечных конструкций высокого давления
RU2733744C1 (ru) * 2019-08-20 2020-10-06 Борис Сергеевич Кокорев Способ создания высокопрочной двухкомпонентной нити на основе пара-арамидных и полиэтиленовых высокомолекулярных волокон

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AU2221892A (en) 1991-06-26 1993-01-25 E.I. Du Pont De Nemours And Company P-aramid ballistic yarn and structure
US5187003A (en) * 1991-11-26 1993-02-16 E. I. Du Pont De Nemours And Company Hybrid ballistic fabric
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US5472769A (en) 1993-12-10 1995-12-05 American Institute Of Criminology International Corp. Soft body armor material with enhanced puncture resistance comprising at least one continuous fabric having knit portions and integrally woven hinge portions
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JP3698219B2 (ja) † 1995-09-07 2005-09-21 東洋紡績株式会社 防護衣料
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Also Published As

Publication number Publication date
AU5550599A (en) 2000-07-12
DE69927712D1 (de) 2005-11-17
CA2346980A1 (fr) 2000-06-29
CN1118677C (zh) 2003-08-20
EP1141649B1 (fr) 2005-10-12
EP1141649B2 (fr) 2011-11-23
HK1040279A1 (zh) 2002-05-31
RU2217682C2 (ru) 2003-11-27
JP2002533651A (ja) 2002-10-08
WO2000037876A1 (fr) 2000-06-29
IL142522A0 (en) 2002-03-10
DE69927712T3 (de) 2012-05-16
JP3794924B2 (ja) 2006-07-12
EP1496331A1 (fr) 2005-01-12
AU755697B2 (en) 2002-12-19
EP1141649A1 (fr) 2001-10-10
CA2346980C (fr) 2004-05-11
DE69927712T2 (de) 2006-07-06
KR100471335B1 (ko) 2005-02-21
DE69939883D1 (de) 2008-12-18
CN1331794A (zh) 2002-01-16
BR9917018A (pt) 2005-04-12
TWI227197B (en) 2005-02-01
BR9917018B1 (pt) 2010-10-19
KR20010089661A (ko) 2001-10-08

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