CN104136212A - 用于生产防弹制品的复合物 - Google Patents
用于生产防弹制品的复合物 Download PDFInfo
- Publication number
- CN104136212A CN104136212A CN201380009910.XA CN201380009910A CN104136212A CN 104136212 A CN104136212 A CN 104136212A CN 201380009910 A CN201380009910 A CN 201380009910A CN 104136212 A CN104136212 A CN 104136212A
- Authority
- CN
- China
- Prior art keywords
- polyvinyl butyral
- butyral resin
- tissue layer
- layer
- compound
- 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.)
- Pending
Links
- 239000002131 composite material Substances 0.000 title abstract 4
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 claims abstract description 61
- 239000000835 fiber Substances 0.000 claims abstract description 52
- 229920005989 resin Polymers 0.000 claims description 57
- 239000011347 resin Substances 0.000 claims description 57
- 150000001875 compounds Chemical class 0.000 claims description 43
- -1 polyethylene Polymers 0.000 claims description 23
- 239000004760 aramid Substances 0.000 claims description 22
- 229920003235 aromatic polyamide Polymers 0.000 claims description 22
- 238000004519 manufacturing process Methods 0.000 claims description 22
- 238000000034 method Methods 0.000 claims description 18
- 239000002759 woven fabric Substances 0.000 claims description 17
- 239000004698 Polyethylene Substances 0.000 claims description 13
- 229920000573 polyethylene Polymers 0.000 claims description 13
- 239000000654 additive Substances 0.000 claims description 8
- 238000002844 melting Methods 0.000 claims description 6
- 230000008018 melting Effects 0.000 claims description 6
- 238000003490 calendering Methods 0.000 claims description 2
- 239000004744 fabric Substances 0.000 abstract description 6
- 239000011888 foil Substances 0.000 abstract 2
- 239000010410 layer Substances 0.000 description 124
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 22
- 229920000642 polymer Polymers 0.000 description 16
- 239000004372 Polyvinyl alcohol Substances 0.000 description 15
- 229920002451 polyvinyl alcohol Polymers 0.000 description 15
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- KJFMBFZCATUALV-UHFFFAOYSA-N phenolphthalein Chemical compound C1=CC(O)=CC=C1C1(C=2C=CC(O)=CC=2)C2=CC=CC=C2C(=O)O1 KJFMBFZCATUALV-UHFFFAOYSA-N 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 7
- 230000000996 additive effect Effects 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 238000006116 polymerization reaction Methods 0.000 description 5
- 239000013068 control sample Substances 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 229920002689 polyvinyl acetate Polymers 0.000 description 4
- 239000011118 polyvinyl acetate Substances 0.000 description 4
- 238000010992 reflux Methods 0.000 description 4
- 235000011121 sodium hydroxide Nutrition 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 239000003381 stabilizer Substances 0.000 description 4
- 238000003860 storage Methods 0.000 description 4
- 238000009941 weaving Methods 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 3
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 3
- ZTQSAGDEMFDKMZ-UHFFFAOYSA-N Butyraldehyde Chemical compound CCCC=O ZTQSAGDEMFDKMZ-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- 150000001412 amines Chemical class 0.000 description 3
- 238000009954 braiding Methods 0.000 description 3
- 238000002788 crimping Methods 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000004014 plasticizer Substances 0.000 description 3
- 239000000523 sample Substances 0.000 description 3
- 238000004448 titration Methods 0.000 description 3
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- 229920002367 Polyisobutene Polymers 0.000 description 2
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 description 2
- 230000021736 acetylation Effects 0.000 description 2
- 238000006640 acetylation reaction Methods 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 125000003158 alcohol group Chemical group 0.000 description 2
- 238000003556 assay Methods 0.000 description 2
- 238000005227 gel permeation chromatography Methods 0.000 description 2
- HHLFWLYXYJOTON-UHFFFAOYSA-N glyoxylic acid Chemical compound OC(=O)C=O HHLFWLYXYJOTON-UHFFFAOYSA-N 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 238000009940 knitting Methods 0.000 description 2
- 238000006386 neutralization reaction Methods 0.000 description 2
- 239000002356 single layer Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- MHSKRLJMQQNJNC-UHFFFAOYSA-N terephthalamide Chemical compound NC(=O)C1=CC=C(C(N)=O)C=C1 MHSKRLJMQQNJNC-UHFFFAOYSA-N 0.000 description 2
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- YAXWOADCWUUUNX-UHFFFAOYSA-N 1,2,2,3-tetramethylpiperidine Chemical compound CC1CCCN(C)C1(C)C YAXWOADCWUUUNX-UHFFFAOYSA-N 0.000 description 1
- RKMGAJGJIURJSJ-UHFFFAOYSA-N 2,2,6,6-Tetramethylpiperidine Substances CC1(C)CCCC(C)(C)N1 RKMGAJGJIURJSJ-UHFFFAOYSA-N 0.000 description 1
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 1
- IRIAEXORFWYRCZ-UHFFFAOYSA-N Butylbenzyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCC1=CC=CC=C1 IRIAEXORFWYRCZ-UHFFFAOYSA-N 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 239000002174 Styrene-butadiene Substances 0.000 description 1
- 239000004699 Ultra-high molecular weight polyethylene Substances 0.000 description 1
- 238000011000 absolute method Methods 0.000 description 1
- DHKHKXVYLBGOIT-UHFFFAOYSA-N acetaldehyde Diethyl Acetal Natural products CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 description 1
- BLAKAEFIFWAFGH-UHFFFAOYSA-N acetyl acetate;pyridine Chemical compound C1=CC=NC=C1.CC(=O)OC(C)=O BLAKAEFIFWAFGH-UHFFFAOYSA-N 0.000 description 1
- 238000007171 acid catalysis Methods 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 229960000250 adipic acid Drugs 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 235000019445 benzyl alcohol Nutrition 0.000 description 1
- 229960004217 benzyl alcohol Drugs 0.000 description 1
- 238000000071 blow moulding Methods 0.000 description 1
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 238000007766 curtain coating Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000012634 fragment Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- OJXOOFXUHZAXLO-UHFFFAOYSA-M magnesium;1-bromo-3-methanidylbenzene;bromide Chemical compound [Mg+2].[Br-].[CH2-]C1=CC=CC(Br)=C1 OJXOOFXUHZAXLO-UHFFFAOYSA-M 0.000 description 1
- 229920003052 natural elastomer Polymers 0.000 description 1
- 229920001194 natural rubber Polymers 0.000 description 1
- XNGIFLGASWRNHJ-UHFFFAOYSA-N o-dicarboxybenzene Natural products OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000002093 peripheral effect Effects 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- AQSJGOWTSHOLKH-UHFFFAOYSA-N phosphite(3-) Chemical class [O-]P([O-])[O-] AQSJGOWTSHOLKH-UHFFFAOYSA-N 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 238000003918 potentiometric titration Methods 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000007127 saponification reaction Methods 0.000 description 1
- 229940116351 sebacate Drugs 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 238000009987 spinning Methods 0.000 description 1
- 238000001370 static light scattering Methods 0.000 description 1
- 239000011115 styrene butadiene Substances 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 229920003051 synthetic elastomer Polymers 0.000 description 1
- 239000005061 synthetic rubber Substances 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 229920000785 ultra high molecular weight polyethylene Polymers 0.000 description 1
- HGBOYTHUEUWSSQ-UHFFFAOYSA-N valeric aldehyde Natural products CCCCC=O HGBOYTHUEUWSSQ-UHFFFAOYSA-N 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
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- B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
- B32B27/302—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising aromatic vinyl (co)polymers, e.g. styrenic (co)polymers
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- B32B5/22—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed
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- B32B5/24—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed one layer being a fibrous or filamentary layer
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- B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
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- B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
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- B32B37/10—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the pressing technique, e.g. using action of vacuum or fluid pressure
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- B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
- B32B5/02—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by structural features of a fibrous or filamentary layer
- B32B5/022—Non-woven fabric
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
- B32B5/02—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by structural features of a fibrous or filamentary layer
- B32B5/024—Woven fabric
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
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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
- F41H5/0478—Fibre- or fabric-reinforced layers in combination with plastics layers
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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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- B32B2260/00—Layered product comprising an impregnated, embedded, or bonded layer wherein the layer comprises an impregnation, embedding, or binder material
- B32B2260/02—Composition of the impregnated, bonded or embedded layer
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- B32B2260/00—Layered product comprising an impregnated, embedded, or bonded layer wherein the layer comprises an impregnation, embedding, or binder material
- B32B2260/04—Impregnation, embedding, or binder material
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/50—Properties of the layers or laminate having particular mechanical properties
- B32B2307/54—Yield strength; Tensile strength
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B32B2309/00—Parameters for the laminating or treatment process; Apparatus details
- B32B2309/08—Dimensions, e.g. volume
- B32B2309/10—Dimensions, e.g. volume linear, e.g. length, distance, width
- B32B2309/105—Thickness
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- B32B2571/00—Protective equipment
- B32B2571/02—Protective equipment defensive, e.g. armour plates or anti-ballistic clothing
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
- B32B27/306—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising vinyl acetate or vinyl alcohol (co)polymers
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- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
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- B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
- B32B37/14—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers
Landscapes
- Engineering & Computer Science (AREA)
- General Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Ceramic Engineering (AREA)
- Textile Engineering (AREA)
- Physics & Mathematics (AREA)
- Fluid Mechanics (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
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Abstract
本发明涉及用于生产防弹制品的复合物，所述复合物包含至少两个包含高拉伸强度纤维的织物层和至少一层聚乙烯醇缩丁醛箔，所述聚乙烯醇缩丁醛箔显示出30-70μm的厚度。本发明的另一目的是由该复合物得到的防弹制品。
Description
本发明涉及用于生产防弹制品的复合物，所述复合物包含至少两个织物层和在至少两个织物层之间的至少一个聚乙烯醇缩丁醛层。本发明还涉及生产这种复合物的方法，和由这类复合物得到的防弹制品如头盔或板。
用于生产防弹制品且包含热塑性聚合材料中间层的复合物是现有技术已知的。
U.S.2010/0307629公开了耐穿孔和渗透的织物结构的连续生产方法，其中中间层置于上层与下层之间，然后该组件通过热或冷压连接在一起。U.S.2010/0307629的中间层由选自包含至少如下的组的聚合物构成：聚氨酯、聚乙烯、聚丙烯、聚酯、苯乙烯丁二烯、聚碳酸酯、苯酚或聚乙烯醇缩丁醛、聚异丁烯、聚异丁烯、天然或合成橡胶、硅聚合物等。
现有技术复合物的缺点是用于中间层的聚合物需要在较高温度下交联和/或不适于长期储存。特别地，如果需要运输中间层所需现有技术聚合物，则该运输必须在低温下进行以避免不想要的早期交联。如果中间层包含苯酚，则储存和运输期间的温度必须不超过-20℃。另外，用于中间层的聚合物不容易均匀地施涂。这些条件提高生产成本并使生产方法复杂。另外，由于稍微长的交联时间，聚合物在生产过程期间可能流走，且可能污染模具和周围区域。
最后但并非最不重要的，对于现有技术中间层，需要溶剂，这样使复合物更昂贵且更难以处理，即从环境观点看。
在US 2009/0297794中，公开了具有基底层和薄膜层的层压物。这种层压物用于日用制品如雨衣、鞋子或伞。薄膜层由聚乙烯醇缩丁醛构成且置于制品的外部。在实施方案中，薄膜层都不置于两个织物层之间。除此之外，该文件中没有公开高强度纤维的使用。
文件DE 10 2009 037 171也公开了由箔和板构成的制品。公开的制品用于航天领域。在所有实施方案中，箔置于板的外表面上，以防止板被鸟等撞击。箔的置换因此不是想要和有用的。除此之外，箔显示出至少100μm的厚度。
因此，本发明的目的是提供至少减少现有技术的缺点的复合物。
该目的通过用于生产防弹制品的复合物实现，所述复合物包含至少两个织物层和在至少两个织物层之间的至少一个聚乙烯醇缩丁醛层，所述织物层包含根据ASTM D-885拉伸强度为至少1100MPa的高拉伸强度纤维，其中聚乙烯醇缩丁醛层为箔并显示出30-70μm，甚至更优选30-50μm的厚度。
令人惊讶的是，尽管应用非常薄的聚乙烯醇缩丁醛层，由本发明复合物得到的制品的防弹性能至少与现有技术的那些在相同水平上。这特别对头盔而言具有优点，因为总重量至少保持在相同水平上。此外，由于聚乙烯醇缩丁醛作为箔应用，它的处理、储存和应用是容易且方便的，且不涉及溶剂。此外，生产本发明防弹制品不需要苯酚树脂和交联剂或硬化剂。
本领域技术人员熟悉通过将聚乙烯醇用优选脂族醛，尤其是正丁醛和/或乙醛酸催化缩醛化而制备聚乙烯醇缩丁醛。EP 0 950 696(其相当于DE19 816 722 A1)中公开的聚乙烯醇缩丁醛和/或它们的制备方法是特别合适的。在文件EP 0 950 696，实施例1中，聚乙烯醇缩丁醛以以下方式公开：将540g的具有360的聚合度和88摩尔％的水解度的聚乙烯醇溶于6600ml水中。在加入269g丁醛以后，反应在0℃下在剂量加入1090ml的20％盐酸下开始。当盐酸剂量完成时，将反应混合物经3小时加热至30℃并在该温度下保持另外2小时。将沉淀的颗粒滤出并用足够的水洗涤。为了易于接受地中和碱化，将悬浮产物用10％氢氧化钠处理并再次轻微加热。通过用水洗涤除去过量碱。然后将产物干燥。所得聚乙烯醇缩丁醛显示出13.5％的残余乙酸盐含量和18摩尔％的残余聚乙烯醇含量。根据(DIN53015)的粘度为在10％乙醇溶液中13.75mPas，在10％乙酸乙酯溶液中8.52mPas。
术语“聚乙烯醇缩丁醛”指将聚乙烯醇用一种或多种脂族醛缩醛化的任何产物。
优选，本发明所用聚乙烯醇缩丁醛具有1-20重量％，特别是1-10重量％的聚乙酸乙烯酯含量和10-35重量％，优选11-27重量％，特别是16-21重量％的聚乙烯醇含量。
聚乙烯醇缩丁醛的聚合度Pw优选为100-1000，特别优选100-800，特别是100-500。
合适的聚乙烯醇缩丁醛具有足够高的分子量以通过挤出或者通过溶剂流延方法形成自持膜。合适的分子量由粘度表示，为5-3000mPas，优选5-2500mPas，特别是5-2000mPas，尤其是20-200mPas。
合适的聚乙烯醇缩丁醛可基于商业，例如由Kuraray Europe GmbH的品级Mowital B 16 H、Mowital B 75 H或Pioloform BL 16得到。
本发明中所用聚乙烯醇缩丁醛箔(在本发明过程中也称为“膜”)通过例如用吹塑薄膜挤出生产线挤出或者优选通过使用平膜模头和冷却辊流延加压方法生产，因为收缩值则是非常低的。挤出生产线的加工温度为200-250℃，优选240-250℃。将平膜模头加热至250-280℃，优选260-275℃。挤出螺杆和熔融泵的旋转涉及压力建立。通常，熔融泵之后的压力为180-200巴。挤出生产线的螺杆速度为25-50rpm且熔融泵的速度为10-25rpm。
膜厚度贡献于流延膜生产线的上卷(up-take)速度且必须布置直至实现所需膜厚度。
这类膜或箔也以10-100μm的膜厚度作为Mowital BF由KurarayEurope GmbH市购。
本发明所用PVB箔可包含至多2重量％，优选小于1重量％添加剂，尤其是小于0.5重量％添加剂。在优选实施方案中，箔由“纯”聚乙烯醇缩丁醛构成，例如包含0重量％添加剂。
作为添加剂，可使用无机填料如颜料、染料或粘土、UV稳定剂、氧化稳定剂、增塑剂或水。
常用的这类增塑剂为三甘醇或四甘醇的脂族二酯，尤其是三甘醇-双-2-乙基己酸酯(3G8)。还使用具有脂族或脂环族酯结构部分的己二酸二烷基酯，例如己二酸二己酯、癸二酸二烷基酯、三有机磷酸酯、三有机亚磷酸酯或邻苯二甲酸酯基增塑剂如邻苯二甲酸苄基丁酯或其氢化产物如二异壬基环己基二羧酸(DINCH)。
合适的UV稳定剂可以为基于胺的，例如四甲基哌啶。次于伯、仲和叔线性胺，称为‘HALS’产品的位阻胺可用作与多核苯酚化合物相关的助稳定剂。
在本发明上下文中，术语“复合物”包括所谓的“预浸料”，其为关于“预浸渍”纤维的术语。这些通常采用编织的形式或者为单向的，但也可以为经线针织或多轴织物。更通常地，它们为纤维网络的形式。它们已包含在生产期间用于将它们结合在一起和与其它组分结合的箔。因此，例如将聚乙烯醇缩丁醛箔层压在织物层的一面或两面上以产生预浸料。这些预浸料中的两种或更多种可置于彼此上面，然后通过热和/或压力处理。
在本发明一个实施方案中，复合物包含至少两个(或更多)织物层和在织物层之间的至少一层聚乙烯醇缩丁醛箔作为中间层。因此，织物层不被箔预浸渍，而是相互分开地组装，然后可随后通过热和/或压力处理。
在本发明的一个实施方案中，复合物的织物层或至少一个织物层为机织物层。
机织物层优选具有平纹、缎纹、篮形和/或斜纹组织。如果使用多于一个机织物层，则机织物层具有相同或不同的编织方式。一个机织物层还可具有多于一个编织方式，其中该机织物层可与具有多于一个编织方式的机织物层或者与具有一种编织方式的一个或多个机织物层组合。在一个实施方案中，至少一个机织物层由具有1000长丝的1680芳族聚酰胺纱线构成。机织物优选具有2000的经/纬线关系且为篮形编织的(2×2)。经纬线/cm为127且面密度为410g/m2。该织物以名称CT 736由Teijin Aramid GmbH出售。也可使用其它织物，例如Teijin Aramid的T750(3360分特)。
在另一优选实施方案中，织物层或织物层中至少一层为单向纤维层。就本文而言，术语“纤维”定义为在垂直于其长度的横截面上具有高长度:宽度比的相对挠性、宏观均匀体。术语“纤维”还包括带形式。纤维横截面可以为任何形状，但通常为圆形的。此处，术语“长丝”与术语“纤维”互换地使用。纤维可以为任何长度。纤维可以为连续长丝，其为通常延伸一米或长得多的长丝。长丝通常作为复丝的一部分以连续形式纺丝，卷绕在线轴上，然后在将所需量放在线轴上以后切割。可将长丝切成具有0.64-12.7cm的长度的短纤维。短纤维可以为直线的(即非卷曲)或以1.4-7.1卷边/cm的卷曲(或重复弯曲)频率卷曲以沿着其长度具有齿形卷边。术语“纱线”为关于织物纤维、长丝或适于针织、编织或缠结以形成织物层的形式的材料的连续丝束的通称。
在单向纤维层中，层中的所有纤维以相同方向排列，其中纤维优选相互近似平行地排列。单向纤维层可具有粘合线和/或粘合聚乙烯醇缩丁醛箔，其将单向纤维连接在一层中。单向纤维层也可具有粘合线，其将多于一个单向纤维层相互连接。如果使用多于一个单向纤维层，各层中的纤维可以相对于后继单向纤维层以一定的角排列。这意指第一单向纤维层以0°取向排列；后继单向纤维层以不同于0°取向，例如以±45°或90°取向排列。后继层中的纤维也可相互平行取向，但相互偏移。
在一个优选实施方案中，多个织物层用于复合物，其中可使用仅机织物层、仅单向纤维层或单向纤维层和机织物层的组合。
优选至少两个织物层中的至少一个织物层包含芳族聚酰胺纤维和/或聚乙烯纤维。尤其优选至少一个织物层包含聚(对苯二甲酰对苯二胺)纤维和/或超高聚乙烯带。还优选至少一个织物层包含芳族聚酰胺的共聚物。
优选使用多个芳族聚酰胺机织物层和多层单向纤维层的组合，其中单向纤维层由带构成，其中带由超高分子量聚乙烯构成。由这类带构成的单向纤维层的结构描述于国际申请PCT/NL2006/000179和EP 1 908 586中，通过引用插入其内容。文件EP 1 908 586公开了：
生产由至少两个聚合物带单层构成的层压物的方法，
聚合物带具有至少200MPa的拉伸强度，
所述方法包括步骤：
·通过将聚合物带预拉伸，随后将聚合物带以单向平行方式置于张力下而形成聚合物带的第一单层，
·以与形成第一单层相同的方式在第一单层上形成至少第二单层，其中
·以这种方式将至少两个聚合物带单层堆叠以致聚合物带的方向在每一单层中是相同的且各单层的聚合物带偏离该单层上面或下面的相邻单层的带，
·将因此堆叠的聚合物带单层加固以得到层压物。
优选将聚乙烯醇缩丁醛箔应用于防弹制品的两个连续织物层之间。优选箔应用于织物层的主延伸面积上。在优选实施方案中，防弹制品由第一织物层、在第一织物层上的箔和在第一织物层的箔上面的第二织物层形成，其中可接着应用具有箔的另一织物层。
箔可位于织物层之间或者例如通过层压固定在该层上。
本发明还涉及用于生产防弹制品的复合物，所述复合物包含至少一个织物层和至少一个聚乙烯醇缩丁醛层，所述织物层包含根据ASTM D-885拉伸强度为至少1100MPa的高拉伸强度纤维，其中聚乙烯醇缩丁醛层为箔并显示出30-70μm的厚度。
包含至少两个织物层的复合物的所有优选实施方案对包含至少一层的复合物而言也是合适和优选的。尤其是添加剂的量，机织或单向层作为织物层，将织物层在一面或两面上用箔预浸渍，且用于织物层的纤维种类优选如同关于包含两个织物层的复合物的描述。
本发明还涉及生产适于生产防弹制品的复合物的方法，所述方法包括如下步骤：
i)提供第一织物层；其包含根据ASTM D-885拉伸强度为至少1100MPa的高拉伸强度纤维；
ii)将聚乙烯醇缩丁醛层排列在第一织物层上；
iii)将包含具有根据ASTM D-885拉伸强度为至少1100MPa的高拉伸强度纤维的第二织物层排列在聚乙烯醇缩丁醛层上；
iv)任选用其它织物层(具有或不具有高强度纤维)和聚乙烯醇缩丁醛层重复步骤ii)和iii)，
其中聚乙烯醇缩丁醛层为显示出30-70μm，更优选30-50μm的厚度的箔。
此外，主张生产适于生产防弹制品的复合物的方法，所述方法包括以下步骤：
i)提供包含根据ASTM D-885拉伸强度为至少1100MPa的高拉伸强度纤维的第一织物层，所述第一织物层在其一面或两面上用聚乙烯醇缩丁醛层预浸渍，
ii)任选将包含根据ASTM D-885拉伸强度为至少1100MPa的高拉伸强度纤维的其它织物层排列在第一织物层上，所述其它织物层任选在一面或两面上用聚乙烯醇缩丁醛层预浸渍，
其中聚乙烯醇缩丁醛层为显示出30-70μm，更优选30-50μm的厚度的箔。
优选将复合物通过温度和压力，例如通过压延进一步处理以将聚乙烯醇缩丁醛箔熔融。
通过该方法制备的复合物的特征在于其织物层中的至少一层包含如上所述芳族聚酰胺纤维和/或聚乙烯纤维。
本发明还涉及由如上所述复合物得到的防弹制品如头盔或板。
板可用于软防弹或硬防弹中。
如果防弹制品是头盔，则头盔优选包含由芳族聚酰胺构成的层和由相同或不同的合适聚合物如聚乙烯构成的其它层。在这种情况下，芳族聚酰胺部分和/或聚乙烯部分由织物层构成，其中至少一个，优选多个织物层形成该部分。芳族聚酰胺部分优选包含由聚(对苯二甲酰对苯二胺)纤维构成的织物层且聚乙烯部分优选包含由超高分子聚乙烯构成的带层。在优选实施方案中，头盔包含(从使用者的头部开始)由芳族聚酰胺机织物层构成的第一部分，由超高分子聚乙烯带构成的第二部分和由芳族聚酰胺机织物层的第三部分，其中所有三个部分彼此连接在一个单一外壳上。这意指聚乙烯部分夹在两个芳族聚酰胺部分之间。
如果聚乙烯层的熔点容许，则层之间的连接可通过简单地将聚乙烯醇缩丁醛箔熔融而实现。在优选实施方案中，上述聚乙烯醇缩丁醛箔排列在芳族聚酰胺部分与聚乙烯部分之间。在另一优选实施方案中，上述聚乙烯醇缩丁醛箔应用于形成芳族聚酰胺部分的织物层之间和芳族聚酰胺本身之间。在优选实施方案中，聚乙烯部分不含所述聚乙烯醇缩丁醛箔且仅芳族聚酰胺部分包含聚乙烯醇缩丁醛箔。
聚乙烯醇缩丁醛箔容许不具有任何溶剂的膜生产，因此无排放。箔和相应复合物中没有留下残留的苯酚和甲醛组分。膜的储存与包含苯酚的标准体系相比是便宜的。聚乙烯醇缩丁醛复合物容许简单、划算的运输条件和在室温下基本无限的可储存性。
通过以下实施例进一步阐明本发明。
a)聚乙酸乙烯酯含量的测定
聚乙酸乙烯酯含量应当理解意指由将1g物质皂化所需氢氧化钾溶液的消耗量产生的乙酰基的比例，以重量％表示。
测定方法(基于EN ISO 3681)：
将约2g待研究物质精确地称重出1mg放入500ml圆底烧瓶中并在回流下溶于90ml乙醇和10ml苄醇中。在冷却以后，相对于酚酞，将溶液用0.01N NaOH中和。随后加入25.0ml的0.1N KOH并在回流下进行加热1.5小时。使烧瓶在密闭状态下冷却并将过量液体用0.1N盐酸相对于酚酞作为指示剂滴定直至得到永久褪色。以相同方式处理对照物。PV乙酸酯含量如下计算：以[％]表示的PV乙酸酯含量＝(b-a)*86/E，其中a＝以ml表示的就试样而言0.1N KOH的消耗量，b＝以ml表示的就对照而言0.1N KOH的消耗量，且E＝以g表示的干状态下称重的待检查物质的量。
b)聚乙烯醇基团含量的测定
聚乙烯醇基团含量(聚乙烯醇含量)为可通过随后用乙酸酐乙酰化而检测到的羟基的含量。
测定方法(基于DIN 53240)：
将约1g Mowital精确地称重至1mg放入300ml锥形瓶中，加入10.0ml乙酸酐吡啶混合物(23:77v/v)并将这加热15-20小时至50℃。在冷却以后，加入17ml的1,2-二氯乙烷并简短地旋转。随后随着搅拌加入8ml水，将烧瓶用塞子密封并进行搅拌10分钟。将烧瓶的颈和塞子用50ml软化水冲洗，用5ml正丁醇覆盖并将游离乙酸用1N苛性钠溶液相对于酚酞滴定。以相同方式处理对照试样。聚乙烯醇含量如下计算：聚乙烯醇含量[％]＝(b-a)*440/E，其中a＝以ml表示的就试样而言1N NaOH的消耗量，b＝以ml表示的就对照试样而言1N NaOH的消耗量，且E＝以g表示的干状态下称重的待检查物质的量。
c)粘度的测定
所用聚乙烯醇缩乙醛的粘度根据DIN 53015在Hoeppler粘度计中在20℃下以在包含5重量％水的乙醇中的10重量％溶液测定。
d)聚合度Pw的测定
聚合度Pw可更容易地关于聚乙烯醇测定，且在缩醛化期间不改变。使用聚乙烯醇缩丁醛作为一个实例，聚合度Pw根据下式计算：
Mw通过关于再乙酰化试样的凝胶渗透色谱法(GPC)与静态光散射(绝对法)组合进行。Mw值的准确度测定为+15％。
水解度(DH[摩尔％])根据下式计算：
酯值(EV)如下并使用下式测定：
其中a＝0.1N KOH的消耗量[ml]，b＝关于对照试样的0.1N KOH消耗量[ml]，E＝称重的聚乙烯醇的准确量。
将约1g聚乙烯醇引入250ml圆底烧瓶中，加入70ml蒸馏水和30ml中和醇，并在回流下加热直至聚乙烯醇完全溶解。在冷却以后，进行相对于酚酞用0.1N KOH进行滴定直至中性。当中和完成时，加入50ml的0.1NKOH并将该混合物在回流下加热1小时。将过量液体相对于酚酞作为指示剂用热0.1N HCl反滴定直至溶液的颜色不再回复。同时用对照试样进行试验。
实施例
实施例涉及由上述复合物得到的头盔。
头盔外壳包含18层芳族聚酰胺机织物层。由Kuraray Europe GmbH得到的具有50μm厚度的聚乙烯醇缩丁醛膜LP BF7-50置于相邻芳族聚酰胺层之间。为对比，生产类似的头盔，其中芳族聚酰胺层而是通过苯酚聚乙烯醇缩丁醛树脂连接。头盔在一个单一模制步骤中生产。
LP BF7-50由具有18-21重量％的聚乙烯醇含量、1-2重量％的聚乙酸乙烯酯含量且具有60-100mPas的粘度的聚乙烯醇缩丁醛组成。膜不包含任何添加剂。
头盔外壳具有1086g的重量。
头盔的防弹性能，即v50值和创伤值根据German Bundeswehr的“Technische Lieferbedingung Gefechtshelm TL8470-0008，日期03.12.03”用1.1g破片模拟弹(FSP)测试。
证明在包含本发明复合物的头盔上测量的v50值(680m/s)比用现有技术材料得到的头盔更高。本发明头盔还显示出相当更低的创伤值，其比用现有技术头盔得到的那些低约10mm(用9mm DM41弹药)。
Claims (14)
1.用于生产防弹制品的复合物，所述复合物包含至少两个织物层和在至少两个织物层之间的至少一个聚乙烯醇缩丁醛层，所述织物层包含根据ASTM D-885拉伸强度为至少1100MPa的高拉伸强度纤维，其中聚乙烯醇缩丁醛层为箔并显示出30-70μm的厚度。
2.根据权利要求1的复合物，其特征在于聚乙烯醇缩丁醛箔显示出30-50μm的厚度。
3.根据权利要求1或2的复合物，其特征在于聚乙烯醇缩丁醛箔包含小于2重量％添加剂。
4.根据前述权利要求中任一项的复合物，其特征在于至少一个织物层为机织物层。
5.根据前述权利要求1-3中任一项的复合物，其特征在于至少一个织物层为单向纤维层。
6.根据前述权利要求1-5中任一项的复合物，其特征在于将至少一个织物层在一面或两面上用聚乙烯醇缩丁醛箔预浸渍。
7.根据前述权利要求中任一项的复合物，其特征在于至少一个织物层包含芳族聚酰胺纤维和/或聚乙烯纤维。
8.生产适于生产防弹制品的复合物的方法，其包括如下步骤：
i)提供第一织物层，其包含根据ASTM D-885拉伸强度为至少1100MPa的高拉伸强度纤维；
ii)将聚乙烯醇缩丁醛层排列在第一织物层上；
iii)将包含具有根据ASTM D-885拉伸强度为至少1100MPa的高拉伸强度纤维的第二织物层排列在聚乙烯醇缩丁醛层上；
iv)任选用其它织物层和聚乙烯醇缩丁醛层重复步骤ii)和iii)，
其特征在于聚乙烯醇缩丁醛层为显示出30-70μm的厚度的箔。
9.生产适于生产防弹制品的复合物的方法，其包括如下步骤：
i)提供包含根据ASTM D-885拉伸强度为至少1100MPa的高拉伸强度纤维的第一织物层，其中所述第一织物层在其一面或两面上用聚乙烯醇缩丁醛层预浸渍；
ii)将包含根据ASTM D-885拉伸强度为至少1100MPa的高拉伸强度纤维的其它织物层排列在第一织物层上，其中所述其它织物层任选在一面或两面上用聚乙烯醇缩丁醛层预浸渍，
其特征在于聚乙烯醇缩丁醛层为显示出30-70μm，更优选30-50μm的厚度的箔。
10.根据权利要求8或9的方法，其特征在于将复合物进一步通过温度和压力，例如通过压延处理以将聚乙烯醇缩丁醛箔熔融。
11.根据权利要求8-9的方法，其特征在于聚乙烯醇缩丁醛箔包含小于2重量％添加剂。
12.根据权利要求8-11的方法，其特征在于至少一个织物层包含芳族聚酰胺纤维和/或聚乙烯纤维。
13.由根据前述权利要求中任一项的复合物得到的防弹制品如头盔或板。
14.用于生产防弹制品的复合物，所述复合物包含至少一个织物层和至少一个聚乙烯醇缩丁醛层，所述织物层包含根据ASTM D-885拉伸强度为至少1100MPa的高拉伸强度纤维，其中聚乙烯醇缩丁醛层为箔并显示出30-70μm的厚度。
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| WO2016116774A1 (en) * | 2015-01-21 | 2016-07-28 | Umm Al-Qura University | Ballistic resistant article and method of producing same |
| US10358821B2 (en) * | 2015-03-02 | 2019-07-23 | The Boeing Company | Thermoplastic truss structure for use in wing and rotor blade structures and methods for manufacture |
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| CA2864943C (en) | 2021-12-14 |
| MX346492B (es) | 2017-03-21 |
| WO2013124147A1 (en) | 2013-08-29 |
| AU2013224291B2 (en) | 2016-01-07 |
| EP2817144A1 (en) | 2014-12-31 |
| IL233758B (en) | 2018-12-31 |
| MY170222A (en) | 2019-07-10 |
| BR112014020357B1 (pt) | 2021-03-02 |
| EP2817144B1 (en) | 2016-04-06 |
| IL233758A0 (en) | 2014-09-30 |
| KR20140133524A (ko) | 2014-11-19 |
| JP2015514952A (ja) | 2015-05-21 |
| ZA201405725B (en) | 2015-04-29 |
| MX2014009988A (es) | 2014-09-16 |
| RU2014138061A (ru) | 2016-04-10 |
| CA2864943A1 (en) | 2013-08-29 |
| US20160016393A1 (en) | 2016-01-21 |
| RU2631813C2 (ru) | 2017-09-26 |
| AU2013224291A1 (en) | 2014-08-14 |
| JP6165181B2 (ja) | 2017-07-19 |
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