JP2008504142A - Method for producing adhesive mixture and impact composite material using the mixture - Google Patents

Abstract

  The present invention relates to an adhesive formulation used in a composite laminate structure that improves impact resistance that limits the penetration of bullets fired from handguns and the like. The composite laminate structure contains a plurality of impact base layers (for example, a polyaramid layer or an olefin layer) and an impact-absorbing adhesive resin or an adhesive composition according to the present invention. The adhesive formulation contains the following components: an impact-absorbing adhesive resin having a melt index of 1-100, an olefin-acrylate copolymer or olefin-methacrylate copolymer having a melt index of about 0.5 to about 100, or An olefin-vinyl acetate copolymer having a melt index of about 0.5 to about 350, an acidic rosin having an acid number of about 20 to 200, a high melting point oxidized wax having a melting point of about 80 to 120 ° C, and about 55 to 90 ° C. A low melting point wax having a melting point of The invention also relates to armor, shields and helmets made from the composite laminate structure according to the invention.

Description

  The present invention relates to an impact-absorbing adhesive resin. The impact resistance of the substrate is improved by applying the adhesive resin onto a ballistic substrate or using the adhesive resin to form a composite of the impact substrate. The present invention also relates to a composite laminar structure having an impact base material and an impact-absorbing adhesive resin.

  The present invention is directed to the provision of impact protection products, for example, impact protection (armor) for combat soldiers. The present invention relates to impact substrates, such as polyaramid fibers and / or elongated olefin fibers, or these fiber layers molded into a composite laminate structure, which exhibit improved impact resistance, and these The present invention also relates to an adhesive resin exhibiting impact resistance and / or fracture resistance, which is used for laminating a base material for impact. The composite laminate structure may be subjected to a wide range of applications (eg, protective armor and helmet, tank shields and infantry armor, helmets and shields used by ship crew).

  The shock-absorbing adhesive resin used to form an impact-resistant substrate into a composite laminate structure is a metal panel or ceramic panel used as an impact base material or automobile or aircraft, for example, as a door panel or roof panel. It may be used to increase the impact resistance of these panels by bonding. The present invention also relates to a method for manufacturing a composite laminated structure, an armor, a helmet, and the like, and a method for improving the impact resistance of metal panels and ceramic panels for automobiles and aircraft.

  A problem that has long been unsolved in the related field is to provide a helmet that provides the necessary protection (i.e., impact resistance) against the projectile and is comfortable for combat soldiers. Such a helmet should provide maximum protection to the wearer, but this requirement is a headgear that is not overly heavy and fits heads of various sizes, hindering the wearer's activity. In addition, it must be achieved in a headgear that is relatively comfortable for a long time. At present, helmets must exhibit minimal resistance to bullets (i.e., resistance to no bullet penetration and depth of penetration not exceeding 44 mm).

  Currently, helmets are manufactured from woven fibers of polyaramid [eg, Kevlar®] and typically have 10-60 woven or non-woven fiber layers. Adjacent layers of these layers are alternately stacked via an adhesive layer that bonds the adjacent layers. The adhesive layer is present inside the thin outer shell of the helmet (eg, a polyester, poxy or polyvinyl butyral prepreg thermoset (phenolic) shell or a polyvinyl ester prepreg thermoset shell). The number of fiber layers used in the production of protective helmets is limited by the weight that is comfortable for combat soldiers (currently about 3 pounds).

  Another problem in the prior art is that conventional Kevlar processing is costly and time intensive. For example, a Kevlar cloth thermosetting prepreg of the prior art requires a curing time of about 30 minutes to form an impact resistant composite. As a result, due to the curing time, the production speed becomes slow and the production cost becomes high.

  Thus, a composite laminate structure that is lightweight, exhibits excellent resistance to bullet impact, and can be easily manufactured (eg, can be manufactured with a relatively low heat and pressure needling and / or a relatively short manufacturing time). It is requested to provide a body.

  In addition, there is a need to provide improved composite laminate structures (eg, protective helmets that are more resistant to bullet impacts than currently available protective helmets of the same weight or heavier). . This type of helmet should meet or exceed the requirements for weight and resistance to bullet impact required for protective helmets.

  The present invention has been made to solve the above-described problems in the field.

  In the present invention, the impact-absorbing adhesive resin is applied to the impact substrate by applying the impact-absorbing adhesive resin composition on the impact substrate or forming a composite material thereof. It is based on the discovery of improving impact properties.

  One aspect of the present invention is a specific type of adhesive formulation (eg, a hot melt adhesive formulation) that includes an impact substrate (eg, an adjacent impact substrate), such as It is directed to an adhesive formulation that is used to adhere a polyaramid substrate layer. The resulting composite laminate structure exhibits significantly improved resistance to bullet impact. Unlike a structure that must be cured using a thermosetting resin, a polyaramid composite laminate structure can be molded thermoplastically by male / female molding methods (eg, armor, helmet or Other desired protective shaped articles can be manufactured). Alternatively, a composite laminate structure (eg, a polyaramid composite laminate structure) joins ceramic panels (eg, an automobile striking surface such as a Humvee or an aircraft striking surface such as a helicopter or fixed wing). Can be applied to the metal panels used to improve the impact resistance, for example by breaking momentum and dissipation momentum

In one embodiment, the polyaramid or stretched / elongated olefin layer can be formed from plain woven or non-woven polyaramid and / or olefin fibers bonded with a hot melt adhesive formulation according to the present invention. Hot melt adhesive formulations are prepared from the following five components:
(I) a copolymer or terpolymer of acrylic acid, methacrylic acid or maleic anhydride and an olefin having a melt index of about 1 to 100;
(Ii) an acrylate-olefin copolymer or methacrylate-olefin copolymer having a low melt index,
(Iii) an acidic rosin having an acid value of about 20 to 200,
(Iv) a high melting point olefin oxide wax, and (v) a long chain fatty acid wax having a low melting point.
Additional components, such as antioxidants, UV inhibitors, flame retardants and reinforcing fillers known in the art may be added. Generally, the content of these additional components is about 0.1 to 20 parts by weight.

In another embodiment, the composite laminate structure comprises at least two impact substrates bonded with an adhesive formulation. The adhesive formulation is prepared from the following five components:
(I) about 20 to 90% by weight of an impact-absorbing adhesive resin having a melt index of 1 to 100;
(Ii) about 3 to 70% by weight of an olefin-acrylate copolymer or olefin-methacrylate copolymer having a melt index of about 0.5 to about 100 or an olefin-vinyl acetate copolymer having a melt index of about 0.5 to 350;
(Iii) about 3-40% by weight of acidic rosin having an acid number of about 20-200,
(Iv) about 1-20% by weight of a high melting point oxidized wax having a melting point of about 80-120 ° C. and (v) about 1-20% by weight of a low melting point wax having a melting point of about 55-90 ° C.

In yet another aspect, polyaramid fabrics or linear stretched olefin fabrics having olefin or polyaramid fibers or fiber layers are bonded together by an adhesive formulation. The adhesive formulation is prepared from the following five components:
(I) about 20 to 90% by weight of an impact-absorbing adhesive resin having a melt index of 1 to 100;
(Ii) about 3 to 70% by weight of an olefin-acrylate copolymer or olefin-methacrylate copolymer having a melt index of about 0.5 to about 100;
(Iii) about 3-40% by weight of acidic rosin having an acid number of about 20-200,
(Iv) about 1-20% by weight of a high melting point oxidized wax having a melting point of about 80-120 ° C. and (v) about 1-20% by weight of a low melting point wax having a melting point of about 55-90 ° C.

In another embodiment, it is prepared from the following five components:
(I) about 20 to 90% by weight of an impact-absorbing adhesive resin having a melt index of 1 to 100;
(Ii) about 3 to 70% by weight of an olefin-acrylate copolymer or olefin-methacrylate copolymer having a melt index of about 0.5 to about 100;
(Iii) about 3-40% by weight of acidic rosin having an acid number of about 20-200,
(Iv) about 1-20% by weight of a high melting point oxidized wax having a melting point of about 80-120 ° C. and (v) about 1-20% by weight of a low melting point wax having a melting point of about 55-90 ° C.

  In another aspect, the composite laminate structure comprises at least two impact substrates integrated as a composite laminate structure with an impact-absorbing adhesive resin having a melt index of about 1-100.

  In yet another embodiment, the laminated structure has an impact-absorbing adhesive resin (melt index: about 1 to 100) coated on a release sheet.

In still another embodiment, the laminated structure has an adhesive resin coated on a release sheet. The adhesive resin contains the following five components:
(I) about 20 to 90% by weight of an impact-absorbing adhesive resin having a melt index of 1 to 100;
(Ii) about 3 to 70% by weight of an olefin-acrylate copolymer or olefin-methacrylate copolymer having a melt index of about 0.5 to about 100 or an olefin-vinyl acetate copolymer having a melt index of about 0.5 to 350;
(Iii) about 3-40% by weight of acidic rosin having an acid number of about 20-200,
(Iv) about 1-20% by weight of a high melting point oxidized wax having a melting point of about 80-120 ° C. and (v) about 1-20% by weight of a low melting point wax having a melting point of about 55-90 ° C.

  In yet another aspect, a method for producing a composite laminate structure is provided that includes a step of applying an impact-absorbing adhesive resin having a melt index of 1 to 100 onto an impact base material.

  The foregoing general description and the following detailed description in the present specification illustrate the present invention in an illustrative manner, and the invention described in the claims is described in further detail below.

  Several aspects of the invention are illustrated in the accompanying drawings. In these drawings, the same numbers indicate similar elements.

1A and 1B are schematic diagrams illustrating an embodiment for producing a composite structure using a hot melt adhesive formulation according to an embodiment of the present invention.
FIG. 2 is a flowchart showing a manufacturing process of a composite laminated structure according to another aspect of the present invention.
FIG. 3 shows a modulated differential scanning calorimetry (DSC) chart of a hot melt adhesive formulation according to an embodiment of the present invention.
FIG. 4 shows the viscosity diagram of a hot melt adhesive formulation according to an example of the present invention.

  In the present invention, the impact-absorbing adhesive resin is used to improve the impact resistance of the impact base material by forming a composite laminate structure using the resin. The impact substrate can be a woven or non-woven fabric or a fiber material, for example polyaramid fibers comprising organic filaments made of aramid fibers (eg aromatic polyamide), for example “Kevlar” aramid, “Heracron” aramid or “Twaron” (Twaron) ”with aramid. Examples of this type of substrate include poly (m-xylylene adipamide), poly (p-xylylene sebacamide), poly (2,2,2-trimethyl-hexamethylene terephthalamide), poly (Piperazine sebacamide), poly (metaphenylene isophthalamide) ("Nomex"), poly (p-phenylene terephthalamide) ("Kevlar") and drawn / slendered fibers such as olefin fibers ( “Spectra” (registered trademark) and the like are included.

  This type of substrate also includes “ZYLON” (registered trademark), which is composed of a rigid rod chain molecule of poly (p-phenylene-2,6-benzobisoxazole) (PBO). Other suitable impact substrates known in the art may be used. Furthermore, these base materials may be used in combination, and this type of impact base material can be processed in various forms. For example, these substrates may be woven or non-woven fabrics or combinations thereof. Non-woven base materials such as metals, ceramics and other composite materials can also be used.

  The polyaramid fiber used to form the cloth layer may be coated with a metal. Examples of this type of fiber include copper-coated fibers disclosed in US Pat. Nos. 5,935,706 and 6,045,680. The disclosure of this patent document also forms part of the present specification. The cloth layer is formed from fibers comprising yarns of about 1000 to about 6000 denier (preferably 1500 to about 4000 denier). Typical yarn density is about 10 to 150 yarns / inch.

  The textures of the exemplified Kevlar materials are plain weave, satin weave, or similar or non-woven random or linear fibers that exhibit a high followability to complex forms. However, plain weaves are very suitable for forming. An exemplary thickness of the cloth material is about 0.006 to about 0.060 inches. Composite fiber fabrics or cloths are available from a number of manufacturers, including, for example, the following manufacturers: ICI fiber light (Tuxon, Arizona), Hexel Corporation (Dublin), BGF Industries Inc. (Greensboro, North Carolina), Warbic Mills (New Ipswich, New Hampshire), Lincoln Fabrics (Geneva, Alabama, Burday, Cambridge, Ontario Canada).

  Moreover, you may manufacture the composite laminated structure by this invention using a Kevlar fabric or a Spectra fabric. For example, a material useful in the present invention includes “Kevlar 29” commercially available from Hexel-Schwebel Corporation as being in the category of “high-grade composite fabric”. The “Kevlar 29” used has a thickness of 0.020 inches, a weight of about 12 ounces / square yard, a 15 × 15 implant and a fineness of about 3000 denier. Other useful polyaramid fabrics include "Twaron high tenacity", "Kevlar 129 fabric" and "Kevlar 9-5000 fabric" are 5H satin weaves, 13.0 Mill thickness, warp and weft thread type K49 / 2160DN, 17x17 thread count, 9.00 ounces / square yard weight, and 920 lb / in (warp) and 970 lb / in (weft) Has a cutting strength of.

The shock-absorbing adhesive resin is an acidic resin having an intermediate melt index and low modulus. Preferably, the shock absorbing resin has a melt index of about 1 to about 100 (preferably about 15-40, more preferably about 4-25). The shock absorbing adhesive resin preferably has a flexural modulus of about 2000 to 8000 psi (more preferably about 2500 to 6300 psi). In a preferred embodiment, the shock absorbing adhesive resin has a solubility parameter δ (square root of cohesive energy density) of about 15-22 J ^1/2 / cm ^3/4 . For solubility parameters and cohesive energy, see for example: W, Van Krevelen, “Polymer properties; correlation with chemical structure”, Chapter 7 (aggregation properties and solubility), 3rd edition, all revised edition, 1997, XXII + 875, ISBON: 0-444-82877. -X. The disclosure content of this document also forms part of this specification. For example, the solubility parameter of polyethylene is 15.8 to 17.1 J ^1/2 / cm ^3/4 and the solubility parameter of poly (methyl acrylate) is 19.9 to 21.3 J ^1/2 / cm ^{3 / 4} .

Examples of the impact-absorbing adhesive resin include the following resins: olefin-acrylic acid copolymer, olefin-methacrylic acid copolymer, olefin-maleic anhydride copolymer, olefin-acrylic acid-acrylate terpolymer, olefin-methacrylic acid- Acrylate terpolymers, olefin-acrylic acid-methacrylate terpolymers, olefin-methacrylic acid-methacrylate terpolymers, olefin-maleic anhydride-acrylate terpolymers, olefin-maleic anhydride-methacrylate terpolymers, and any mixtures thereof. Olefinic monomers C ₁ -C ₆ olefin, preferably be an ethylene or propylene. Representative resins of suitable shock absorbing adhesive resins include ethylene-acrylic acid-metal acrylate terpolymers, ethylene-acrylic acid copolymers, n-butyl acrylate-acrylic acid-maleic anhydride terpolymers, and the like.

  Shock-absorbing adhesive resins useful in the present invention are resins that improve the toughness, flexibility and adhesion of the material or substrate. Preferred shock-absorbing adhesive resins are also useful as heat-activated seals, polyolefin compound fixers (eg, bipolar fixers), engineering thermoplastic impact modifiers and hot melt adhesives. is there. Many types of commercially available copolymer resin products and terpolymer resin products may be used. Examples of such products include “Primacore” from Dow, “Escore resin” from Exxon, and resins from DuPont. Etc. are exemplified. The shock-absorbing adhesive resin may be blended with additional components such as antioxidants, UV inhibitors, flame retardants and reinforcing fillers known in the art. In general, the amount of such additional ingredients is about 0.1 to 20 parts by weight.

  Among the ethylene-acrylic acid-acrylate terpolymers useful as shock-absorbing adhesive resins, particularly preferred terpolymers include about 6% acrylic acid monomer and about 20% acrylate monomer (eg, methyl acrylate, ethyl acrylate). , N-butyl acrylate, propyl acrylate, etc.). The acidic monomer imparts ion binding ability to the resin, and as the content of the acidic monomer increases, the adhesive ability of the resin to the inorganic substrate increases. Ester monomers also impart high polarity to the resin, resulting in improved adhesion to organic substrates (eg, polar organic substrates). Increasing the length or degree of branching of the ester side chain (eg changing from a methyl group to a butyl group) decreases the polarity of the ester monomer, which adjusts the resin adhesion for specific applications It becomes possible to do. Also, the higher the acrylate ester content, the greater the polar interface for bonding to the polar substrate, which results in improved adhesion.

  Exxon's “Escore resin” is a preferred shock-absorbing adhesive resin for use in the present invention. A preferred resin of this type is “Exxon Escore AT325”. This resin is an ethylene-methyl acrylate-acrylic acid terpolymer containing about 74%, 20% and 6% ethylene, methyl acrylate and acrylic acid, respectively. This type of Escore resin adheres well to many non-polar materials (eg, polypropylene, polyethylene and ethylene-propylene diene rubber) and polar materials (eg, aramid, polyamide and polyester) via the ethylene chain. It is an acidic terpolymer based on ethylene-methyl acrylate-acrylic acid terpolymer.

  As is known in the art, these resins exhibit a Shore hardness (A scale; 15S) of about 50-90 according to ASTM D2240. In addition, these resins exhibit good adhesion to metals and glass due to the acidic function of the resin. As known in the art, “Escore AT325 terpolymer” has a melt index of about 20 g / 10 min (value according to ASTM D1238), a Vicat softening point of about 101 ° F. (value according to ASTM D1525), and about 2680 psi. Bending elastic modulus (value according to ASTM D790).

  In one aspect of the present invention, a shock-absorbing adhesive resin or a shock-absorbing adhesive resin described below is produced on a composite material of an impact base material or on a release sheet (for example, silicon release paper). The present invention relates to the production of a layered structure having a resin layer coated with the contained adhesive composition. That is, in order to facilitate the production of the layered structure, the adhesive layer is interposed between the two release layers. The release layer may be subsequently removed to apply the adhesive layer to the impact substrate. In order to produce a composite laminated structure, an impact-absorbing adhesive resin or an adhesive formulation containing the resin is coated on one surface of the impact substrate. An additional layer of impact substrate may be applied over the exposed coating.

  The composite laminated structure may be formed using an impact base material layer and an adhesive resin layer. The exposed substrate of the adhesive resin may be used to adhere the impact substrate to the surface to be protected by the impact composite laminate structure. In one arrangement, this aspect includes applying a coating layer of an impact-absorbing adhesive resin onto the release sheet, which is then impacted by heat and / or pressure. It may be applied on a surface or other surface. The release sheet is peeled before, during or after this application process, thereby exposing the adhesive resin layer.

  In another aspect, the impact-absorbing adhesive resin is combined with one or more resins into an adhesive formulation (preferably a hot melt adhesive formulation) used to coat the impact material. Blended. This formulation imparts better wettability to the surface area and fluidizes with less heat and / or pressure than films made of pure copolymers or terpolymers. In this embodiment, the shock-absorbing adhesive resin is blended as an adhesive blend containing the following five components (i) to (v).

  (I) About 20 to 90% by weight (more preferably about 35 to 55% by weight) of the shock-absorbing adhesive resin. For example, a copolymer or terpolymer of acrylic acid or methacrylic acid and an olefin having a melt index of about 1 to 100 (preferably 5 to 40) and an acid number of 10 or more. Preferred ethylene-acrylic acid or methyl acrylate terpolymers are selected from “Exon Escore resin”, particularly preferably “Exon Escore AT325 resin”.

(Ii) about 30-70% by weight of an olefin- (meth) acrylate [meaning acrylate or methacrylate] copolymer or olefin-vinyl acetate copolymer having a melt index of about 0.5-100 (preferably about 2-30) More preferably about 15 to 35% by weight). Olefin monomers may be _C 1 -C ₆ olefin (preferably ethylene or propylene). In a preferred embodiment, the olefin- (meth) acrylate resin has a solubility parameter δ (square root of cohesive energy density) of about 15-26 J ^1/2 / cm ^3/4 . For example, the solubility parameters of polyethylene, poly (methyl acrylate) and poly (methyl methacrylate) are 15.8 to 17.1 J ^1/2 / cm ^3/4 and 19.9 to 21.3 J ^1/2 / cm ^{3 /, respectively. With} solubility parameters of ⁴ and 18.6 to 26.2 J ^1/2 / cm ^3/4 .

Typical copolymers include the following polymers: polymerized ethylene-methyl acrylate, polymerized ethylene-methacrylate, polymerized ethylene-n-butyl acrylate, ethylene-butyl acrylate (EBA) copolymer, ethylene ethyl acrylate (EEA). Copolymers and ethylene-methyl acrylate (EMA) copolymers. More preferably, the acrylate monomer has a solubility parameter of 18.5-26 J1 / ² / cm3 / ⁴ . Also, methyl vinyl acetate (MVA) copolymer, ethyl vinyl acetate (EVA) copolymer, propyl vinyl acetate (PVA) copolymer and butyl vinyl acetate (BVA) copolymer may be added or used.

  Preferred olefin- (meth) acrylate copolymers contain about 15-35% methyl acrylate. A preferred commercial product is an olefin-methyl acrylate copolymer such as “Optema” manufactured by Exxon. As is known in the art, this type of copolymer has a melt index of about 1.0-100 (value according to ASTM D1238), a Vicat softening point of about 90-130 ° F. (value according to ASTM D1525), about 2500 It has a flexural modulus of ~ 6000 psi (value according to ASTM D790) and a Shore hardness (A scale; 15S) of about 70-90 (value according to ASTM D2240). A particularly preferred “Optema” copolymer is “Optema TC-221 or TC-220” from Exxon. This type of copolymer is an ethylene-methyl acrylate copolymer containing about 27% methyl acrylate.

  Ethylene-methyl acrylate (EMA) copolymers are high pressure process PE copolymers that are very thermally stable. This copolymer is a conventional thermoplastic processing method (eg, extrusion coating, extrusion lamination, blow / cast single layer, co-extrusion film, injection molding, sheet extrusion, profile extrusion, blow molding and Processed by a foam extrusion method or the like). In addition, the copolymer can be used to prepare alloys, blends and compounds, and can be subjected to extrusion when softness and flexibility are required. Furthermore, the copolymer uses include coextruded tie layers for flexible packaging materials, compatibilizers or impact modifiers for engineering thermoplastics, hot melt adhesives and sealants, and the like. .

  Component (ii) of the adhesive formulation may be or contain an olefinic ethylene-vinyl acetate copolymer. The vinyl acetate monomer may be methyl vinyl acetate (MVA), ethyl vinyl acetate (EVA), propyl vinyl acetate (PVA) or butyl vinyl acetate (BVA). A preferred olefinic ethylene-vinyl acetate copolymer is the commercial product “Evaloy AC resin” manufactured by DuPont. As is known in the art, the resin contains about 15-28% by weight vinyl acetate monomer and has a melt index of about 1-10.0 g / 10 min (value according to ASTM D1238), and It has a Vicat softening point of about 100-200 ° F. (value according to ASTM D1525).

  A preferred olefinic vinyl acetate copolymer is an ethylene-vinyl acetate copolymer. These copolymers may be added to the mixture or used independently as component (2). In use, these copolymers promote increased adhesion to polycarbonate materials, ceramics such as tile materials, aromatic urethanes, plastics, ABS, and metals. Examples of commercially available ethylene-vinyl acetate copolymers include “Elvax resin” manufactured by DuPont. Particularly preferred products of this type are “Elbax 4210” and “Elbax 4260”. . This type of EVA copolymer contains at least about 28% by weight vinyl acetate, and has a melt index of about 5 to 500 g / 10 min (value according to ASTM D1238) and about 140 to 350 ° F. (value according to ASTM E28). It has a ring and ball softening point of

  (Iii) About 3 to 40% by weight (more preferably 15 to 40% by weight) of acidic rosin (for example, tall oil rosin, gum rosin and wood rosin). The acidic rosin has an acid value of about 20 to 200 (preferably about 100 to 160) and a melting point of about 60 to 130 ° C (preferably about 65 to 100 ° C). Preferred acidic rosins, such as “Unitac rosin” available from Union Camp or Arizona, and “Stabilite gum rosin” from Hercules may be used.

  (Iv) about 1 to 20% by weight (more preferably about 5 to 15% by weight) of a high melting point oxidized wax having a melting point of about 80 to 120 ° C. (preferably about 95 to 125 ° C.) and an acid value of about 5 to 50 . Suitable representative oxidized waxes include oxidized high density polyethylene, oxidized microcrystalline wax, oxidized fishertrop wax, oxidized paraffin wax, and the like. A preferred wax is “Marcos Wax 3500” (softening point: about 235 ° F., acid number: 24, specific gravity: about 0.97) manufactured by Marcos Chemical Co. (Houston, Texas).

  (V) about 1 to 20% by weight (more preferably about 5 to 15% by weight) of a low melting wax having a melting point of about 55 to 90 ° C. (preferably about 59 to 70 ° C.) and an acid number of about 10 to about 100. . The low melting point wax may be compatible with other resins in the adhesive formulation or may be incompatible. Suitable representative low melting waxes include long chain fatty alcohols, esters, amides (including but not limited to stearic acid that has been subjected to the pressing process three times), oleates, stearamides, and other meltables. Contains wax. Preferably, the low melting point wax is triple pressed stearic acid having a softening point of about 30-150 ° F. and / or low density to high density polyethylene having a low softening point of about 85-115 ° C.

  The low melting point wax acts as an external plastic oil type lubricant (different from the solvent type lubricant). As is known in the art, low melting waxes promote and facilitate resin flow without lowering the Vicat softening or creep temperature, and also act as an anti-sticking agent by surface blooming. .

  Additional components other than the above components, for example, antioxidants, UV inhibitors, flame retardants and energy-absorbing reinforcing fillers known in the art may be incorporated into the adhesive formulation. it can. The typical amount of these additional ingredients is about 0.1 to 20 parts by weight.

The adhesive formulation according to the present invention can be prepared by methods known in the art. For example, in one embodiment, the adhesive formulation can be prepared in a heated mixer with a sigma blade or a hot kettle with a stirrer. Also, as is known in the art, the adhesive formulation can be compounded in an extruder using a static mixer in an adapter or on a mixing head extrusion screw (eg, Madox head). it can. Typical mixing temperatures are about 250-400 ° F. Of course, as will be appreciated by those skilled in the art, such mixing temperatures depend on the characteristics of the ingredients (eg, viscosity, etc.). Polymer components (i) and (ii) may be mixed first and the mixture blended with the remaining components. Alternatively, the adhesive formulation according to the present invention may be prepared, for example, by extruding the above components simultaneously using a single or twin screw mixing extruder.

  The adhesive formulation according to the invention has an acid number greater than 12 (preferably about 50-140). In a preferred embodiment, the above copolymers (i) and (ii) have a solubility parameter of about 18-25. By blending a solvent-based wax and a tackifier, the adhesive formulation according to the present invention is a suspension that provides longer pressure sensitivity and open tack time when heated above about 150 ° F. Shows conversion effect and supercooling effect. This makes the adhesive formulation suitable for use as a hot melt adhesive. The adhesive formulation according to the invention exhibits long-term resistance to aromatic and aliphatic oils.

  The adhesive formulation according to the present invention advantageously has a tensile strength test in the width direction of about 6 to 20 pounds / percent when used to bond "1 inch" strips of "Kevlar" at room temperature. Inch bond strength was indicated. The adhesive formulation also allows a “Spectra” or “Kevlar” cloth to be bonded to a standard ceramic bulletproof armor with a tensile load of about 6-20 pounds per inch strip. It was. The adhesive formulation according to the present invention can bond "Kevlar" to "Spectra" with a tensile load of about 6-20 pounds / inch, and this bonding can be done at 220-245 ° F. The linear orientation of the “Spectra” fibers is not impaired. In the most advantageous embodiment, the adhesive formulation adheres “Spectra” to “Kevlar” or ceramic and metal in the same laminate at a temperature of about 245 ° F. or less (preferably about 220 ° F.). be able to.

  While not being bound by theory, the shock-absorbing adhesive resin and adhesive formulation according to the present invention melts to some extent by the impact of the projectile and impact substrate (especially woven or fibrous impact). For example, "Kevlar") and become elongated in the direction of the projectile's trajectory to absorb more energy. This elongation during impact occurs due to the low modulus of the adhesive that damps the woven substrate and the melting of the adhesive initiated by the impact of the projectile. Thus, an impact-absorbing adhesive resin and adhesive formulation provides a transition from an amorphous structure to a linear structure and a composite phase transformation from a solid state to a liquid / molten state during projectile impact and penetration. To absorb energy at millisecond intervals. Related conventional composites are believed to be inferior in impact resistance because they do not melt and / or stretch upon impact and break or shear.

  The composite layered structure according to the present invention (for example, a laminated structure made of polyaramid) has an adjacent layer (for example, usually about 5 to 100 fiber layers, preferably about 9 to about 65 polyaramid fibers) of an impact base material. Produced by interposing an impact-absorbing adhesive resin or adhesive formulation between the layers). The shock-absorbing adhesive resin melts the adhesive formulation and applies the melt as a continuous or discontinuous layer on one side of the substrate, or as a dot about 1/8 to It is applied or applied onto the substrate by printing onto the substrate at a 3/4 inch spacing (preferably about 3/8 to 1/2 inch). The thickness of the series of dots in the adhesive layer is about 0.0002-0.020 inches (preferably about 0.0004-0.005 inches).

  Other methods of application of the adhesive layer that may be used are mentioned below. As described above, the adhesive may be applied as a continuous layer or dots from a layered structure having an adhesive coated on a release sheet. After the impact substrate is applied to the exposed adhesive layer and the release sheet is removed, the next impact substrate is applied.

  A preferred composite laminate structure according to the present invention is formed from a woven or non-woven fabric of polyaramid fibers (eg, “Kevlar” manufactured by EI DuPont de Nemours). The laminated composite laminate structure according to the present invention contains a polyaramid fiber layer, and an impact-absorbing adhesive resin or adhesive composition according to the present invention is interposed between the fiber layers. The shock-absorbing adhesive resin / adhesive blend fills between the yarns and adheres adjacent layers. In a preferred embodiment, the composite laminate structure comprises about 12-20 polyaramid fiber layers and about 12-20 impact absorbing adhesive resin / adhesive blend layers.

  In general, this type of composite material is manufactured by applying the resin / blend to one side of each layer and bonding the coated surface to the uncoated surface of the next layer. Alternatively, both sides of each layer may be coated with the resin / blend. The thickness of the shock-absorbing adhesive resin / adhesive blend layer can be about 0.0005 to 0.030 inches and the coating thickness on one side is about 0.0004 inches. When tested using a bullet that reaches 16 feet forward from the barrel of 44 Magnum Remington, the penetration depth of a bullet into a composite laminate structure having 10 layers is 32 mm or less, and a composite having 12 layers The penetration depth of the bullet into the laminated structure was 16 mm or less.

  The composite laminate structure can also be used as shielding and can be applied to plastic, ceramic or metal panels. That is, after heating the panel to a temperature sufficient to soften or melt the shock-absorbing adhesive resin of the composite laminate structure (about 245 ° F.), the composite laminate structure is applied to the panel. Press. Alternatively, after the composite laminated structure is placed on the panel, the laminated structure covered with the shock-absorbing adhesive resin can be adhered to the metal or ceramic panel by heating both of them. Good. A convection heating method, an autoclave heating method, or a microwave heating method may be used. The composite laminate structure is preferably cut so as to cover the form of the panel to which the structure is applied. The composite laminate structure may be bonded using an exposed layer of a shock-absorbing adhesive resin / adhesive blend. In one embodiment, the composite laminate structure is formed on a layered structure having a release sheet, and the release sheet remains in place during manufacture. The release sheet is then removed to expose the adhesive layer for adhesion to the substrate.

  One advantage of the shock-absorbing adhesive resins and preferably hot melt adhesive formulations according to the present invention is that the impact substrate (eg, “Kevlar” or “Spectra”) can be made of metal and ceramic panels. By adhering to both, armor, shield, helmet, vehicle, etc. are protected from impact. The shield may be sized to be carried with an arm and may have a window. Impact resistant ceramics include silicon carbide, boron carbide, phase transformed alumina and other oxide ceramics. When used with a ceramic panel, the composite laminated structure according to the present invention is preferably applied between the vehicle and the ceramic panel. Impact ceramics include silicon carbide, boron carbide, phase-transformed alumina and other oxide ceramics. A metal and an alloy (for example, aluminum and steel) may be combined.

  1A and 1B are schematic diagrams illustrating a method of preparing a composite laminate structure using a hot melt adhesive formulation according to one embodiment of the present invention. Other composite laminated structures described above according to the present invention can be prepared in the same manner as the preparation method.

  In this embodiment, the impact-absorbing adhesive resin is a hot-melt adhesive formulation formulated as described above, and the formulation is applied onto at least one impact substrate to form a composite laminate structure. Form. The hot melt adhesive formulation may be applied by methods known in the art. For example, the formulation may be applied to the impact substrate by extrusion coating, knife coating or roll coating, or a series of dots or other patterns (eg, reticular or linear patterns) or It may be printed on the impact substrate as a continuous film. Other conventional coating methods such as a sinter coating method known in the art or a lamination coating method from a release sheet can also be used.

  In FIG. 1A, a hot melt adhesive formulation is applied onto at least one impact substrate 105 using at least one application method (roll coating, printing, extrusion, or other conventional application). To do. If desired, additional impact substrates (e.g., layers of additional impact substrates 110, 115, and 120) may also be coated with the hot melt adhesive formulation. As this type of impact base material, the base materials already described in detail may be used in combination. Further, the number of impact substrates is optional, and in one embodiment, the number of polyaramid fiber layers is about 5-250. The impact substrate may be heated by a conventional heating device 125 (eg, oven, microwave heating device, autoclave, steam heating device), or may be heated by any combination of these devices.

  If desired, as shown in FIG. 1B, the impact substrate may be placed in a flexible vacuum bag 130 under reduced pressure, or may be placed in a suitable pressure device. The reduced pressure may be in a pressure range close to atmospheric pressure, or may be higher or lower than this. In this embodiment, a ceramic 135 such as a tile is bonded to other impact substrates 140, 145 and 150. The order in which the hot melt adhesive is applied to the various impact substrates is optional and is based on the desired manufacturing aspect. For example, a tile-like ceramic 135 is disposed on a pre-formed composite laminate structure. In this embodiment, the preformed composite laminate structure is an impact substrate (eg, 140, 145 and 150) that has been cooled by application of a hot melt adhesive. Or you may form the whole composite laminated structure on the spot. During preparation, a pressure (for example, higher or lower than atmospheric pressure) to be adjusted using a vacuum bag is applied to the composite laminated structure.

  In another embodiment, an impact-absorbing adhesive resin used to form a composite laminate structure from an impact substrate is applied.

  FIG. 2 is a flowchart showing the net manufacturing process of the composite laminated structure. In this embodiment, the shock-absorbing adhesive resin is a copolymer or terpolymer of acrylic or methacrylic acid and olefin having a melt index of about 1 to about 100 (preferably about 5 to about 40). In step 210 of FIG. 2, the shock-absorbing adhesive resin is introduced into the extruder. In this embodiment, a preferred shock-absorbing adhesive resin is a terpolymer containing acrylic acid and methacrylic acid (eg, “Escore AT325”).

  In step 215, the appropriate die is adjusted to suit the desired application (eg, the die width and thickness are adjusted). For example, the width of the die may be adjusted to be about 0.005 to 75.0 inches or greater, and the desired extrusion thickness may be adjusted to be about 0.0003 to 0.050 inches or greater. . In a more limited and particularly preferred embodiment, the extrusion die is adjusted to have a width of 52 inches and a thickness of 0.0005 inches. The adhesive formulation may be applied as a continuous layer onto the release sheet using methods known in the art (eg, those described above) or printed in a desired pattern.

  A second release sheet may be applied, and the adhesive layer may be sandwiched between the two release sheets. After applying the release sheet, the laminated structure may be cut into a sheet shape or wound on a roll. Preferably, the laminated structure is continuously extruded and then wound on a roll (for example, a 4000-yard roll).

  In step 220, the extruder is operated so that the raw material in the extruder is extruded onto the release sheet. The release sheet is release paper coated with silicon or other release material sheet known in the art.

  In step 225, the extruded material is used to coat the desired substrate that is applied to the impact substrate when the release sheet is removed.

  If desired, the release sheet may be omitted by applying the adhesive formulation directly onto the desired impact substrate to form a composite material (e.g., a composite material layer), omitting the release sheet. This simplifies the manufacturing process of the composite laminated structure. For example, the extruder is operated so that the raw material in the extruder is applied directly onto the impact substrate to form a composite laminate structure. According to this aspect, the number of manufacturing steps is minimized and the manufacturing method is simplified. As is known in the art, multi-layer structures may be manufactured by sequential processes.

  In one embodiment, Step 225 includes a process of manufacturing a composite laminated structure using a laminating machine. The impact substrate is used to form a composite laminate structure. For example, a release sheet and an aramid fiber woven or non-woven fabric are fed into a laminating machine, and the woven or non-woven fabric and / or release sheet is heated to a desired temperature, whereby the adhesive on the release sheet becomes a substrate. Melt up. Of course, a composite laminate structure having a release sheet can be produced by using another method known in the art.

The following examples are given to illustrate the present invention, and the present invention is not limited to these examples.
Example 1
The hot melt adhesive composition having the following composition was measured by modulation differential scanning calorimetry (DSC).

Formulation 1:
A hot melt adhesive was prepared by mixing the following ingredients in an adhesive stirrer at a high temperature of about 325 ° F. for about 2 hours.
1. 10 parts of “Exon AT325” (about 47% by weight). “Escore” resin: ethylene-acrylic acid-methyl acrylate terpolymer. Melt index: 25.
2. 6 parts of "Exon TC-221 or 220" (about 28% by weight). “Optima” resin: EMA (ethylene-methyl acrylate) copolymer. Methyl acrylate content: 27%. Melt index: about 5.
3. “Unitac” (acid rosin made by Union Camp or Arizona) 7.5 parts (about 35% by weight). Acid value: about 128-145. Melting point: about 78-85 ° C.
4). 1.7 parts (about 8.4% by weight) of “Marx wax 3500” (oxidized high-density polyethylene having an acid value of 24. Melting point: 112 ° C.
5. 1.7 parts (about 8.4% by weight) of “stearic acid subjected to the pressing process three times”. Melting point: + 60 ° C. Acid value: about 30 (value for initial flow at low temperature).

  FIG. 3 shows the measurement results by modulation DSC for the hot melt adhesive according to this example. DSC is used to measure a wide range of physical properties of the material being measured, such as glass transition temperature (Tg), melting point (Tm), and solid-solid transition. In this measurement method, the sample and reference material are processed by a controlled temperature program. When a phase transition such as melting occurs in the sample, it is necessary to supply energy in order to keep the sample and the reference material at the same temperature. A DSC chart is obtained by recording this energy difference as a function of temperature.

  Modulated DSCs not only provide quantitative and qualitative information about physical and chemical changes as in conventional DSCs, but also provide specific thermochemical data that cannot be obtained by conventional DSCs. It is done. The sensitivity of the system is increased because the effects of baseline slope and curvature are reduced. Overlapping events such as molecular relaxation and glass transition can be separated. Heat capacity can be measured directly by modulated DSC in a minimum number of experiments.

  FIG. 3 shows the measurement result of modulated DSC for a sample of about 10.68 mg. For the measurement, a TA device Q-100 for modulation DSC was used. The log method indicates experimental parameters. In particular, the experiment was modulated at ± 1.00 ° C. every 60 seconds (heating rate up to 200 ° C .: 2.00 ° C./min). As is apparent from the obtained graph, the test material has a wide melting point (peak: 62.7 ° C.). This broad melting point indicates that the test material is a multi-component mixture where each component has a different melting point. Further, as apparent from the chart of FIG. 3, the test material exhibits a glass transition temperature of about 16.2 ° C.

  FIG. 4 shows the viscosity diagram of the hot melt adhesive according to this example. In this case, the data relating to the viscosity of the same hot melt adhesive formulation according to the above formulation 1 was measured using a device TA AR500 manufactured by Texas. The raw phase is a set point line to ensure that the data was obtained within the internal parameters of the measuring device. As shown, the original phase is less than about 80 ° C., indicating that the data is characterized by being accurate and acceptable within the tolerance of the measuring device.

  Storage modulus is a measure of the energy stored during deformation and is related to the solid-like or elastic portion of the elastomer. “E ′” is used for extensional deformation, and “G ′” is used for torsional or torsional deformation. Loss modulus is a measure of the loss of energy during deformation (usually heat loss) and is related to the liquid-like or viscous part of the elastomer. “E ″” is used for extensional deformation, and “G ″” is used for torsional or torsional deformation. Tangent delta (tan δ) is a measure of the energy dissipation ability of the test material. In this case, the following relational expression holds: tan δ = E ″ / E ′ = G ″ / G ′. These parameters are understood by those skilled in the art.

  In FIG. 4, the storage modulus (G ′) drops to about 50 × E7 Pa at about 70-75 ° C. and reaches a final value of about 1000 Pa at 100 ° C. This indicates that the test material is solid up to about 70 to 75 ° C., but melts as the storage modulus decreases. tan δ represents the ratio of loss modulus to storage modulus. Data relating to tan δ indicates that the test material goes through two molten states. The entire chart shown in FIG. 4 shows that the test material starts from a solid state and melts as the temperature rises.

Example 2
In this example, a woven fabric made of polyaramid fiber “Kevlar 29” having 3000 denier was cut into swatches (18 × 18 inches). Ten woven fabrics coated on one side with a hot-melt adhesive layer (thickness: 0.005 inch) are laminated, and these woven fabrics have a helmet form by hot-melt adhesive interposed between the woven fabrics. Molded into an integral composite structure (weight: 2.25 pounds). In this case, the hot melt adhesive composition is a composition having the same composition as the composition 1.

  A laminate composed of 12 layers obtained by applying the thermoplastic adhesive in a thickness of 0.005 / 1000 inch to a Kevlar woven fabric having a thickness of 0.020 / 1000 inch is manufactured. When you do, you get unexpected results.

  A 12-layer laminate is heated in a convection oven or microwave oven, introduced into a polyethylene bowl, formed into a preliminary form, introduced into a female mold, and then the cold male mold is The laminate was molded by pressing into a female mold and allowed to cool. The resulting laminate exhibited twice the strength required in five shooting tests and an average 24% higher energy absorption than conventional Kevlar composites.

  In one test, the helmet-like laminate was fixed to a fixation device, and the total distance from the muzzle of a handgun with a 10-inch barrel to the helmet-like laminate was set to 16 feet. The results obtained are shown in Table 1 below. In the table, “Mag Rem” indicates “Magnum Remington Gun”, and “Gr JHP” indicates “the hollow point of the cartridge case filled with drug granules”.

  According to these specifications, the penetration distance under the test conditions used in this example is 44 mm. As shown in Table 1, the results obtained using the composite laminate structure according to the present invention were as short as 22 mm.

Example 3
In this example, a 3000 denier “Kevlar” fiber yarn was used. The areal density of uncoated "Kevlar" fibers is 12 ounces / square yard (0.083 pounds / square foot). The areal density of 20 uncoated “Kevlar” fiber layers is 1.67 pounds per square foot. The specific gravity of the adhesive formulation of Example 2 is 0.98 (0.354 lb / in 3). When a resin having the same composition as Formulation 1 is coated at a thickness of 0.005 inches, the surface density of the single resin layer is 0.0255 pounds per square foot, and the surface density of the 20 layers is 0.00. 51 pounds per square foot. The overall density of the 20 coated fiber layers is 2.18 pounds per square foot (1.67 pounds per square foot + 0.51 pounds per foot). The total resin content is 23.4% by weight with respect to the fibers.

Projectile Testing According to the US Army historical database, V ₅₀ (0.30 caliber FSP) for bonded “Kevlar” fibers with an areal density of 2.18 pounds per square foot (34.9 ounces per square yard) The predicted value of is about 1600 feet / second. The V ₅₀ of the 20-layer panel subjected to the test was 1786 feet / second. This value indicates a 11.6% increase in projectile speed and a 24.6% increase in projectile energy. The results obtained are shown in Table 2 below.

  The resin content in the panel subjected to the test was somewhat higher and not lower than that of the traditional armored adhesive laminate. The shock-absorbing adhesive resin is hypothesized to aid in the projectile stopping action of “Kevlar” fibers. In other words, the impact-absorbing adhesive resin according to the present invention can be referred to as an “impact” resin, unlike the traditional “structural” resin that does not contribute to the impact resistance of the fiber reinforced laminate.

Example 4
A woven fabric (denier: about 3000, weave: 17 × 17) made of polyaramid fiber (“Kevlar 29”) was used. A single composite was prepared by bonding approximately 18 cloth layers coated on one side to each other with an adhesive layer interposed between adjacent cloth layers at a thickness of 0.002 inches. An outer layer of a rigid thermoplastic surface (eg, a “Lexan” or similar thermoplastic surface) was overlaid on the composite surface. The laminate is heated in an oven to a temperature of about 250 ° F. in a vacuum bag, then placed in a polyethylene shield and stretched for about 15 minutes under a pressure below atmospheric pressure to a thickness of about 400 Inch preforms were prepared. The adhesive layer was formed using a formulation having the same composition as in the case of the formulation 1.

  The test was conducted according to NIJ0101081 test method according to pass / fail criteria. The minimum impact speed of the two weapons (9mm Parabellum gun and 0.44 Magnum gun) is 1400 feet / second. As is apparent from the results shown in Table 3 below, no penetration by a 9 mm parabellum gun or a 44 magnum gun was observed under the test conditions used in this example. These results indicate that the test substance exhibits high impact resistance.

Table 4 below shows the results obtained from MIL-STD-622F of the same composite laminate structure as in Example 4. These results indicate that 50% of the bullets completely through the barrier, 50% shows a theoretical threshold of partially penetrates into the barrier, these results are called V _50. The higher the V _50, the protection level of the barrier is higher. Generally speaking, the barrier is less than about 150 feet / second (fps) than the minimum test speed for pass / fail tests (this speed is called V ₀ because no bullet penetrates the barrier). Fast V ₅₀ is shown. The speed shown for the composite material described in Example 3 is 1713 fps, which is 313 fps faster than the minimum test speed and is very good. See Table 4 below showing all results.

  The results shown in Table 4 indicate that the test substance is a substance with high impact resistance. As will be apparent to those skilled in the art, those skilled in the art can make various modifications and variations to the various aspects described above without departing from the spirit or scope of the present invention. Therefore, as long as such modifications and variations of the present invention are included in the scope of the claims of the present application and their equivalents, the modifications and variations are also encompassed by the present invention.

FIG. 1A is a schematic diagram showing a method for producing a composite laminate structure using a hot melt adhesive formulation according to the present invention. FIG. 1B is a schematic view showing another method for producing a composite laminate structure using a hot melt adhesive composition according to the present invention. FIG. 2 is a flowchart showing the net manufacturing process of the composite laminated structure. FIG. 3 is a chart showing the measurement results of the hot melt adhesive according to the present invention by modulation DSC. FIG. 4 is a viscosity diagram of a hot melt adhesive according to the present invention.

Claims (31)

A composite laminate structure comprising at least two impact substrates bonded with an adhesive formulation containing the following components (i) to (v):
(I) about 20 to 90% by weight of an impact-absorbing adhesive resin having a melt index of 1 to 100;
(Ii) about 3 to 70% by weight of an olefin-acrylate copolymer or olefin-methacrylate copolymer having a melt index of about 0.5 to about 100 or an olefin-vinyl acetate copolymer having a melt index of about 0.5 to 350;
(Iii) about 3-40% by weight of acidic rosin having an acid number of about 20-200,
(Iv) about 1-20% by weight of a high melting point oxidized wax having a melting point of about 80-120 ° C. and (v) about 1-20% by weight of a low melting point wax having a melting point of about 55-90 ° C.   The composite laminate structure according to claim 1, wherein at least one of the at least two impact substrates contains 5 to 250 polyaramid fabric layers. The composite laminate structure according to claim 1, wherein the impact base material is selected from the following group:
Poly (m-xylylene adipamide), poly (p-xylylene sebacamide), poly (2,2,2-trimethyl-hexamethylene terephthalamide), poly (piperazine sebacamide), poly (meta Phenylene isophthalamide), poly (p-phenylene terephthalamide), drawn olefin fiber, rigid rod chain molecule of poly (p-phenylene-2,6-benzobisoxazole), metal, ceramic, and any of these blend. The impact-absorbing adhesive resin is selected from the following group and contains about 3 to 70 wt% of an olefin-acrylate copolymer or olefin-methacrylate copolymer having a melt index of about 0.5 to about 350. Composite laminated structure:
Olefin-acrylic acid copolymer, olefin-methacrylic acid copolymer, olefin-maleic anhydride copolymer, olefin-acrylic acid-acrylate terpolymer, olefin-methacrylic acid-acrylate terpolymer, olefin-acrylic acid-methacrylate terpolymer, olefin-methacrylic acid -Methacrylate terpolymers, olefin-maleic anhydride-acrylate terpolymers, olefin-maleic anhydride-methacrylate terpolymers, and any mixtures thereof.   The composite laminate structure of claim 1, wherein the shock-absorbing adhesive resin has a Shore A hardness of about 50-90 and the olefin-acrylate copolymer or olefin-methacrylate copolymer has a Shore A hardness of about 70-90. The composite laminate structure of claim 1, wherein the olefin-acrylate copolymer or olefin-methacrylate copolymer has a solubility parameter of about 15 to 26 J1 / ² / cm3 / ⁴ .   The composite laminate structure according to claim 1, wherein the composite laminate structure has a form of an armor, a shield, a helmet, a vehicle, or an aircraft. The composite laminate structure according to claim 1, comprising the following components (i) to (v):
(I) about 35 to 55% by weight of an impact-absorbing adhesive resin;
(Ii) about 15-35% by weight of an olefin-acrylate copolymer or olefin-methacrylate copolymer;
(Iii) about 15-40% by weight of acidic rosin,
(Iv) about 5-15% by weight of high melting point oxidized wax, and (v) about 5-15% by weight of low melting point wax.   Magnum Remington, which is a composite laminated structure containing 12 to 14 layers of polyaramid material bonded with an impact-absorbing adhesive resin, and is loaded with bullets in which 240 drug particles are filled in the hollow case The composite laminated structure has a penetration limiting ability for a bullet fired from a handgun of 32 mm or less (distance between the composite laminated structure and the handgun: 16 to 17 feet).   The composite laminated structure according to claim 9, wherein the penetration limiting ability is 22 mm or less.   The composite laminated structure according to claim 9, which has the form of an armor, a shield, or a helmet. Olefin fiber or polyaramid fiber bonded with an adhesive composition containing the following components (i) to (v) or a polyaramid fabric or a stretched linear olefin fabric including these fiber layers:
(I) about 20 to 90% by weight of an impact-absorbing adhesive resin having a melt index of 1 to 100;
(Ii) about 3 to 70% by weight of an olefin-acrylate copolymer or olefin-methacrylate copolymer having a melt index of about 0.5 to about 50;
(Iii) about 3-40% by weight of acidic rosin having an acid number of about 20-200,
(Iv) about 1-20% by weight of a high melting point oxidized wax having a melting point of about 80-120 ° C. and (v) about 1-20% by weight of a low melting point wax having a melting point of about 55-90 ° C. Adhesive formulations containing the following components (i) to (v):
(I) about 20 to 90% by weight of an impact-absorbing adhesive resin having a melt index of 1 to 100;
(Ii) about 10-70% by weight of an olefin-acrylate copolymer or olefin-methacrylate copolymer having a melt index of about 0.5 to about 100 or an olefin-vinyl acetate copolymer having a melt index of about 0.5 to 350;
(Iii) about 3-40% by weight of acidic rosin having an acid number of about 20-200,
(Iv) about 1-20% by weight of a high melting point oxidized wax having a melting point of about 80-120 ° C. and (v) about 1-20% by weight of a low melting point wax having a melting point of about 55-90 ° C. 14. The adhesive formulation of claim 13, having a Brookfield viscosity of about 10,000 to 100,000 cps / 380 [deg.] F. and a melting point (ring and ball method value) greater than 140 [deg.] F.   The adhesive formulation of claim 14, having a Brookfield viscosity of about 40,000 to 90,000 cps / 380 ° F. The adhesive formulation of claim 13, wherein the shock-absorbing adhesive resin is selected from the following group:
Olefin-acrylic acid copolymer, olefin-methacrylic acid copolymer, olefin-maleic anhydride copolymer, olefin-acrylic acid-acrylate terpolymer, olefin-methacrylic acid-acrylate terpolymer, olefin-acrylic acid-methacrylate terpolymer, olefin-methacrylic acid -Methacrylate terpolymers, olefin-maleic anhydride-acrylate terpolymers, olefin-maleic anhydride-methacrylate terpolymers, and any mixtures thereof.   The adhesive formulation of claim 13, wherein the shock-absorbing adhesive resin has a Shore A hardness of about 50-90, and the olefin-acrylate copolymer or olefin-methacrylate copolymer has a Shore A hardness of about 70-90. 14. The adhesive formulation of claim 13, wherein the shock-absorbing adhesive resin has a solubility parameter of about 15-22 J1 / ² / cm3 / ⁴ . The adhesive formulation according to claim 13, comprising the following components (i) to (v):
(I) about 35 to 55% by weight of an impact-absorbing adhesive resin;
(Ii) about 15-35% by weight of an olefin-acrylate copolymer or olefin-methacrylate copolymer;
(Iii) about 15-40% by weight of acidic rosin,
(Iv) about 5-15% by weight of high melting point oxidized wax, and (v) about 5-15% by weight of low melting point wax.   A composite laminate structure comprising at least two impact substrates bonded to a composite laminate structure form using an impact-absorbing adhesive resin having a melt index of about 1-100.   21. The composite laminate structure of claim 20, wherein the impact-absorbing adhesive resin is selected from the following group: olefin-acrylic acid copolymer, olefin-methacrylic acid copolymer, olefin-maleic anhydride copolymer, olefin-acrylic acid-acrylate. Terpolymer, olefin-methacrylic acid-acrylate terpolymer, olefin-acrylic acid-methacrylate terpolymer, olefin-methacrylic acid-methacrylate terpolymer, olefin-maleic anhydride-acrylate terpolymer, olefin-maleic anhydride-methacrylate terpolymer, And any mixtures thereof.   21. The composite laminate structure of claim 20, wherein at least one of the at least two impact substrates comprises 5 to 200 layers of polyaramid fabric or elongated olefin fabric. The composite laminate structure according to claim 20, wherein the impact base material is selected from the following group:
Poly (m-xylylene adipamide), poly (p-xylylene sebacamide), poly (2,2,2-trimethyl-hexamethylene terephthalamide), poly (piperazine sebacamide), poly (meta Phenylene isophthalamide), poly (p-phenylene terephthalamide), drawn olefin fiber, rigid rod chain molecule of poly (p-phenylene-2,6-benzobisoxazole), metal, ceramic, and any of these blend.   A layered structure containing an impact-absorbing adhesive resin having a melt index of about 1 to 100 coated on a release sheet. The layered structure according to claim 24, wherein the shock-absorbing adhesive resin is selected from the following group:
Olefin-acrylic acid copolymer, olefin-methacrylic acid copolymer, olefin-maleic anhydride copolymer, olefin-acrylic acid-acrylate terpolymer, olefin-methacrylic acid-acrylate terpolymer, olefin-acrylic acid-methacrylate terpolymer, olefin-methacrylic acid -Methacrylate terpolymers, olefin-maleic anhydride-acrylate terpolymers, olefin-maleic anhydride-methacrylate terpolymers, and any mixtures thereof. An adhesive resin containing the following components (i) to (v), wherein the layered structure contains the adhesive resin applied on a release sheet:
(I) about 20 to 90% by weight of an impact-absorbing adhesive resin having a melt index of 1 to 100;
(Ii) about 3 to 70% by weight of an olefin-acrylate copolymer or olefin-methacrylate copolymer having a melt index of about 0.5 to about 100 or an olefin-vinyl acetate copolymer having a melt index of about 0.5 to 350;
(Iii) about 3-40% by weight of acidic rosin having an acid number of about 20-200,
(Iv) about 1-20% by weight of a high melting point oxidized wax having a melting point of about 80-120 ° C. and (v) about 1-20% by weight of a low melting point wax having a melting point of about 55-90 ° C.   The manufacturing method of a composite laminated structure including the process of apply | coating the impact-absorbing adhesive resin which has a melt index of 1-100 on the base material for an impact.   The impact-absorbing adhesive resin is applied by at least one method selected from an extrusion coating method, a knife coating method, a roller coating method, a print coating method, and any combination of these methods. 28. The method of claim 27, including the step of applying a resin onto the impact substrate.   29. The method of claim 28, further comprising adhering at least one subsequent impact substrate to the applied impact substrate using at least one subsequent impact-absorbing adhesive resin.   30. The method of claim 28, further comprising molding the composite material into at least one product of a helmet, armor and shield on a pre-defined mold structure.   29. The method according to claim 28, wherein the method of applying the shock-absorbing adhesive resin includes an aspect in which the shock-absorbing adhesive resin is applied from the release sheet.

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