CN101336360A - Flame retardant shield - Google Patents
Flame retardant shield Download PDFInfo
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- CN101336360A CN101336360A CNA2006800524250A CN200680052425A CN101336360A CN 101336360 A CN101336360 A CN 101336360A CN A2006800524250 A CNA2006800524250 A CN A2006800524250A CN 200680052425 A CN200680052425 A CN 200680052425A CN 101336360 A CN101336360 A CN 101336360A
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- China
- Prior art keywords
- fiber
- fire retardant
- resistant
- fabrics
- flame resistant
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Classifications
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- 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
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- 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
- A41D31/08—Heat resistant; Fire retardant
- A41D31/085—Heat resistant; Fire retardant using layered materials
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- 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
- A41D31/245—Resistant to mechanical stress, e.g. pierce-proof using layered materials
Abstract
Flame resistant, ballistic resistant composite fabrics are provided. More particularly, structures are formed from a material having excellent flame and ballistic resistance. The fabrics and structures incorporate a non-halogen containing charring flame retardant that is preferably intumescent, whereby the material being charred forms a char foam, providing an insulating barrier when exposed to heat. While adding flame retardance, the fabrics and structures retain the excellent optimum ballistic resistant properties of the original material.
Description
Background of invention
Invention field
The present invention relates to flame resistant, ballistic resistant composite fabrics.More particularly, the present invention relates to by having the excellent fire-retardant structure that forms with material bullet-proof.
Description of related art
The ballistic-resistant article that has an excellent properties for deformable projectiles that comprises high strength fibre is known.For example the goods of bullet-proof vest, the helmet, vehicle panel and military equipment structure member are typically made by the fabric that comprises high strength fibre.Normally used high strength fibre comprises polyethylene fibre, to aramid fibre as poly-(paraphenylene terephthalamide's phenylenediamine), graphite fibre, nylon fiber, glass fibre etc.For a lot of application, for example vest or parts of vests, can be used in described fiber woven or knit goods in.For a lot of other application, described fiber is encapsulated or is embedded in the host material, form rigidity or or flexible fabric.
The multiple ballistic structure that is used to form goods such as the helmet, panel and vest is known.For example, United States Patent (USP) 4,403,012,4,457,985,4,613,535,4,623,574,4,650,710,4,737,402,4,748,064,5,552,208,5,587,230,6,642,159,6,841,492,6,846,758 have described the ballistic composite that comprises the high strength fibre that is become by for example extended chain ultrahigh molecular weight polyethylene, and it all is combined in here as a reference.These composites demonstrate penetration-resistant in various degree for the high speed impact from bullet such as bullet, shell case, canister shot etc.
For example, United States Patent (USP) 4,623,574 and 4,748,064 discloses the simple composite structure that comprises the high strength fibre that is embedded in the elastomeric matrices.United States Patent (USP) 4,650,710 disclose the flexible article that comprises a plurality of products by the fibroplastic flexible layer of high strength extended chain polyolefin (ECP).Described network fibres applies with low modulus elastomeric material.United States Patent (USP) 5,552,208 and 5,587,230 disclose the goods of a kind of network that comprises at least one high strength fibre and base composition and have prepared the method for these goods, and described base composition comprises vinyl esters and diallyl phthalate.United States Patent (USP) 6,642,159 disclose a kind of a plurality of fibrolaminar shock-resistant rigid composite materials that have, and it comprises the long filament network that is arranged in the matrix, has elastic layer therebetween.Described composite is bonded on the hardboard, to strengthen the protection to armor-piercing bullet.
A problem of ballistic fabric and goods existence at present is their limited anti-flammabilitys.The anti-flammability of bullet resistant material is high expectations, so that the protection that ballistic-resistant article provides maximization.Usually, the approach that preferably can improve the polymeric material anti-flammability in polymer in conjunction with flame-retardant additive.Fire retardant works by the combustion process of disturbing polymer or other material.Can use dissimilar additives, its every kind provides fire-retardant by different binding modes usually.For example, a class that is called the phase reactive-type flame retardant that condenses (condensed-phase active flame retardants) promotes charing by reducing or limiting combustible fuel quantity.The another kind of fire retardant that is called volatilization phase reactive-type flame retardant (volatile-phaseactive flame retardants) suppresses described combustion process by reducing the heat that discharges during the burning.
The non-removing property of the additive of particular type ground comprises the charing type additive that promotes the material charing; The heat absorption additive, as aluminium hydroxide and magnesium hydroxide, it absorbs heat and heat is dissipated in the ambient atmosphere; The Toxic inhibitor, when adding it in combustible material, one or more toxic gases that it significantly reduces or prevents to produce during the thermal decomposition; With the additive combination that utilizes synergy, i.e. optimum organization have difference but the multiple additives of active pattern of cooperation.Thereby, compare different flame retardant with other fire retardant and may be effectively in the different phase of combustion process and different flame retardant based on its mode of action, for application-specific, compare also with other additive and can have specific advantage or deficiency.
For example, United States Patent (USP) 5,480,706 provide a kind of halogenated fire-retardants such as halogenated paraffin of combining to increase the flame resistant, ballistic resistant goods of anti-flammability.Yet halogenated fire-retardants is not expected based on environment and security consideration.For example, halogenated fire-retardants produces high toxicity gas such as chlorine and bromine during burning.Further, when these materials mix with water, form extremely strong acid.Except that bringing environmental hazard, these accessory substances also are extremely harmful for the ballistic-resistant article user.Other additive types can have appreciable impact for the physical property of original polymer.In certain applications, need the fire retardant of relatively large amount, whether play the effect of plasticizer or filler according to described fire retardant, can there be bigger variation in balance of properties.For example, mass filler material such as clay or sand can be used to improve anti-flammability, but it can not be used for bullet resistant material, because this class material significantly increases the weight of ballistic-resistant article, has limited its practicality.
Therefore,, under the condition of not damaging bullet-proof, provide to have excellent flame retardancy, and user and environment are all had low dangerous bullet resistant material is high expectations and favourable in the ballistic-resistant article field.The present invention provides a solution for this demand.The invention provides a kind of flame resistant, ballistic resistant fabrics that is combined in the high strength fibre in the base composition that comprises, this base composition comprises the charing fire retardant.Described base composition generally includes adhesive material (matrix polymer) and on this adhesive material or the charing fire retardant that can mix with this adhesive material.Charing is a kind of burn incompletely process, and it removes dehydrogenation and oxygen from incendiary material, make charcoal mainly be made up of carbon.The advantage that forms charcoal comprises the volatile matter quality of reduction, during wherein part carbon and hydrogen remain on and condenses mutually, reduces the volatile combustible degraded fragment quality of sending; The thermal capacity that increases, wherein the formation of charcoal-polymeric blends is compared with carbonated material not, improves the thermal capacity of described material; With stop fuel gas, thereby charred surface can play the effect of physical barriers layer, stop by lower floor not the fuel gas that produces of carbonated material degraded flow, and hinder oxygen and arrive described polymer surfaces.Further, charcoal forms heat insulation also is provided, thereby when depolymerization, is not remaining formation charcoal layer on the carbonizing polymer, the thermal conductivity that this layer is lower makes it play adiabatic effect, thereby input of absorption portion heat and reduction arrive the not heat flux of carbonizing polymer.Described charing fire retardant does not preferably discharge halogen, and preferred intumescent (intumescent type) fire retardant, thereby describedly when exposing is expanded by the material volume of charing, formation foam and provide insulation barrier when hot when being exposed to.For example,, compare, have better insulation characterisitic with the hard crisp dense char that typically forms by halogenated fire-retardants by the non-halogenated expansion charcoal that a large amount of vesicles are formed.The expansion charing behavior that also has been found that the flame-retardant additive of institute's combination has negligible influence to the bullet-proof of fabric of the present invention, has kept the best bullet-proof of original material.
Summary of the invention
The invention provides a kind of flame resistant, ballistic resistant fabrics, comprising: a) a plurality of fibers that are arranged to array, described fiber combine and form fabric, and described fiber has about 7g/ danier or higher toughness and about 150g/ danier or higher stretch modulus; And b) base composition that comprises the charing fire retardant on described fiber.
The present invention also provides a kind of flame resistant, ballistic resistant fabrics, it comprises (consolidated) network of fibers that at least one is fixed, described fixed network of fibers comprises a plurality of overlappings (cross-plied) fibrage, and each fibrage comprises a plurality of fibers of arranging with substantially parallel array (array); Described fiber has about 7g/ danier or higher toughness and about 150g/ danier or higher stretch modulus; Described fiber has base composition thereon, and this base composition comprises the charing fire retardant; Described a plurality of cross-plied fiber layers is fixed with described base composition, to form described fixed network of fibers.
The present invention further provides a kind of flame resistant, ballistic resistant goods, it comprises flame resistant, ballistic resistant fabrics, and this flame resistant, ballistic resistant fabrics comprises:
A) a plurality of fibers that are arranged to array, described fiber combine and form fabric, and described fiber has about 7g/ danier or higher toughness and about 150g/ danier or higher stretch modulus; With
B) base composition that comprises the charing fire retardant on described fiber.
The present invention further provides a kind of method of production flame resistant, ballistic resistant fabrics, comprising:
A) form at least two fibrages, each fibrage forms by a plurality of fiber cloth being set to substantially parallel unilateral array; Described fiber has about 7g/ danier or higher toughness and about 150g/ danier or higher stretch modulus; Described fiber uses the base composition that comprises the charing fire retardant to apply;
B) arrange described fibrage, wherein the unilateral array with every layer of fiber overlaps with respect to each adjacent layer; With
C), thereby form fabric at the layer that is enough to form the described overlapping of bonding under the condition of single-layer, consolidated network.
Detailed description of the preferred embodiment
The present invention proposes fire resistant fabric composite with excellent in resistance ballistic penetration.Based on purpose of the present invention, the fabric with excellent in resistance ballistic penetration has been described for deformable projectiles and has been demonstrated those of excellent properties.Flame-retardant textile of the present invention is preferably included in this area and is called the elasticity of base composition or the single-layer, consolidated network of fibers in the rigid polymer composition, and wherein said base composition comprises at least a charing fire retardant.Described network of fibers comprises a plurality of fibrages that are stacked, each fibrage comprise that the described base composition of a plurality of usefulness applies and with the fiber of substantially parallel arranged in arrays and described fibrage by fixed to form described single-layer, consolidated network.Described consolidated network also comprises the plurality of yarns that applies, forms a plurality of layers and be consolidated into fabric with this base composition.
Based on purpose of the present invention, " fiber " is a kind of extrusion (elongate body), and its length dimension is much larger than the lateral dimension of width and thickness.Being used for fibre section of the present invention can change in relative broad range.They can have circle, flat partially or elliptic cross-section.Therefore, the term fiber comprises long filament with rule or irregular section, band, bar etc.They can also be irregular or regular multiple leaf-shaped sections, have one or more rules that highlight from the linear axle or the longitudinal axis of described fiber or irregular leaf.Preferred described fiber is single leaf, and has the basic circular cross section that is.
As used herein, " yarn " is interlocking fiber (interlocked fibers) bundle." array " described orderly layout and " parallel array " of fiber or yarn and described being arranged in parallel in order of fiber or yarn.Fiber " layer " is described the horizontal layout of braiding (woven) or non-woven (non-woven) fiber or yarn.Fiber " network " a plurality of interconnective fibers of expression or thread layers.Network of fibers can have multiple structure.For example, described fiber or yarn can be used as felt (felt) or another kind of woven, non-woven or knit goods formation, or form network by any other routine techniques.According to particularly preferred consolidated network configuration, with a plurality of fibrage combinations, thereby each fibrage comprises that unidirectional array becomes array so that the fiber that they are parallel to each other substantially along common fiber direction." fixed network " described the consolidated combination of fibrage and base composition.As used herein, " individual layer " structure is meant by the fixed structure of forming for single integrally-built one or more independently fibrages.Usually, " fabric " can relate to braiding or non-woven material.
As used herein, " the high tensile modulus fibers of high strength " is a kind of like this fiber, its have by ASTM D2256 measure preferred at least about 7g/ danier or higher toughness, preferably at least about 150g/ danier or higher stretch modulus and preferred at least about 8J/g or higher energy to failure.As used herein, term " danier " is meant linear density unit, equals in per 9000 meters fibers of gram or quality of yarn.As used herein, term " toughness " is meant the tensile stress of the power with per unit linear density (danier) (gram) expression of the sample that do not stretch (unstressed specimen)." initial modulus " of fiber is the material character of its deformation resistance of expression.Term " stretch modulus " is meant that toughness changes the ratio with strain variation, and described toughness changes with the every danier of fors (g/d) expression, and described strain variation is expressed as the mark (in/in) of initial fiber length.
The high tensile modulus fibers material of Shi Yi high strength comprises the extended chain polyolefin fiber especially, as height-oriented high molecular weight polyethylene fiber, particularly superhigh molecular weight polyethylene fibers, and polypropylene fiber of superhigh molecular weight.Same suitable be the pure fiber of extended chain polyethylene, extended chain polyacrylonitrile fibre, to aramid fibre (para-aramid fibers), polybenzoxazole fiber (polybenzazole fibers) as polybenzoxazole (PBO) and polybenzothiozole (PBT) fiber and liquid crystal copolymerization of polyester fiber (liquid crystal copolyester fibers).Every kind of these fiber type all is well known in the art.
Under the polyethylene situation, preferred fiber is for having the extended chain polyethylene of at least 500,000 molecular weight, and preferred molecular weight is at least 100 ten thousand and more preferably 2,000,000-5,000,000.This extended chain polyethylene (ECPE) fiber can form in the solution spinning technique, for example at United States Patent (USP) 4,137,394 or 4,356, as described in 138, it is combined in here as a reference, or can be by the solution spinning to form gel structure, for example at United States Patent (USP) 4,551,296 and 5, as described in 006,390, it is combined in here as a reference equally.
Most preferably being used for polyethylene fibre of the present invention is at trade mark by Honeywell International Inc.
The polyethylene fibre of following sale.
Fiber is well-known in the art, and for example at the United States Patent (USP) of owning together 4,623,547 and 4,748 of investing people such as Harpell, description is arranged in 064.With Unit Weight (ounce for ounce),
High-performance fiber intensity is 10 times of iron and steel, and is also enough light simultaneously, can swim in waterborne.Described fiber also has other critical nature, comprises resistance to impact, moisture-proof, wear-resistant, chemical resistance and paracentesis resistance.
Suitable polypropylene fibre is included in United States Patent (USP) 4,413, height-oriented extended chain polypropylene (ECPP) fiber of describing in 110, and it is combined in here as a reference.Suitable polyvinyl alcohol (PV-OH) fiber for example is described in United States Patent (USP) 4,440, and in 711 and 4,599,267, it is combined in here as a reference.Suitable polyacrylonitrile (PAN) fiber is for example at United States Patent (USP) 4,535, and open in 027, it is combined in here as a reference.All these fibers all are known, and can be extensively commercially available.
Suitable aromatic polyamides (aromatic polyamide) or to the commercially available acquisition of aramid fibre, and for example be recorded in the United States Patent (USP) 3,671,542.For example spendable poly-(poly P phenylene diamine terephthalamide) long filament is existed by Dupont company
Commodity production under the trade name.Also spendable in the present invention's practice is to be existed by Dupont
Poly-(mpd-i) fiber of commodity production under the trade name.The suitable commercially available acquisition of polybenzoxazole fiber that is used for the present invention's practice, and for example disclosing in the United States Patent (USP) 5,286,833,5,296,185,5,356,584,5,534,205 and 6,040,050, it all is combined in here as a reference.Preferred polybenzoxazole fiber is Toyobo Co's
The board fiber.Be applicable to the commercially available acquisition of liquid crystal copolymerization of polyester fiber that the present invention puts into practice, and at United States Patent (USP) 3,975, open in 487,4,118,372 and 4,161,470, it all is combined in here as a reference.
The fiber that other is applicable to fiber that fiber type of the present invention comprises glass fibre, formed by carbon, formed by basalt (basalt) or other material,
The combination of fiber and all above-mentioned materials, its all commercially available acquisition.
Fiber is by Richmond, and the MagellanSystems International of Virginia produces, and for example is described in United States Patent (USP) 5,674, and in 969,5,939,553,5,945,537 and 6,040,478, it all is combined in here as a reference.Particularly preferred fiber comprises
Fiber, polyethylene
Fiber, poly-(poly P phenylene diamine terephthalamide) and poly-(to penylene-2,6-benzo-dioxazole (benzobisoxazole)) fiber.Most preferably, described fiber comprises the high strength and modulus polyethylene
Fiber.
Based on purpose of the present invention, most preferred fiber is the high stretch modulus extended chain polyethylene of a high strength fiber.As above-mentioned record, the high tensile modulus fibers of high strength is for having preferred about 7g/ danier or higher toughness, the preferred fiber of about 150g/ danier or higher stretch modulus and preferably about 8J/g or higher energy to failure by ASTM D2256 measurement.In preferred implementation of the present invention, the toughness of described fiber should be about 15g/ danier or higher, preferably about 20g/ danier or higher, more preferably from about 25g/ danier or higher, most preferably from about 30g/ danier or higher.Fiber of the present invention also has about 300g/ danier or higher preferred tensile modulus, 400g/ danier or higher more preferably from about, 500g/ danier or higher more preferably from about, more preferably from about 1,000g/ danier or higher and most preferably from about 1,500g/ danier or higher.Fiber of the present invention also has preferred about 15J/g or higher energy to failure, 25J/g or higher more preferably from about, more preferably from about 30J/g or higher and most preferably have about 40J/g or a higher energy to failure.The high strength properties of these combinations can obtain by adopting known solution growth or gel fiber processes.United States Patent (USP) 4,413,110,4,440,711,4,535,027,4,457,985,4,623,547,4,650,710 and 4,748,064 has usually discussed the preferred high strength extended chain polyethylene fiber that adopts among the present invention.
Fiber of the present invention is by applying base composition to described fiber, fixed then this base composition-fiber combinations and be coated with described base composition, be impregnated with described base composition, be embedded in the described base composition or be applied with described base composition." fixed " expression is combined into single integral layer with described host material and each individual fiber layer.Fixed by drying, cooling, heating, pressure or their combination enforcement.
Fabric composites of the present invention can adopt multiple host material preparation, and described host material comprises low modulus elastomeric matrices material and high modulus, rigid matrix material.As used herein, term " matrix " is well-known in the art, is used to represent adhesive material such as polymeric adhesive material, and it bonds together described fiber after fixed.Term " composite " is meant the consolidated combination of fiber and host material.The suitable non-removing property of host material ground comprises having and is lower than about 6, the low modulus elastomeric material of the initial tensile modulus of 000psi (41.3MPa), with have at least about 300, the high-modulus rigid material of 000psi (2068MPa) initial tensile modulus, it is all measured down at 37 ℃ by ASTMD638.As used in this article, the elastic modelling quantity measured by ASTM D638 of the ASTM 2256 of elastic modelling quantity measure by to(for) fibring of term stretch modulus and represent for host material.
Elastomeric matrix composition can comprise multiple polymerization and non-cohesive material.Preferred elastomeric matrix composition comprises low modulus elastomeric material.Based on purpose of the present invention, low modulus elastomeric material has about 6 according to ASTM D638 test method measuring, 000psi (41.4MPa) or lower stretch modulus.Preferably, described elastomeric stretch modulus is about 4,000psi (27.6MPa) or lower, and 2400psi (16.5MPa) or lower more preferably from about, more preferably 1200psi (8.23MPa) or lower most preferably is about 500psi (3.45MPa) or lower.Described elastomeric glass transition temperature (Tg) preferably is lower than about 0 ℃, more preferably less than-40 ℃ approximately, most preferably is lower than-50 ℃ approximately.Described elastomer also has preferably the elongation at break at least about 50%, more preferably at least about 100% with most preferably have a elongation at break at least about 300%.
Can use multiple elastomeric material with low modulus and prescription as described matrix.Suitable elastomeric exemplary has the Science at Encyclopedia of Polymer, Elastomers-Synthetic part (John Wiley ﹠amp among the Volume 5; Sons Inc.1964) structure of Zong Jieing, character, prescription and cross-linking method.Preferred low modulus elastomeric matrices material comprises polyethylene, crosslinked polyethylene, chlorine sulfination polyethylene, ethylene copolymer, polypropylene, propylene copolymer, polybutadiene, polyisoprene, natural rubber, ethylene-propylene copolymer, ethylene-propylene-diene terpolymer, polysulfide polymer (polysulfide polymers), polyurethane elastomer, polychlorobutadiene, use the polyvinyl chloride of one or more plasticizer well known in the art (as dioctyl phthalate) plasticising, the butadiene acrylonitrile elastomer, poly-(isobutene-copolymerization-isoprene), polyacrylate, polyester, unsaturated polyester (UP), polyethers, fluoroelastomer, silicone elastomer, thermoplastic elastomer (TPE), phenoplasts, bunching butyraldehyde (polybutyrals), epoxy polymer, polystyrene (styrenic) block copolymer, as styrene-isoprene-phenylethene or s-B-S type and other low modulus polymers and copolymer that can under fiber fusing point as described in being lower than, solidify.The blend of the also blend of preferred different elastomeric materials, or elastomeric material and one or more thermoplastics (thermoplastics).
Useful especially is the block copolymer of conjugated diene and vinyl aromatic monomers.Butadiene and isoprene are preferred conjugated diene elastomers.Styrene, vinyltoluene and t-butyl styrene are preferred conjugated aromatic monomers.The thermoplastic elastomer (TPE) that the block copolymer hydrogenation that is combined with polyisoprene can be had saturated hydrocarbons elastomer fragment with production.Described polymer can be simple A-B-A type triblock copolymer, (AB)
n(n=2-10) type segmented copolymer or R-(BA)
x(x=3-150) the star structure copolymer of type; Wherein A is the block from conjugated diene elastomers from the block of polyvinyl aromatic monomer and B.A lot of these polymer are by Houston, and the Kraton Polymers of TX is commercial to be made, and is recorded in " Kraton Thermoplastic Rubber ", in the SC-68-81 communique.Most preferred matrix polymer comprise by Kraton Polymers commodity production at trade mark
The styrene block copolymer of following sale.
Preferred high modulus, rigid matrix material used herein comprises the material of vinyl ester polymer for example or styrene-butadiene block copolymer, and the polymeric blends material of vinyl esters and diallyl phthalate mixture or phenolic resins and polyvinyl butyral resin mixture for example.Being particularly preferred for rigid matrix materials of the present invention is thermosetting polymer, and it preferably dissolves in carbon-to-carbon saturated solvent such as the MEK, and has at least about 1 * 10 when measuring by ASTM D638 after curing
6The high stretch modulus of psi (6895MPa).Particularly preferred rigid matrix materials is for being recorded in United States Patent (USP) 6,642, those in 159, and it is combined in here as a reference.
Rigidity, shock resistance and the bullet-proof of the goods that formed by Fabric composites of the present invention are influenced by the stretch modulus of matrix polymer.For example, United States Patent (USP) 4,623,574 disclose by having and have been lower than about 6000psi (41, the fibre reinforced composites that the elastomeric matrices of stretch modulus 300kPa) makes up, with compare by the composite of the polymer construction of high-modulus more and with the identical fibre structure that does not contain matrix, have excellent bullet-proof.Yet low stretch modulus matrix polymer has also caused the composite of lower rigidity.Further, in some applications, particularly in those application that composite must all work, need the excellent combination of bullet-proof and rigidity under shellproof and tactic pattern.Therefore, the optimum type of the matrix polymer of use will change according to the product type that is formed by fabric of the present invention.For realizing the coordination of two kinds of character, suitable base composition low modulus capable of being combined and high modulus material form the single-matrix composition.
In preferred implementation of the present invention, proportion of fibers preferably accounts for the about 95 weight % of about 70-of composite, more preferably accounts for the about 91 weight % of about 79-of composite and most preferably accounts for the about 89 weight % of about 83-of composite.The remainder of composite is the combination of matrix and fire retardant.Described base composition also can comprise filler such as carbon black or silica, and usable oils is filled, or available sulphur, peroxide, metal oxide or the sulfuration of radiation curing system, just as known in the art.Described base composition can further comprise antioxidant, as
Those that trade mark is sold down, it can be commercially available by Switzerland Ciba Specialty Chemicals Corporation, is especially
1010 ((four-(methylene-(3,5-di-t-butyl-4-hydroxyl cortex cinnamomi acid ester) methane)); With the surfactant that prevents fire retardant sedimentation in base composition, as
Those that trade mark is sold down, it can be commercially available by Dutch Uniqema, particularly
G1096 (polyoxyethylene sorbitan ester).
According to the present invention, described base composition comprises at least a charing fire retardant.During burning, this charing fire retardant and fiber and host material are combined to form charcoal.As used herein, term " charing fire retardant " is meant flame-retardant compound, composition or the mixture that produces charcoal or promote the material charing, wherein charing is a kind ofly to remove dehydrogenation and oxygen from incendiary material, so that stay mainly the burn incompletely process of the material of being made up of carbon.Preferred charing fire retardant comprises the expanding material that does not discharge halogen.As used herein, term " expansion " is meant when being exposed to heat or surpassing the flame of specified temp, the material of volumetric expansion.The suitable non-removing property of non-halogenated charing fire retardant ground comprises that metal hydroxides such as aluminium hydroxide (alumina trihydrate) and magnesium hydroxide (or hydrous magnesium (hydrated magnesium)), hydrated carbonate, calcium carbonate, boracic fire retardant comprise that Firebrake ZB, aromatic boric acid are as 1,4-benzene hypoboric acid and phenylboric acid, pentaerythrite, novolaks (novolacs), the iron additive that does not discharge halogen such as iron oxide and polyphenylene oxide and phosphorus, phosphorus-containing compound such as diphenyl phosphate and triphenyl phosphate, and the combination of above-mentioned substance.Wherein, most preferably phosphorus and phosphor-included additive.
In the charing classes of flame retardants, different kind of material or blend can work by different way.For example, phosphine flame retardant mainly in condensing mutually usually by forming phosphoric acid (when the heating) by promoting charing, and reduce combustible volatile and discharge and play a role.When heating during phosphorus compound, phosphoric acid takes place to be formed, this acid combines with carbon in the polymer and causes charcoal.Alternatively, metal hydroxides such as magnesium hydroxide or aluminium hydroxide decompose under flame heat, and discharge hydrate water.This class material is also as pressing down fumicants.These fire retardants also can be used as second additive in the flame-retardant polymer system that wherein has other fire retardant (for example phosphorio compound).
In optimal way of the present invention, the fire retardant of described charing type preferably includes the blend of material.Charing fire retardant for example of the present invention preferably includes the blend that contains additive, described additive for example improves the synergist (synergists) that charcoal forms efficient for one or more, and charcoal is blown afloat foaming agent (spumific agent) that forms form of foam or the charing catalyst that improves charing speed.Suitable synergist comprises melamine polyphosphate (melamine polyphosphate), APP and nitrogen releasable material; Suitable foaming agent (blowing agent) mainly discharges multiple other blowing agent of nitrogen when comprising amine/acid amides, melamine, dicyandiamide, urea and heating; Suitable catalyst comprises the material that discharges boric acid, phosphoric acid or sulfuric acid in the combustion process, described acid combines with the polymer of described composite in combustion process and forms charcoal, for example phosphorus compound such as ammonium phosphate and phosphate, aromatic boric acid and above-mentioned boron compound.For example, described foaming agent melamine discharges nitrogen, increases the height (loft) of charcoal, and combines with the described material of charing with for example phosphorus.The nitrogen that this melamine discharges still is the also retarded combustion process of inertia.Therefore, Shi Yi charing fire retardant preferably includes the blend of above-mentioned material.
Particularly preferred charing fire retardant comprise can
(be called Maxichar in the past
TM),
With
Material, particularly Newark that trade mark obtains down, the BroadviewTechnologies of NJ sell
The expansion blend that comprises melamine pyrophosphate (melamine pyrophosphate) and two (melamine pyrophosphoric acid) (bis (melaminepyrophosphoric) acid) that trade mark obtains down; Germany Chemische Fabrik BudenheimKg Limited Partnership sell can
The expansion blend that comprises APP that the 3077BG trade mark obtains down; With Switzerland Clariant International Ltd. sell can
The expansion blend that comprises APP that AP 752 trade marks obtain down.
The charing fire retardant preferably adopts the adhesive blend in technology well known in the art and the base composition.For example described charing fire retardant is sneaked in the solvent in the bulk container with propeller-type blender, assist so that this fire retardant is remained in the solution by surfactant, the dissolved matrix binder polymer is with the preparation blend then.In preferred implementation of the present invention, described charing fire retardant accounts for the about 20 weight % of about 1 weight %-of whole base compositions, more preferably from about 3%-about 10% and most preferably account for about 5%-about 7% of whole base compositions.Alternatively, described charing fire retardant can use techniques well known to be applied on the base polymer layer, thereby forms for example two layer matrix composition.Not with described charing flame retardant materials and matrix polymer blend, with described fire retardant before being applied on the matrix polymer be under the situation of powder type, this fire retardant and independent adhesive such as epoxy resin, acrylic acid series material or other polymerization well known in the art or non-cohesive material are combined.In preferred implementation of the present invention, described base composition comprises the blend of charing fire retardant and matrix polymer binder, for example phosphorus or phosphorous charing fire retardant with
The blend of polymer.
Usually, flame resistant, ballistic resistant fabrics of the present invention forms by high strength fibre being arranged to one or more fibrages.Every layer of array that can comprise individual fibers or yarn.Preferably before or after described layer forms, base composition is applied on this high strength fibre, then described host material-fiber combinations is consolidated, form multilayer composite.
Described matrix can be applied on the fiber in many ways, for example passes through spraying or roller coat base composition solution to fiber surface, and is dry then.A kind of method is applied on the fiber as the particle in liquid, sticky solid or the suspended substance or as fluid bed (fluidized bed) for the straight polymer with coating material.Alternatively, solution or emulsion that described coating can be used as in suitable solvent apply, and wherein said solvent can not have a negative impact to fibre property applying under the temperature.For example, fiber or yarn can be transmitted the solution that passes through described base composition, with this fiber of abundant coating or yarn, dry then fiber or the yarn that applies that form.The coated fiber that obtains or yarn arrangement can be become the network structure of expectation then.In another kind of paint-on technique, at first arrange fibrage, then this layer immersion contained in the solution bath of host material, and then by the evaporating solvent drying.If need, can repeat this impregnation steps for several times, on fiber, to form the host material coating of desired amount.
Can dissolve arbitrarily or the liquid of dispersed polymeres although can use, but preferred group of solvents comprises water, paraffin oil and aromatic solvent or hydrocarbon solvent, and illustrative concrete solvent comprises paraffin oil, dimethylbenzene, toluene, octane, cyclohexane, MEK (MEK) and acetone.The technology at solvent dissolving or dispersion coatings polymer of being used for will be that routine is used for applying those of similar material on different substrate materials.
Can use coating is coated to other technology on the fiber, be included in before described fiber stands drawing by high temperature and handle, from fiber, remove desolvate before or after, apply high-modulus precursor (gelatinous fibre) (if adopting gel-spun fiber to form technology).Fiber can be stretched at elevated temperatures then, to produce the fiber that applies.
Can be with described gelatinous fibre solution by suitable coated polymer under the condition that obtains the expectation coating.Before fiber fed described solution, the crystallization of heavy polymer can take place or not take place in the gelatinous fibre.Alternatively, fiber can be clamp-oned in the fluid bed of suitable polymer powder.In addition, if implement stretched operation or other operating process such as exchange of solvent, drying etc., described coating can be applied on the precursor material of final fiber.In most preferred embodiment of the present invention, at first fiber of the present invention is applied with base composition, then a plurality of fiber cloth are inserted in braiding or the fibrous nonwoven layer.Such technology is well known in the art.
The base composition coated fiber that applies preferred use selection of described host material or at least one surface of yarn preferably apply or encapsulate each independent fiber substantially.After applying host material, before fixed, the individual fibers in the layer can bond or bonding mutually not mutually, and this is fixed by forcing together and fusing fiber that (fusing) so apply and a plurality of fibers or thread layers are combined.Fabric composites of the present invention preferably includes a plurality of braidings or the fibrous nonwoven layer that is consolidated into the single-layer, consolidated network of fibers.In preferred implementation of the present invention, described layer comprises non woven fibre, and each independent fibrage of described consolidation fibre network preferably includes the fiber that is arranged parallel to each other along common fiber direction.The succeeding layer of the fiber of this unidirectional array can be with respect to preceding one deck rotation.Preferably, with the individual fibers layer overlapping of composite, so that the machine direction of unidirectional fibre is with respect to the machine direction rotation of unidirectional fibre in the adjacent layer in each individual course.An example is five laminates, wherein second, third, the 4th and layer 5 with respect to ground floor be rotated+45 ° ,-45 °, 90 ° and 0 °, but be not must be according to this order.Based on purpose of the present invention, adjacent layer can be almost with respect to the longitudinal fiber direction of another layer with the align at random angles between about 0 °-Yue 90 °.Preferred example comprises having 0 °/90 ° of orientations two-layer.The unidirectional array of this rotation for example is described in the United States Patent (USP) 4,457,985,4,748,064,4,916,000,4,403,012,4,623,573 and 4,737,402.Described network of fibers can make up by multiple known method, for example by being recorded in United States Patent (USP) 6,642, and the method in 159.Should be appreciated that single-layer, consolidated network of the present invention can comprise the alternating layer of any amount usually, for example the needs according to different purposes can comprise about 20-about 40 layers or more layer.
In preferred implementation of the present invention, can at first fiber of the present invention be adopted one of above-mentioned technology to apply with elastomeric matrix composition, then a plurality of fiber cloth are set to fibrous nonwoven layer.Preferably, independent fiber is adjacent and be in contact with one another placement, and be arranged to the wherein said fiber of sheet-like fiber array and arrange substantially in parallel to each other along common fiber direction.In the special otherwise effective technique that fiber cloth is set to described structure, described fiber is pulled through the bath that contains elastomeric material solution, subsequently around and be wound in the single sheet layer along suitable framework such as cylindrical length direction spiral.To stay the prepreg of the fiber that is arranged in parallel from the solvent evaporation of described solution then, it can take off and be cut into desired size from described cylindrical frame.Alternatively, a plurality of fibers can be pulled through simultaneously elastomer solution and bathe, and closely be arranged in substantially parallel mutually on the suitable surface.Stayed fibrous prepreg by elastomer coated by evaporating solvent, wherein said fiber is substantially parallel and arrange along common fiber direction.
Preferably follow said method with at least two unidirectional fiber layers of formation, thereby described fiber is applied by base composition substantially on all fibres surface.After this, preferably described fibrage is consolidated into the single-layer, consolidated network of fibers.This can bond together it with the heat setting general structure under heating and pressure then by described independent fibrage is piled up mutually, makes described host material flow into and occupy any residue void space and realizes.As known in the art, when individual fiber layer is overlapped so that the fiber alignment direction in one deck during with certain angle rotation, has obtained excellent bullet-proof with respect to the fiber alignment direction in another layer.For example, preferred construction has two fibrages of the present invention that are arranged together, and makes longitudinal fiber direction of one deck and the longitudinal fiber direction quadrature of another layer.
In most preferred embodiments, the fiber that two layers of unidirectional is arranged overlaps with 0 °/90 ° structures, and molding forms precursor then.Described two fibrages can overlap continuously, preferably by one of described layer being cut into the length that can pass through the width placement of another layer subsequently with 0 °/90 ° orientations, form one-way tape well known in the art (unitape).United States Patent (USP) 5,173,138 and 5,766725 have described the equipment that is used for continuous overlapping.Continuous two lamellas (two-ply) structure that obtains can be wound in the volume that all has separating layers of material at every interlayer then.When preparing the final use of formation structure, parting material is untied and removed to described volume.Then described two lamella sub-assemblies (sub-assembly) are cut into discrete sheet, pile up with multi-disc layer form, and then through be heated and pressure to form net shape and if necessary, solidify described matrix polymer.Similarly, when a plurality of yarn arrangement are formed individual layer, the unidirectional layout of described yarn also can be overlapped in a similar manner, fixed then.
The suitable bonding condition that is used for described fibrage is consolidated into single-layer, consolidated network or Fabric composites comprises the lamination that routine is known.Typical laminating technology is included in about 110 ℃ and under about 200psi (1379kPa) pressure described cross-plied fiber layers was forced together about 30 minutes.Of the present invention fibrolaminar fixed preferably under about 200 (～93 ℃)-Yue 350 (～177 ℃) temperature, more preferably under about 200-Yue 300 (～149 ℃) temperature, most preferably under about 200-Yue 280 (～121 ℃) temperature and about 25psi (～172kPa)-implement under Yue 500psi (3447kPa) or the higher pressure.As this area is known usually, fixed can in autoclave, enforcement.
When heating, can make described matrix not become sticky under the condition of fusing fully or flow.Yet, if usually make the host material fusing, need relatively little pressure to form described composite, and if only host material is heated to bonding point (sticking point), then typically need bigger pressure.Consolidation step can need about 10 seconds-Yue 24 hours usually.Yet temperature, pressure and time are usually by polymer type, polymer content, technology and fiber type decision.
The thickness of separate fabric layer will be corresponding with the thickness of individual fibers.Therefore, the preferred single-layer, consolidated network of the present invention will have the thickness of the preferred about 500 μ m of about 25 μ m-, the more preferably from about about 385 μ m of 75 μ m-and the most preferably from about about 255 μ m of 125 μ m-.The thickness of even now is preferred, can produce other thickness satisfying particular demands but should understand, and still fall within the scope of the invention.
After described fabric forms, can use it in the multiple application.For the one or more temperature that are exposed to and/or the pressure of the described single-layer, consolidated network of fibers that carries out molding fiber changes according to the high strength fibre type of using.For example, armour plate (armor panels) can by the about 400psi of about 150-(1,030-2,760kPa), the about 250psi of preferably about 180-(1, make under the temperature of pressure 240-1720kPa) and about 104 ℃-Yue 127 ℃ by the lamination of described of molding.The helmet can be made by the lamination of described of molding under the about 3000psi of about 1500-(10.3-20.6MPa) pressure and about 104 ℃-Yue 127 ℃ of temperature.Same suitable is for example in the United States Patent (USP) 4,623,574,4,650,710,4,748,064,5,552,208,5,587,230,6,642,159,6,841,492 and 6,846,758 record be applicable to the technology that forms goods.
Fabric composites of the present invention is particularly useful for forming flame resistant, ballistic resistant " firmly " armor articles." firmly " plate armour is meant to have enough mechanical strengths so that it keeps structural rigidity and can not need to support and the goods that can not collapse when standing a large amount of stress, for example the helmet, military vehicle panel or protectiveness guard shield.Described network of fibers can keep the high flexibility feature of textile fabric independently, and preferred the maintenance is separated from each other, and promptly do not bond together.Alternatively, multiply cloth can be stitched together or use binding material or other thermoplasticity or non-thermoplastic fiber or material to bond together.Thereby goods of the present invention can comprise a plurality of woven, flame resistant fabrics that are assembled into bonding or non-bonding array.This single-layer, consolidated network can be cut into a plurality of discrete sheets, and pile up, or they can form the precursor that is used to form goods subsequently with the formation goods.Such technology is well known in the art.
Clothes of the present invention can form by means commonly known in the art.Preferably, described clothes can form by flame-retardant textile of the present invention being attached to clothes product.For example vest can comprise the common fabric vest that is combined with flame-retardant textile of the present invention, wherein fabric of the present invention is inserted in the pocket of key position setting.This makes it possible to maximization of ballistic protection, minimizes the weight of described vest simultaneously.As used herein, term " combination " or " combined " are intended to comprise adheres to as stitching or adhesion etc., and with other fabric non-adhere to be connected or and put, make that so described flame resistant, ballistic resistant fabrics can randomly be easy to remove from vest or other clothes product.Vest and other clothes product of being made up of according to the fabric of the present invention's structure multilayer have good flexibility and comfortableness, and have excellent ballistic protection and anti-flammability.The fabric that is used to form flexible structure such as flexible sheets, vest and other clothes is preferably formed by the fabric that adopts low stretch modulus base composition.The boardy product such as the helmet and the armor are preferably formed by the fabric that adopts high stretch modulus base composition.
The anti-flammability of fabric adopts standard test method well known in the art to measure.For example, in test method ASTM E1354 (Cone Calorimeter Testing), a large amount of heat and flame (equaling the heat of 50KW) are applied on the sample.During sample combustion, write down some parameters then.
Bullet-proof adopts standard test method known in this field to measure.For example, the Protective Research of ballistic composite adopts the non-distortion steel disc of 22 bores (Mil-Spec.MIL-P-46593A (ORD)) with specified weight, hardness and size usually.
The protective capacities of structure or penetration resistance usually by reference 50% bullet penetrate described composite, simultaneously 50% impact speed when being stopped by guard shield is represented, is also referred to as V
50Value.As used herein, " penetration resistance " of goods is to the resistance that penetrates that specify to threaten, and described appointment for example threatens to physical objects and comprises for example impact generated by explosion ripple of bullet, fragment, canister shot etc. and non-physical objects.For the composite of identical faces density, surface density be weight with composite panel divided by surface area, V
50High more, the protective of composite is good more.The bullet-proof of fabric of the present invention can change especially for the fiber type of producing described fabric according to multiple factor.Yet, have been found that with the charing fire retardant be incorporated in the described base composition not can negative effect fabric of the present invention bullet-proof, as can be finding among the following embodiment.
Following non-limiting example is used to illustrate the present invention.
Embodiment 1 (contrast)
By high-modulus polyethylene fibres (HMPE) (
1000,1100 denier fibers) layer forms the non-woven composite of 0 °/90 ° of overlappings of two lamellas.Make fiber form first one-way tape that unilateral array prepares the HMPE fiber by comb from several fiber bobbin cradles.Described fiber applies with matrix, is placed on the carrier web then.Described matrix polymer is to be dissolved in the cyclohexane solvent
The solution of polymer.The fiber that makes the coating with 39gsm fiber areal densities then is by baking oven, with the evaporating cyclohexane solvent.After the drying, this network of fibers is wrapped on the roller.The width of this roller is 63 ".Polymer content on the described network of fibers is 20 weight %.
Prepare the second similar one-way tape independently.With two networks of fibers with 0 °/90 ° overlappings, and heat and pressure under fixed with formation bullet resistant material continuous volume.The total areal density of described cross-plied material is 98gsm.
By piling up 50 layers of cross-plied material molded 0.22 " the first thick one-way tape 12 " * 12 " plates.The molded condition of described plate is 240 heating and 500psi pressure 20 minutes.Adopt the MIL-STD-662F test method, use the bullet-proof of the described plate of 17grain FragmentSimulating Projectile (FSP) test that meets MIL-P-46593A.The V of this plate
50Be 1750 feet per seconds (fps).
By piling up 0.1 " slab of 22 layers of molded second one-way tape of cross-plied material.The molded condition of this plate is same as described above.Downcut 4 " * 4 " sample from above-mentioned plate, and the test anti-flammability.On this sample, adopt 50KW heat energy to implement ASTM E1354-Cone Calorimeter Test.The average quality loss late of this specimen is 12.269kg/m
2, the peak value heat liberation rate, heat release rate is 645.17KW/m
2, the average heat liberation rate, heat release rate during the burning is 325.43KW/m
2And to the time of peaking heat liberation rate, heat release rate be 110 seconds.
Embodiment 2 (contrast)
Repeat embodiment 1, water base except using
Polymer emulsion forms first and second one-way tapes.Polymer content is 16%.Using the preparation of four lamellas (0 °, 90 °, 0 °, 90 °) structure to overlap rolls up.The total areal density of this four lamellas overlapping volume is 250gsm.
By piling up 20 layers of cross-plied material molded 0.22 " the first thick one-way tape 12 " * 12 " plates.The molded condition of described plate is 240 heating and 500psi pressure 20 minutes.The bullet-proof that the 17grain FragmentSimulating Projectile that adopts the use of MIL-STD-662F test method to meet MIL-P-46593A tests described plate.The V of this plate
50Be 1825fps.
By piling up 0.1 " slab of 9 layers of molded second one-way tape of cross-plied material.The molded condition of this plate is same as described above.Downcut 4 " * 4 " sample from above-mentioned plate, and the test anti-flammability.On this sample, adopt 50KW heat energy to implement ASTM E1354-Cone Calorimeter Test.The average quality loss late of this specimen is 12.334kg/m
2, the peak value heat liberation rate, heat release rate is 752.45KW/m
2, the average heat liberation rate, heat release rate during the burning is 308.42KW/m
2And to the time of peaking heat liberation rate, heat release rate be 135 seconds.
Embodiment 3
Repeat embodiment 1, except will be by composite 5 weight %'s
3077BG charing flame retardant blends with
Polymer solution mixes.This base composition comprises following prescription, and it comprises the charing fire retardant that contains the expansion blend, and described expansion blend contains APP and contains the material of melamine:
Cyclohexane (solvent) 79.48wt%
Irganox
TM1010 (antioxidant) 0.31wt%
Kraton polymer (matrix polymer) 15.14wt%
Described two lamellas overlap and roll up the total areal density with 98gsm.
By piling up 50 layers of fire-retardant cross-plied material molded 0.22 " the first thick one-way tape 12 " * 12 " plates.The molded condition of described plate is 240 heating and 500psi pressure 20 minutes.The bullet-proof that the 17grain FragmentSimulating Projectile that adopts the use of MIL-STD-662F test method to meet MIL-P-46593A tests described plate.The V of this plate
50Be 1795fps.
By piling up 0.1 " slab of 22 layers of molded second one-way tape of cross-plied material.The molded condition of this plate is same as described above.Downcut 4 " * 4 " sample from above-mentioned plate, and the test anti-flammability.On this sample, implement ASTM E1354-Cone Calorimeter Test, wherein on this sample, apply big calorimetric and flame (50KW heat energy).The average quality loss late of this specimen is 9.930kg/m
2, the peak value heat liberation rate, heat release rate is 521.12KW/m
2, the average heat liberation rate, heat release rate during the burning is 274.73KW/m
2And to the time of peaking heat liberation rate, heat release rate be 100 seconds.
These embodiment show, add charing type fire retardant and bring anti-flammability in the base composition of ballistic fabric, and can not reduce the bullet-proof or the structural property of fabric.
Embodiment 1-3 the results are summarized in the following table:
| Embodiment 1 (contrast) | Embodiment 2 (contrast) | Embodiment 3 (comprising the charing fire retardant) | |
| Thickness of sample (mm) | 2.5 | 2.5 | 2.5 |
| Mass loss rate (g) | 1.66 | 1.79 | 1.59 |
| Average quality loss late (kg/m 2) | 12.269 | 12.334 | 9.930 |
| Peak value heat liberation rate, heat release rate (Kw/m 2) | 645.17 | 752.45 | 521.12 |
| Burning period average heat liberation rate, heat release rate (Kw/m 2) | 325.43 | 308.42 | 274.73 |
| To the time (second) of peaking heat liberation rate, heat release rate | 110 | 135 | 100 |
| Average V 50(fps), for 1lb/ft 2Plate 17grain FSP | 1750 | 1825 | 1795 |
Embodiment 4
Use following matrix formulations to repeat embodiment 3, described prescription comprises the charing fire retardant that contains the expansion blend, and described blend contains the APP with nitrogenous synergist:
Cyclohexane (solvent) 79.17wt%
Irganox
TM1010 (antioxidant) 0.28wt%
Embodiment 5
Use following matrix formulations to repeat embodiment 3, described prescription comprises the charing fire retardant that contains the phosphorous blend that expands:
Cyclohexane (solvent) 76.30wt%
Irganox
TM1010 (antioxidant) 0.40wt%
Although the present invention has carried out special demonstration and explanation with reference to preferred implementation, it is readily appreciated by a person skilled in the art that and to carry out various changes and improvements under purport of the present invention and the scope not breaking away from.Claim should be explained replacement form and all equivalent form of values thereof of doing to cover disclosed embodiment, above-mentioned discussion.
Claims (40)
1. flame resistant, ballistic resistant fabrics comprises:
A) a plurality of fibers that are arranged to array, described fiber is combined together and form fabric, and described fiber has about 7g/ danier or higher toughness and about 150g/ danier or higher stretch modulus; With
B) base composition that contains the charing fire retardant on described fiber.
2. the flame resistant, ballistic resistant fabrics of claim 1, wherein said base composition comprises the charing fire retardant with the adhesive blend.
3. the flame resistant, ballistic resistant fabrics of claim 1, wherein said base composition is included in the charing fire retardant on the adhesive.
4. the flame resistant, ballistic resistant fabrics of claim 1, wherein said charing fire retardant comprises the expanding material that does not discharge halogen.
5. the flame resistant, ballistic resistant fabrics of claim 1, wherein said charing fire retardant comprises the foaming material that does not discharge halogen.
6. the flame resistant, ballistic resistant fabrics of claim 1, wherein said charing fire retardant comprises phosphorated material.
7. the flame resistant, ballistic resistant fabrics of claim 1, wherein said charing fire retardant comprises the material that contains APP.
8. the flame resistant, ballistic resistant fabrics of claim 1, wherein said charing fire retardant accounts for the about 20 weight % of about 1 weight %-of described fabric.
9. the flame resistant, ballistic resistant fabrics of claim 1, wherein said charing fire retardant accounts for the about 10 weight % of about 3 weight %-of described fabric.
10. the flame resistant, ballistic resistant fabrics of claim 1, wherein said charing fire retardant accounts for the about 7 weight % of about 5 weight %-of described fabric.
11. the flame resistant, ballistic resistant fabrics of claim 1, wherein said fiber comprise the material that is selected from extended chain polyolefin fiber, aramid fibre, polybenzoxazole fiber, vinal, Fypro, pet fiber, polyethylene naphthalate fiber, polyacrylonitrile fibre, liquid crystal copolymerization of polyester fiber, glass fibre, carbon fiber and their combination.
12. the flame resistant, ballistic resistant fabrics of claim 1, wherein said fiber comprises polyethylene fibre.
13. the flame resistant, ballistic resistant fabrics of claim 1, wherein said base composition 37 ℃ measure down have about 6,000psi or littler initial tensile modulus.
14. measuring down at 37 ℃, the flame resistant, ballistic resistant fabrics of claim 1, wherein said base composition have at least about 300 the initial tensile modulus of 000psi.
15. a flame resistant, ballistic resistant fabrics that comprises the network of fibers that at least one is fixed, wherein said fixed network of fibers comprises a plurality of cross-plied fiber layers, and each fibrage comprises a plurality of fibers with substantially parallel arranged in arrays; Described fiber has about 7g/ danier or higher toughness and about 150g/ danier or higher stretch modulus; Described fiber has base composition in the above, and described base composition comprises the charing fire retardant; The fibrage of described a plurality of overlappings is fixed by described base composition, forms described fixed network of fibers.
16. according to the flame resistant, ballistic resistant fabrics of claim 15, wherein said base composition comprises the charing fire retardant with the adhesive blend.
17. according to the flame resistant, ballistic resistant fabrics of claim 15, wherein said base composition is included in the charing fire retardant on the adhesive.
18. according to the flame resistant, ballistic resistant fabrics of claim 15, wherein each described fibrage overlaps with 90 ° of angles with respect to the machine direction of each adjacent fiber layer.
19. according to the flame resistant, ballistic resistant fabrics of claim 15, wherein said charing fire retardant comprises the expanding material that does not discharge halogen.
20. according to the flame resistant, ballistic resistant fabrics of claim 15, wherein said charing fire retardant comprises the foaming material that does not discharge halogen.
21. according to the flame resistant, ballistic resistant fabrics of claim 15, wherein said charing fire retardant comprises phosphorated material.
22. according to the flame resistant, ballistic resistant fabrics of claim 15, wherein said charing fire retardant comprises the material that contains APP.
23. according to the flame resistant, ballistic resistant fabrics of claim 15, wherein said charing fire retardant accounts for the about 20 weight % of about 1 weight %-of described fabric.
24. the flame resistant, ballistic resistant fabrics of claim 15, wherein said charing fire retardant account for the about 10 weight % of about 3 weight %-of described fabric.
25. the flame resistant, ballistic resistant fabrics of claim 15, wherein said charing fire retardant account for the about 7 weight % of about 5 weight %-of described fabric.
26. the flame resistant, ballistic resistant fabrics of claim 15, wherein said fiber comprise the material that is selected from extended chain polyolefin fiber, aramid fibre, polybenzoxazole fiber, vinal, Fypro, pet fiber, polyethylene naphthalate fiber, polyacrylonitrile fibre, liquid crystal copolymerization of polyester fiber, glass fibre, carbon fiber and their combination.
27. the flame resistant, ballistic resistant fabrics of claim 15, wherein said fiber comprises polyethylene fibre.
28. the flame resistant, ballistic resistant fabrics of claim 15, wherein said base composition 37 ℃ measure down have about 6,000psi or littler initial tensile modulus.
29. measuring down at 37 ℃, the flame resistant, ballistic resistant fabrics of claim 15, wherein said base composition have at least about 300 the initial tensile modulus of 000psi.
30. flame resistant, ballistic resistant goods that comprise flame resistant, ballistic resistant fabrics, described flame resistant, ballistic resistant fabrics comprises:
A) a plurality of fibers that are arranged to array, described fiber is combined together and form fabric, and described fiber has about 7g/ danier or higher toughness and about 150g/ danier or higher stretch modulus; With
B) base composition that contains the charing fire retardant on described fiber.
31. according to the flame resistant, ballistic resistant goods of claim 30, it comprises molded panel.
32. according to the flame resistant, ballistic resistant goods of claim 30, it comprises clothes, wherein said flame resistant, ballistic resistant fabrics comprises a plurality of layers of the described fiber that is consolidated into single layer network, and wherein one or more described networks are attached to described clothes.
33. according to the flame resistant, ballistic resistant goods of claim 30, wherein said charing fire retardant comprises the expanding material that does not discharge halogen.
34. according to the flame resistant, ballistic resistant goods of claim 30, wherein said charing fire retardant comprises the foaming material that does not discharge halogen.
35. according to the flame resistant, ballistic resistant goods of claim 30, wherein said charing fire retardant comprises phosphorated material.
36. according to the flame resistant, ballistic resistant goods of claim 30, wherein said charing fire retardant comprises the material that contains APP.
37. a method of producing flame resistant, ballistic resistant fabrics comprises:
A) form at least two fibrages, each fibrage forms by a plurality of fiber cloth being set to substantially parallel unilateral array; Described fiber has about 7g/ danier or higher toughness and about 150g/ danier or higher stretch modulus; Described fiber uses the base composition that comprises the charing fire retardant to apply;
B) arrange described fibrage, the unilateral array of every layer of fiber is overlapped with respect to each adjacent layer; With
C), thereby form fabric at the layer that is enough to form the described overlapping of bonding under the condition of single-layer, consolidated network.
38. according to the method for claim 37, wherein said charing fire retardant comprises not halogen-containing expanding material.
39. according to the method for claim 37, wherein said charing fire retardant comprises not halogen-containing foaming material.
40. according to the method for claim 37, wherein said charing fire retardant comprises phosphorated material.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US29508105A | 2005-12-06 | 2005-12-06 | |
| US11/295,081 | 2005-12-06 |
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| CN101336360A true CN101336360A (en) | 2008-12-31 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNA2006800524250A Pending CN101336360A (en) | 2005-12-06 | 2006-11-30 | Flame retardant shield |
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| Country | Link |
|---|---|
| EP (1) | EP1957931A1 (en) |
| JP (1) | JP2009518618A (en) |
| CN (1) | CN101336360A (en) |
| IL (1) | IL191969A0 (en) |
| WO (1) | WO2007067405A1 (en) |
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| US3916060A (en) * | 1973-09-19 | 1975-10-28 | Nasa | Fiber modified polyurethane foam for ballistic protection |
| US4748064A (en) | 1985-01-14 | 1988-05-31 | Allied Corporation | Ballistic-resistant composite article |
| US4650710A (en) | 1985-02-25 | 1987-03-17 | Allied Corporation | Ballistic-resistant fabric article |
| US4737402A (en) | 1985-02-28 | 1988-04-12 | Allied Corporation | Complex composite article having improved impact resistance |
| FR2625516B1 (en) * | 1988-01-04 | 1990-06-01 | Duflot & Fils | PROTECTIVE TEXTILE BARRIER AGAINST MECHANICAL AND / OR THERMAL ASSAULT |
| US5167876A (en) * | 1990-12-07 | 1992-12-01 | Allied-Signal Inc. | Flame resistant ballistic composite |
| US5552208A (en) | 1993-10-29 | 1996-09-03 | Alliedsignal Inc. | High strength composite |
| US6197415B1 (en) * | 1999-01-22 | 2001-03-06 | Frisby Technologies, Inc. | Gel-coated materials with increased flame retardancy |
| US6642159B1 (en) | 2000-08-16 | 2003-11-04 | Honeywell International Inc. | Impact resistant rigid composite and method for manufacture |
| US6846758B2 (en) | 2002-04-19 | 2005-01-25 | Honeywell International Inc. | Ballistic fabric laminates |
| US6841492B2 (en) | 2002-06-07 | 2005-01-11 | Honeywell International Inc. | Bi-directional and multi-axial fabrics and fabric composites |
| US6890638B2 (en) * | 2002-10-10 | 2005-05-10 | Honeywell International Inc. | Ballistic resistant and fire resistant composite articles |
-
2006
- 2006-11-30 EP EP06838644A patent/EP1957931A1/en not_active Withdrawn
- 2006-11-30 CN CNA2006800524250A patent/CN101336360A/en active Pending
- 2006-11-30 WO PCT/US2006/045790 patent/WO2007067405A1/en active Application Filing
- 2006-11-30 JP JP2008544375A patent/JP2009518618A/en not_active Withdrawn
-
2008
- 2008-06-05 IL IL191969A patent/IL191969A0/en unknown
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103753903A (en) * | 2013-11-27 | 2014-04-30 | 北京同益中特种纤维技术开发有限公司 | Preparation method for flame-resistant bulletproof composite material and prepared composite material |
| CN103753903B (en) * | 2013-11-27 | 2016-01-20 | 北京同益中特种纤维技术开发有限公司 | A kind of preparation method of flame resistant, ballistic resistant composite and obtained composite |
| CN105671722A (en) * | 2016-03-07 | 2016-06-15 | 杭州柯力达家纺有限公司 | Flame-retardant polyester yarn and sofa cloth made of same |
| CN105671722B (en) * | 2016-03-07 | 2017-12-12 | 杭州柯力达家纺有限公司 | A kind of flame-resistant terylene yarn and using sofa cloth made of the spun polyester thread |
Also Published As
| Publication number | Publication date |
|---|---|
| EP1957931A1 (en) | 2008-08-20 |
| JP2009518618A (en) | 2009-05-07 |
| IL191969A0 (en) | 2008-12-29 |
| WO2007067405A1 (en) | 2007-06-14 |
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Open date: 20081231 |