JP2018510791A - Systems and methods for transfer of color and other physical properties to fibers, blades, laminate composites, and other articles - Google Patents

Abstract

Applying dye to the transfer paper to make the dye transfer paper, placing the colored transfer medium in contact with a fiber, blade or composite material and placing it on an inflatable structure such as an inflatable rig or metal tube, heat, Applying at least one of pressure, or vacuum, to inject the dye into the fiber, blade or composite material, so that the colored fiber, blade or Making a composite material, and transferring the dye to a fiber, blade or composite material. [Selection figure] None

Description

Detailed Description of the Invention

[Background of the invention]
[0001] The present invention relates generally to providing systems and methods related to coloring single fibers, blades and laminate materials.

  [0002] In the textile industry, fiber coloring is a requirement for many commercial, apparel, industrial, medical and aerospace applications, but not for most military applications. However, the laminated reinforcing material is a solid color and is not useful for dyeing or coloring. One known technique for adding color to a laminate material is to paint the material. However, painting the material causes the underside of the paint to peel off during use and fades in the sun over time. These drawbacks can be very significant in flexible laminate materials. In another prior art embodiment, the laminated reinforcing material is combined with an additional layer of film or other material to produce a fiber reinforced flexible fabric. Other additional materials may include more traditional woven fabrics that can be dyed. This type of material is generally found in applications that require high performance, and the visual or cosmetic appearance is less important. The typical accepted appearance is plain as manufactured and / or has no visible color, pattern, or graphic.

  [0003] Ultra high molecular weight polyethylene (UHMWPE) fibers have traditionally been available in only one color, ie milky white only. Such fibers are sold, for example, under the trade names Dyneema (R) and Spectra (R). End-use products that are otherwise suitable by limiting the ultra-high molecular weight polyethylene fiber to only one shade of white, but need a color other than white to meet the required product requirements or specifications In many areas where these requirements cannot be met, the suitability of ultra high molecular weight polyethylene fibers is limited.

  [0004] Previous attempts to dye or color ultra high molecular weight polyethylene fibers, such as Dyneema® or Spectra® fibers, have been resistant to abrasion, environmental exposure, cleaning, or chemical degradation. It is generally not successful because it cannot coat a fiber surface with a typical, non-discolored finish. The lack of dye or colorant adhesion and / or color fastness means that discoloration and possible migration to other surfaces or to the environment is contaminated, discolored or toxic, infected or in the case of medical applications. Particularly problematic in applications that can cause destruction of engineering surface properties such as surface tension, coefficient of friction, lubricity and wettability.

  [0005] Also, attempts to add colorants into polyethylene polymer precursors prior to spinning and drawing operations are primarily due to the effects of chain scission and polymer degradation or interaction between the polymer and the colorant. Often because of the unacceptable degradation of mechanical properties of more than 50%, and the manufacturing complexity and operation that must provide processing difficulties, supply chain issues, and multiple different colored forms of the precursor polymer And due to the cleaning and re-setup of the equipment for different colored fibers, it has not been successful. Even with the use of long downtimes for cleaning, it is very difficult to avoid cross-contamination between different runs of different colors of fibers.

  [0006] Accordingly, it is desirable to produce colored fibers, blades, and laminated reinforcing materials that are colored or colorable, patterned, or otherwise enhanced in other physical properties such as fade resistance.

[Summary of Invention]
[0007] In various embodiments of the present disclosure, dye sublimation coloring techniques are used for coloring ultra high molecular weight polyethylene materials. In various embodiments, the ultra high molecular weight polyethylene material comprises any one of fibers, blades, and laminate composites. For example, the ultra high molecular weight polyethylene material colored according to the method of the present disclosure may comprise drawn ultra high molecular weight polyethylene fibers made by gel spinning techniques such as Dyneema® fibers. The coloring method according to the present disclosure allows a colorant to be injected into the gel spun ultra high molecular weight polyethylene fibers themselves under controlled heat and pressure conditions. In addition to being an effective method of fiber coloring, various embodiments of the dye sublimation coloring method of the present disclosure use a number of readily available coating or transfer methods in a wide range of colors, It can be performed at many points in the fiber or blade manufacturing process after spinning from the polymer solution. This processing flexibility increases process utility and economic efficiency while allowing color to be applied at some point in the product stream that streamlines and simplifies the invention and process flow.

  [0008] More importantly, although other coloring techniques can adversely degrade the mechanical properties of ultra high molecular weight polyethylene fibers by as much as 50% or more, the colorant on the fibers themselves by the dye sublimation method of the present disclosure Injection should be achieved without significantly changing the mechanical properties of the fiber, such as strength and engineering Young's modulus, both important for ultra high molecular weight polyethylene fibers and for the primary selling point of this fiber Can do.

  [0009] In various embodiments of the present disclosure, ultra high molecular weight polyethylene fibers and blades do not (a) reduce fiber / blade tensile strength by more than 10% and (b) leave excessive colorant residue. And (c) without surface coating (colorant / dye only) and was colored in more than one color in multiple portions along each fiber or fiber blade. In various embodiments, the method includes winding the fiber around an inflatable mandrel and expanding the mandrel to stretch the fiber during the coloring process.

  [0010] In various embodiments, a method of transferring a dye to a composite material includes applying a dye to a transfer medium to make a colored transfer medium, placing the colored transfer medium in contact with the composite material, and autoclaving. Applying at least one of heat, external pressure, and vacuum pressure, such as by use, to inject the dye into the composite material to produce a colored composite material. The method may further include cooling the composite material to a temperature such that the composite material maintains a desired shape. In various embodiments, the method may further comprise curing the dye by applying at least one ultraviolet or electron beam radiation to the composite material. The method may further include adding a coating (eg, polyimide) to the composite material. Further, the method may further comprise adding a polyvinyl fluoride (PVF) film to the composite material and / or adding a nylon and / or urethane coating to the composite material. In various embodiments, the film is used as a color transfer medium that remains as a film coating on the composite material after the coloring process.

  [0011] In various embodiments, the composite material comprises a non-woven material or a woven material. In various embodiments, the composite material includes at least one layer of woven material and at least one layer of non-woven material. The transfer medium may include at least one of transfer paper, a transfer laminate, or a transfer film. The dye may be applied to the transfer medium in the form of a pattern, graphic or logo where the composite material is injected with a matching pattern, graphic or logo, respectively. In addition, the dye may be applied to the transfer medium using direct printing.

2 illustrates an exemplary embodiment of a rotating color transfer system. 2A and 2B show an exemplary embodiment of a heated press color transfer system and the corresponding pressure graph. Shows a flowchart of a typical hot press process; 4A and 4B show an exemplary embodiment of the autoclave color transfer system and the corresponding pressure graph. A flow chart of a typical autoclave method is shown. 1 illustrates an exemplary embodiment of a linear color transfer system. 2 illustrates an exemplary embodiment of a multi-layer color transfer laminate. 3 illustrates an embodiment of an inflatable structure according to the present disclosure. FIG. 4 illustrates an embodiment of an autoclave cure schedule for fiber and blade specimens plotted as temperature versus time for both autoclave temperature (° F.) and part temperature (° F.). FIG. 4 illustrates an embodiment of an autoclave cure schedule for fiber and blade specimens plotted as pressure / vacuum versus time for both autoclave pressure (psi) and vacuum (psi). Figure 8 shows the results of a tensile test of a Spectra (R) fiber blade of as received material. FIG. 5 shows tensile test results for a Spectra® fiber blade of as received material in a plot form. The tensile test result of the Spectra (registered trademark) fiber 1740 dtex blade of the dyeing material is shown. Figure 8 shows the tensile test results of a Spectra (R) fiber 1740 dtex blade of dyed material in plot form. FIG. 5 shows a plot of toughness versus tensile strain for Spectra® 1000, 400 denier fiber as received. Figure 5 shows a plot of toughness versus tensile strain for dyed Spectra (R) 1000, 400 denier fibers.

[Mode for Carrying Out the Invention]
[0028] While exemplary embodiments have been described herein in sufficient detail to enable those skilled in the art to practice the invention, other embodiments may be implemented, and It should be understood that logic material, electrical, and mechanical changes may be made without departing from the spirit and scope of the invention. Accordingly, the following detailed description is presented for illustrative purposes only.

[0029] [Material]
[0030] In various embodiments, fibers, blades, fabrics, and laminate materials are colored according to the present disclosure. Various types of fibers and blades include, for example, Dyneema® or Spectra® brand ultra-high molecular weight polyethylene materials. In various embodiments, ultra high molecular weight polyethylene fibers are colored and improved by the method according to the present disclosure. Ultra high molecular weight polyethylene is a type of polyolefin made from very long chains of polyethylene. Trade names include Dyneema (registered trademark) and Spectra (registered trademark). Ultra high molecular weight polyethylene is also referred to in the industry as high modulus polyethylene (HMPE) or high performance polyethylene (HPPE). The molecular weight (MW) of ultra-high molecular weight polyethylene is often expressed as "Intrinsic Viscosity Number" (IV), which is typically at least 4 dl / g and preferably at least 8 dl / g. Generally, the intrinsic viscosity of ultra high molecular weight polyethylene is less than about 50 dl / g, preferably less than about 40 dl / g. In various embodiments, the ultra high molecular weight polyethylene fiber comprises extruded polymer chains. In various embodiments, the ultra high molecular weight polyethylene fiber comprises drawn polymer chains.

  [0031] Various types of composite materials include both woven and non-woven materials. In an exemplary embodiment, the woven material includes a number of low denier tows (ie, a lightweight woven material). Woven materials include fibers that pass up and down one another in the weave, which can provide some degree of crimp to the fibers. Further, in the woven material, when the crimped fibers are going to be straight, the tensile load generates a lateral load in the overlapping portion of the fibers. Lateral loads reduce the conversion from fiber strength to fabric strength and reduce long-term fatigue and creep rupture performance. In an exemplary embodiment, higher performance engineering fibers have more pronounced crimp reduction properties. This is particularly noticeable in fibers where the axial filament properties are optimized to reduce the transverse properties of the filament.

  [0032] As used herein, a composite material is defined as one or more layers of unidirectional fibers and a polymer matrix monolayer oriented in one or more directions. For example, unidirectional fibers in adjacent single layers may be offset at an angle between those directions. In contrast, in an exemplary embodiment, the nonwoven composite material uses a high denier tow for easier manufacturability. Nonwoven composites, such as felt, contain fibers that do not pass up and down with each other and therefore do not have crimps. The advantage of nonwoven composites is that the fiber area weight, which is the weight of fibers per unit area, is unlimited. In other words, thicker fibers can be used in non-woven materials versus woven materials. Another advantage of nonwoven composites is that composites can be formed from multiple layers of fibers oriented at any angle to the fibers in other layers. Further, in an exemplary embodiment, the nonwoven composite material is designed to have optimal weight, thickness, and strength at a particular location or along a desired predetermined load path. Furthermore, nonwoven composites made from high modulus fibers can have predictable and linear properties for industrial design.

  [0033] According to an exemplary embodiment, colors are injected into the composite material during the manufacturing process. In various embodiments, the composite material can be, for example, ultra-high molecular weight polyethylene (eg, commercially available as Dyneema®), Vectran®; aramid; polyester; carbon fiber; Zylon PBO, or resin or It includes one or more layers of thinly spread high strength fibers such as other materials coated and / or embedded with other materials, or any combination thereof. Certain preferred embodiments of the present invention relate to the coloring of composite materials comprising one or more layers of thinly spread high strength ultra high molecular weight polyethylene fibers.

[0034] In the context of the present invention, "high strength" has a tensile strength of at least 1.5 GPa, preferably 2.5 GPa, more preferably at least 3.6 GPa and most preferably at least 4.2 GPa. Fibers that are colored according to the methods disclosed herein may be characterized by various physical properties in addition to characterization by specific chemical composition. These properties relate to, for example, fiber stretch and strength. Tensile properties (measured at 25 ° C.): Tensile strength (or strength), tensile modulus (or modulus) and elongation at break (or EAB) are nominal gauge length of 500 mm fiber, 50% / min Stipulated and determined with multifilament yarns as specified in ASTM D885M. Based on the measured stress-strain curve, the elastic modulus is determined as a strain gradient between about 0.3-1%. For elastic modulus and strength calculations, divide the measured tensile force by the titer determined by weighing 10 meters of fiber; assuming a density of 0.97 g / cm ³ , the value in GPa is calculate.

  [0035] Polymers such as polymers used for fibers are generally in accordance with ASTM D1601-2004 (at 135 ° C in decalin) by extrapolating the viscosity measured at different concentrations to zero concentration. The dissolution time is 16 hours and has an “intrinsic viscosity number” (IV) that can be determined using DBPC in an amount of 2 g / l solution as an antioxidant.

[0036] Linear polymers may also be characterized by the amount of side chains present. For example, to determine the number of side chains in an ultra high molecular weight polyethylene sample by FTIR on a compression molded film of 2 mm thickness, based on NMR measurements (eg as disclosed in EP 0269151) The calibration curve is used to quantify the absorption of infrared light at a wavelength of 1375 cm ⁻¹ .

  [0037] The injected color may appear as a solid color, pattern, or any type of graphic such as a picture or logo on one or both sides of the composite material. Other possibilities include producing composite materials having stripes, polka dots, figures, shapes, etc. In an exemplary embodiment, the laminate film and / or fabric may also interact with the color process, synergize, or other sublimable or non-sublimable tints, color base, modified, pre-mixed to improve. It can have a quality agent or UV or color stabilizer.

  [0038] Colorants that can be used for sublimation / diffusion according to the present disclosure may include dyes or pigments or combinations thereof. For example, the sublimation dyes used herein typically range from the following classes of dyes: acid dyes, vat dyes, pigments, disperse dyes, direct dyes and reactive dyes. In various embodiments, disperse dyes and direct dyes are preferred. These dyes are prepared from a class of organic chemicals known as azo, anthroquinone and phthalocyanine dye systems. In other embodiments, the color possibilities include titanium dioxide, carbon black, phthalo blue, quinacridone red, organic yellow, phthalo green, dark yellow ocher, ercolano orange, venetian red, burnt amber, viridan green, ultramarine blue and pewter. Pigments such as gray are included. In some embodiments of fiber, blade and composite coloration, royal blue, aqua blue, black, steel head gray, process yellow, fire red, scarlet red, process red, rubin red, magenta, navy blue, process blue , And Kelly Green sublimation dyes are useful and can be used alone or in various combinations for coloring patterns. The terms “dye” and “pigment” are used interchangeably herein to refer generally to colorants for a process.

  [0039] In other various embodiments, the composite material also has various coatings applied to alter various surface properties of the material. Various coatings can be in addition to or as an alternative to the color dyes added to the material. In a first exemplary embodiment, a thin film coating is added to the material. Use specific thin film coatings to increase or decrease the tensile strength, toughness, chemical and dimensional stability, weldability, gas barrier properties, electrical properties, high heat resistance, UV or infrared performance of composites And / or the coefficient of friction can be reduced. In a second exemplary embodiment, a polyimide coating is added to the composite material. Polyimide coatings can change the electrical and dielectric properties of the material. Furthermore, the polyimide coating may be configured to increase the stability of the material properties over a wide range of temperatures. In a third exemplary embodiment, a film, such as a polyvinyl fluoride (PVF) film (Tedlar®) is added to the composite material. Films such as PVF films promote additional weather resistance, long-term durability, and environmental stability. Similarly, in a fourth exemplary embodiment, the nylon and urethane coatings both increase toughness, reduce mechanical properties and permeability, and are flexible. In other embodiments, the dye transfer medium includes a dye-coated film that remains behind as a layer of composite material after the coloring process.

  [0040] According to exemplary embodiments, a composite composite may be made by layering a woven coating on a composite. A woven coating can be introduced to increase wear resistance. For example, the woven coating on the composite material may include a nylon woven layer. Further, in an exemplary embodiment, the hybrid composite material may be designed to combine various material properties of the composite material and the coating to provide a high strength, dimensionally stable flexible composite material. Typical applications for hybrid composites include military applications such as advanced visual camouflage and / or infrared signature reduction. Another example is the use in ballistic armor vests.

  [0041] In an exemplary embodiment, sublimation implantation is performed to add various things to the composite material. This includes, for example, color, pattern and gloss applications, improved specular or infrared reflectivity, antimicrobials or agents, surface adhesion modifiers, nanomaterial injection, dielectric modifiers, electrical / Printing of conductive metal or polymer materials to add dielectric conductivity features or electrical circuit patterns, and / or introduction of synergistic components for flame retardant or flame retardant materials in laminates, surface films, or surface fabrics May be included. In an exemplary embodiment, UV stabilizers or curing additives are introduced into the material. These additives can extend the useful life of the composite material.

  [0042] Further, in various embodiments, a flame retardant adhesive or polymer is used with the composite material. Furthermore, a flame retardant may be added to the flammable matrix or film to improve the flame resistance of the composite material. Flame retardants may function in several ways, such as endothermic decomposition, heat shielding, gas phase dilution or gas phase radical quenching. Examples of flame retardants include DOW D.D. E. R. 593 brominated resins, DOW Corning 3 flame retardant resins, and polyurethane resins with antimony trioxide (eg, EMC-85 / 10A from PDM Neptec Ltd.), although other flame retardants are also known to those skilled in the art May be suitable as such. Still other examples of flame retardants that may be used to improve flame resistance include Fyrol FR-2, Fyrol HF-4, Fyrol PNX, Fyrol 6, and SaFRon 7700, but other additives may also be used. May be suitable as known to those skilled in the art. In various embodiments, flame retardant and self-extinguishing features are also added to the fiber by either using flame retardant fibers, ceramic or metal wire filaments, intrinsic flame retardant fibers, or coating the fibers. May be. Examples of flame retardant fibers include Nomex® or Kevlar®. Intrinsically flame retardant fibers include fibers in which a flame retardant compound is added directly to the fiber formulation during the fiber manufacturing process. In addition, the fibers may be coated with a sizing polymer or adhesive that introduces a flame retardant compound, such as the flame retardant compounds described herein or other suitable compounds known to those skilled in the art. In yet another various embodiment, any woven or scrim material used in the composite material is pretreated for flame retardancy by the supplier or coated with a flame retardant compound during the manufacturing process. Or injected. In an exemplary embodiment, UV stabilizing or curing additives are introduced into the composite material. These additives can extend the useful life of the material.

  [0043] In various embodiments, the composite material is assembled as a multi-layer composite of outer layers that may be colored or textured by any of the various application methods presented herein. The outer layer may be a unidirectional monolayer, film, nonwoven fabric or felt, woven fabric, weldable thermoplastic membrane, waterproof breathable membrane and woven scrim. These exterior materials may have an initial coloring or patterning that complements various methods of injection transfer, sublimation transfer or roll transfer to achieve the desired cosmetic or visual effect. In addition, various powder tints, coloring dyes or sublimation colorants to adjust the saturation, hue, opacity or light transmission of the finished coloring material can also be used as unidirectional single layer adhesives or laminating resins. Can be added to the ingredients. One or more opaque or shading tinted films may be added between one or more single layer interfaces to further adjust the saturation, hue, opacity or light transmission of the finished coloring material.

  [0044] Industrial and technical textiles, apparel, sports equipment, water sports, boating and sailing materials, canvas, hunting and fishing, balloons and light aircraft, commercial fabrics, upholstery, inflatable structures, military apparel, gear In addition to medical or protective articles or devices, tensile structures, seismic structural reinforcement materials, banners and signage, there are several applications that are suitable for composite materials in other flexible materials or textile applications, where flexible High performance, light weight, high strength, tear resistance, high flexibility, flex life, durability, weather resistance and unique properties of highly functional composites are highly desirable, but cosmetic or visible coloration, patterns, graphics and other Visual characteristics or effects are also an important component of the intended purpose of a material or product. . Also, absorption or reflection of various wavelengths of ultraviolet, visible, infrared, or other regions of the electromagnetic spectrum and / or surface texture or shape, gloss or glitter, opacity, light transmission or blocking, or color fastness Also desirable are properties such as fading resistance.

  [0045] Apparel, outdoor, with special requirements or characteristics such as flame resistance or fire resistance, anti-odor, anti-mold or anti-microbial resistance, water resistance and / or breathability, chemical resistance or abrasion resistance Many combinations of these potential uses are consumer-oriented, such as sports equipment, hunting and fishing, water sports, boating and sailing, or medical textiles or textiles, so any combination of methods and materials It is believed to achieve desirable properties for the intended application.

[Color application method]
[0046] Various methods may be implemented to facilitate transfer of the dye to the composite material. These methods are generally two types of processes: continuous processes and batch processes. A continuous process is a method in which material is unwound at a constant web speed or at a constant stepwise stop start speed. The material is assembled, consolidated, colored, textured, and then rewound on a rewind roll. In a batch process, the composite components and colorant are loaded into a press, vacuum bag or autoclave and then subjected to a heating / curing process.

  [0047] In accordance with exemplary embodiments, various methods of dye transfer include thermal transfer from a print or impregnated carrier; direct printing onto a laminate or surface film with an ink jet or dye sublimation printer; dye, tint, or sublimation. Introducing a color or pattern directly onto or into the composite material or matrix; thermal transfer onto the composite material or film; and bath or dip injection may be included. In typical embodiments, sublimation inks are used for more durable and permanent coloration.

  [0048] Color is applied to the composite material using a transfer carrier substrate according to typical methods. As a first step, a transfer carrier such as film or paper is selected. The applied color may be a solid color or it may be a pattern or graphic placed on the transfer carrier. The transfer carrier coloring method may use at least one of an inkjet printer, a gravure roll coater, a slot die coating head, a dip bar tank coating, an anilox roll coating, a roll type knife coater, a reverse roll coater, and an air knife coater. Good. In various exemplary embodiments, the application of solid color to the composite material can be done by direct printing or on the desired surface, layer, or interface of the laminate material using an autoclave, belt press, vacuum furnace, etc. It may be facilitated by transcription.

  [0049] In various exemplary embodiments of direct printing, applying the pattern or graphic to the composite material is at least one of the use of inkjet printers, sublimation printers, flexographic printer methods, anilox roll printing, and offset printing. You may be encouraged by one.

  [0050] Various methods for transferring, injecting, or sublimating a color or pattern onto a composite material using a separate carrier, regardless of whether a solid color is transferred or a pattern / graphic is transferred And the transfer carrier substrate is in close proximity to the composite so that heat can be applied by the system.

  [0051] Various systems and methods applied to achieve color transfer to composite materials include heated rotation systems, heated press systems, autoclave systems, dye injection systems, heated linear color transfer systems, vacuum furnaces and mothers. Material pigment tint coloring is included.

[Heating rotation system]
[0052] In an exemplary embodiment and with reference to FIG. 1, a rotating color transfer system 100 includes a rotating heat roll 110, a stretch belt 120, a roll 130 of color receiving material, and a color transfer carrier 140. . The rotating color transfer system 100 is a continuous roll-to-roll process for applying colors or graphics to the material 130. The color receiving material 130 may be a woven fabric, a cloth, a film, or a laminated material. In that case, films or fabrics can be used in the manufacture of composite materials. For example, a roll of finished composite, film or fabric precursor may be fed into the rotating color transfer system 100 to place or inject color. In an exemplary embodiment, the material 130 may be pre-coated or pre-printed with color before being fed through the belt press portion of the rotating color transfer system 100.

  [0053] In other embodiments, the color transfer carrier 140 may be a film or paper. The color transfer carrier 140 can be fed from an unwinding roll and processed through the rotating color transfer system 100 to transfer a color or pattern to a material 130 such as a film, fabric, and composite material. Therefore, the extension belt 120 is in contact with the rotating heat roll 110. Further, the material 130 and the color transfer carrier 140 are processed while being brought into contact with each other, and are unwound between the rotary heat roll 110 and the stretching belt 120. The color can be applied to the material 130 by direct printing, either inline or offline. The in-line process comprises applying or coating a color or pattern on a composite material, film or fabric, or color transfer carrier 140 as part of the belt press portion of the rotating color transfer system 100. The offline process involves applying or coating a color or pattern to a laminate, film or fabric, or color transfer carrier 140 as part of a separate batch process before being placed on the belt press portion of the rotating color transfer system 100. Have. In an exemplary embodiment, the heated rotating belt 120 can be used in-line with the lamination process. In addition, colors can be transferred from the color transfer carrier 140. In an exemplary embodiment, a vacuum is created between the rotating heat roll 110 and the stretch belt 120 to facilitate color injection and transfer. Various methods may be used to create the vacuum as known to those skilled in the art.

  [0054] In an exemplary embodiment, and as shown in FIG. 1, the color transfer carrier 140 is closest to the rotating heat roll 110 and the material 130 is closest to the stretch belt 120. In other exemplary embodiments, the material 130 is closest to the rotating heat roll 110 and the color transfer carrier 140 is closest to the stretch belt 120. In an exemplary embodiment, material 130 and color transfer carrier 140 are both individual rolls that are unwound and processed by the rotating belt process described above, and then rewound onto the individual rolls.

[Heating press system]
[0055] In accordance with an exemplary embodiment and with reference to FIGS. 2A and 2B, a heated press color transfer system 200 includes two plates 210 or other similar hard surfaces, a color receiving material 220, and a color carrier. 230. In another embodiment, the hot press color transfer system 200 further includes a pressure intensifying layer 240 made from natural rubber or synthetic rubber. By way of example, suitable backing rubber is manufactured by Torr Technologies or Airtech International. The boost layer 240 is coupled to the inside of at least one of the two plates 210 such that the boost layer 240 is between the two plates 210 and is in contact with the composite material 220 and / or the color carrier 230. To. In an exemplary embodiment, the pressure intensifying layer 240 has at least some compression capability. By compression, additional pressure is applied to the two plates 210 and transferred to the material 220 and the color carrier 230. In various embodiments, the pressure intensifying layer 240 is a combination of one or more smooth mirror surfaces, a smooth matte surface, and a textured or patterned surface that provides the desired surface gloss or texture that complements the colorant. You may have.

  [0056] In a typical method and with reference to FIG. 3, the hot press method 300 comprises four main steps. First, color tint / dye transfer to a color carrier, which may comprise a composite material having a surface film or fabric surface on one or both sides, or may comprise a transfer paper / film carrier (310). Apply. In various embodiments, the film or fabric surface may introduce a complementary color or pre-printed pattern, image or design on one or both sides of the laminate. Further, the transfer paper / film carrier may comprise a solid color, one or more color patterns or printed graphics to form an image, design, or picture. In addition, the transfer medium may also comprise a smooth or textured surface that provides a surface having a desired degree of gloss or smooth texture pattern on one or both of the colored surfaces. Second, the color tint / dye transfer is placed in contact with the composite material (320). Third, heat and pressure are applied to transfer, sublimate, and / or inject color, graphics, textures or patterns into the material (330). The temperature typically ranges from about 70 ° F. to about 650 ° F., and the pressure ranges from a minimum pressure to maintain the material in intimate contact, typically from 2 psi up to 10,000 psi. The temperature and pressure applied will depend on the particular colorant used, the substrate to which the colorant is applied, and the degree of lamination or compaction required. Fourth, cooling the material to a temperature such that the finished product remains flat or in the desired shape and is free of damage, deformation, or delamination of the finished colored material. When the system is below the removal temperature, the material and color carrier are removed from the hot press (340).

  [0057] In yet another exemplary embodiment, the heated press color transfer system further includes a vacuum to increase pressure in the process. A typical vacuum may be created either by sealing the press platen in a sealable vacuum chamber or by sealing the laminate in a vacuum bag system. The applied vacuum can range from about 5 to about 29 inches of mercury (Hg). When vacuum is applied, the assembly is placed in the press so that the press platen applies the appropriate pressure profile between the heating and cooling cycle profiles.

  [0058] By introducing a vacuum, the sublimation colorant helps to enter the substrate, lowers the temperature at which sublimation colorant transfer occurs, removes any trapped air or bubbles from the material, and more Useful to prevent oxidation at high temperatures. Where appropriate, the material may be exposed to ultraviolet or electron beam radiation to cure or harden the curable tint or dye.

[Autoclave system]
[0059] In accordance with an exemplary embodiment and with reference to FIGS. 4A and 4B, an autoclave color transfer system 400 includes a rigid or reinforced elastomer tool plate 410 and, optionally, a rigid or elastomeric backing plate 420 within a vacuum bag 430. Including. In various embodiments, the tool plate 410 is typically a rigid plate with a smooth surface, while the caul plate 420 may be thinner and / or more familiar with the tool plate 410. The vacuum bag 430 may be made from a flexible impervious material or may be a flexible impervious elastomeric diaphragm. Alternatively, the decompression bag 430 may be sealed to the side surface or the outer surface of the first caul plate 410. The vacuum bag 430 is typically 0.001 to 0.015 inch thick nylon or other film sealed with a tape or strip of adhesive high temperature caulk. Suitable bags and sealant materials include Airtech Securlon L500Y nylon vacuum bag and TMI adhesive tape or Aerotech AT-200Y sealant tape. In addition, when a diaphragm is used instead of a vacuum bag, the diaphragm is typically a low durometer, high heat resistant silicone rubber and generally has a thickness of 0.032 to 0.060 inches.

  [0060] Instead of direct printing or color transfer to the material, the autoclave system 400 further includes one or more color transfer carriers 440 and a colorant-receiving material or laminate 450. The color transfer carrier 440 is placed in contact with the receiving material 450, where both are between the tool plate 410 and the backing plate 420. For embodiments where there is high pressure and high temperature work or where there is a large area, a permeable felt or non-woven breather material is provided on the backing plate to provide uniform compaction pressure, under the vacuum bag 430 Air may flow freely. An example of a suitable breather material is Airtech Airweave 10. Air inside the vacuum bag 430 is removed by a vacuum tap 460 that creates a pressure differential within the system 400 to provide compaction pressure to the parts inside the vacuum bag 430. In an exemplary embodiment, the vacuum bag 430 may be placed in a pressurized autoclave 470 so that the high pressure in the autoclave 470 outside the vacuum bag 430 is raised to a predetermined level. This predetermined level may be from ambient atmospheric pressure to 1000 psi to provide compaction force, while the pressure under vacuum bag 430 is maintained at a vacuum of less than 2 inches to about 29 inches Hg. .

  [0061] In an exemplary embodiment, heat is more easily generated in a high pressure environment to facilitate transfer of the dye to the receiving material 450. The temperature in the autoclave may be set to a predetermined heating rate profile, temperature holding and cooling profile. Typical temperature ramp rates vary from 2-50 ° F./min up to temperatures in the range of 70 ° F. to 600 ° F., and cooling rates range from 2-20 ° F./min. Due to the cooling profile, the material is cooled to a temperature such that the finished product remains flat or in the desired shape and is free of damage, deformation or delamination of the finished colored material. When the system is below the removal temperature, the material and color carrier are removed from the autoclave and removed from the bag. In an exemplary embodiment, the autoclave color transfer system 400 is very effective and can be introduced into the composite manufacturing process.

  [0062] In an exemplary method and with reference to FIG. 5, the autoclave method 500 includes four main steps:

  [0063] (1) Applying color tint / dye transfer to a color carrier or transfer paper / film carrier, which may comprise a laminate having a surface film or fabric surface on one or both sides (510) . The film or fabric surface may introduce complementary colors or pre-printed patterns, images or designs on either or both sides of the laminate. The transfer paper or media may comprise a continuous area of a single color, a single color or multiple color pattern, or a printed graphic of any combination of colors to form an image, design or picture. The transfer medium may also comprise a smooth or textured surface that provides a surface having a predetermined degree of gloss or a smooth texture pattern on one or both sides of the colored surface.

  [0064] (2) Placing the color tint / dye transfer in contact with the composite (520).

  [0065] (3) Applying heat and pressure and vacuum to transfer and / or inject or sublimate a color, graphic, texture, or pattern into the material (530). The temperature typically ranges from about 70 ° F. to about 650 ° F., and the pressure ranges from the minimum pressure to keep the material in intimate contact, typically from ambient atmospheric pressure up to 1000 psi. The temperature and pressure applied will depend on the particular colorant used, the substrate to which the colorant is applied, and the degree of lamination or compaction required. and

  [0066] (4) Cooling the material to a temperature such that the finished product remains flat or in the desired shape and is free from damage, deformation, or delamination of the finished colored material. When the system is below the removal temperature, the material and color carrier are removed from the vacuum bag tool assembly (540). In various suitable embodiments, the material may be exposed to ultraviolet or electron beam radiation to cure or harden the curable tint or dye.

[Linear color transfer system]
[0067] In an exemplary embodiment and with reference to FIG. 6, a linear color transfer system 600 includes a rotating horizontal belt press 610, a film or membrane 620, and a color transfer carrier 630. The endless rotating belt forms a continuous process in which uniform, continuous compaction pressure can be applied to the composite material 650 and the color transfer film or paper carrier 630 to maintain adhesion for injection or sublimation color transfer. The material is heated to a sufficient temperature, color injection is performed in the pressurized heating zone, and then the composite material and the color transfer medium are cooled to a temperature that is below the safe removal temperature of the composite material. The linear color transfer system 600 may be a continuous roll-to-roll process for applying colors or graphics to the composite material 650. The color-receiving composite material 650 may be a woven fabric, cloth, film, or laminate material. In that case, the film or fabric 620 may be used in the manufacture of composite materials. For example, a web of laminated layers of finished composite, film or fabric 620 precursor rolls may be fed into the linear color transfer system 600 to place or inject color. In an exemplary embodiment, the material 650 may be pre-coated or pre-printed with color before being fed through the belt press portion 610 of the linear color transfer system by a printer, coater or processor 660.

  [0068] The colored composite material is then optionally fed into a set of calenders or embossing rolls 670 to apply a smooth glossy or matte surface to the composite material or to apply a texture to one or both of the outer surfaces. You may apply. The optional roll 670 may be heated, cooled, or brought to room temperature depending on the desired surface finish, surface texture, exit temperature of the composite material from the belt portion of the press, or a specific material. Typical feed rates for composite webs range from 2 to 250 feet / minute. The roll 670 and the belt portion of the press 610 are set to a predetermined gap, or set to a preset pressure so as to be a preset roll gap, or set to a predetermined pressure by setting the gap to zero with the preset pressure. Complete consolidation with a distribution can be ensured. Typical gap settings range from 0.0002 inches to 0.125 inches and typical pressures range from 5 to 1000 lbf / line inch width. The roll and belt system can be heated to consolidate the material and / or transferred, injected or sublimated onto one or both sides of the composite material. Individual monolayers of composite may be unwound from a roll by hand layup, by automated tape layup or by automated robotic pick and place operations and laid on the composite web. Typical heating temperature setpoints range from 70 ° F to 550 ° F.

  [0069] Further, typical heating temperature setpoints range from 70 ° F to 550 ° F.

  [0070] Radiation curing systems such as electron beam or ultraviolet lamp arrays can be placed in-line. One advantage of a linear system is thereby the assembly of layers of unidirectional fiber monolayers to structural reinforcement, the application of colorants, the introduction of various optional internal or surface film layers, nonwoven material layers and woven layers. Can be integrated to form a multi-stage integrated manufacturing process in which the unidirectional fiber base monolayer is converted to a finished colored roll article.

[Color injection of multilayer composite materials]
[0071] In an exemplary embodiment, color injection of a multilayer composite material can be performed using either a heated press color transfer system, such as system 200, or an autoclave color transfer system, such as system 400. In either process and with reference to FIG. 7, a multi-layer laminate comprising a plurality of caul plates 710, a barrier / breather layer 720, a color carrier 730 and a laminate 740 is described in system 200 and system 400. And a single laminate of color carriers.

[Batch dye injection]
[0072] In an exemplary embodiment, composite materials, surface films, and surface fabrics can also introduce color by batch dyeing or pouring. In this process, a roll of composite material, film or fabric is impregnated with a color medium or tint, placed in a container and subjected to an appropriate heat, pressure or vacuum profile for use in injecting the color medium. The film or fabric thus treated may then be introduced into the laminate.

[Base material pigment and tint coloring]
[0073] As an alternative to dye sublimation / diffusion into fibers and blades, pigments may be added to the adhesive resin used in the unidirectional fiber monolayer manufacturing process, thereby making it later in composite manufacturing. It may result in the color-implanted unidirectional tape being used. For example, materials that can be added directly into the adhesive resin include, but are not limited to, titanium dioxide, carbon black, phthalo blue, quinacridone red, organic yellow, phthalo green, dark yellow ocher, ercolano orange, venetian red, burnt amber, Pigments such as Viridjan Green, Ultramarine Blue and Pewter Gray are included. The colored composite material obtained by the use of colored unidirectional fiber monolayers in the exemplary embodiment is the process described above, namely, heated rotation system 100, heated press system 200/300, autoclave system 400/500, linear system 600. Further coloration using multi-layer laminate color injection 700 and / or batch dye injection may be used.

[0074] [Fiber and Blade Coloring Under Stretching Conditions-General Issues]
[0075] In various embodiments, the fibers or blades are under tension during coloring. Stretching while coloring is believed to stretch the fiber to some extent, offsetting the shrinkage of the fiber and negating the additional weight of colorant added per fiber line length. While not wishing to be bound by any particular theory, it is believed that controlling the inherent shrinkage of the fiber by stretching during heating minimizes disruption of the stretched polymer chains in the fiber. The stretching may be kept relatively constant during coloring, or the stretching may change (increase or decrease) while coloring. Also, pre-stretched fibers may subsequently relax to some extent when exposed to heat during coloring, even if the fiber tension during coloring is less than the pre-stretch applied before coloring. Means good.

  [0076] In one variation, a fiber or blade is wrapped around an adjustable rig and pre-stretched to the desired tension (ie force) before the start of the coloring process. Such inflatable structures are, for example, inflatable tubular structures such as expansion cylinders having circumferentially arranged segments that are separated from each other by the action of bolts having a diameter larger than the inner diameter (ID) of the unexpanded segment. May be included. Such a rig is sometimes referred to as an “expansion clamp for maintaining the inner diameter”. More elaborate variants of rigs push the paired elements (such as rods) in the opposite direction, increasing the distance between the pairs, thus increasing the tension applied to the fibers or blades wrapped around them. An increasing ratcheting mechanism may be included. The fiber or blade pre-stretch can be up to any level of stretch that is numerically less than the break point of the fiber or blade. That is, the fibers or blades may be pre-stretched to a percentage (<100%) of their breaking strength. For example, to color ultrahigh molecular weight polyethylene fibers having a tensile strength of about 3.6 GPa, pre-stretching the fibers at 20 ° C. to 1-30% of their breaking strength is from 36 MPa to about 0.00. Equivalent to prestretching the fiber before coloring to a force of 36 GPa. In various embodiments, the fiber is pre-stretched around a suitable rig at 20 ° C. to a force equal to 1-30% of the fiber's breaking strength. In other embodiments, the fiber is pre-stretched at 20 ° C. to a force equal to 2-20% of the fiber's breaking strength. In other embodiments, the fiber is pre-stretched at 20 ° C. to a force equal to 3-10% of the fiber's breaking strength. The dye transfer paper may be placed on the rig before winding the fiber on the paper and before pre-stretching with an expansion bolt or ratcheting mechanism. In various embodiments, another layer of dye transfer paper is placed over the prestretched fibers. Next, an assembly rig having one or more dye transfer papers on one or both sides of the wound and pre-stretched fibers is heated to sublimate and diffuse the colorant from the transfer paper into the fibers. In other embodiments, the fiber is pre-stretched on a stretch rig and then the rig is simply dipped into a heated dye container until the stretch fiber is colored.

  [0077] In another variation, the fiber or blade is wrapped around a structure that expands during the coloring process, in which case there is little or no tension at the beginning of the coloring process when the fiber or blade is stretched. To the desired tension during the coloring process. Such a structure may expand at a measurable and predictable rate when heated at least about 10 ° C. above ambient temperature. For example, the diameter of an aluminum tube or mandrel expands at a known rate upon heating based on the known coefficient of thermal expansion (CTE) of aluminum. For example, a gradual increase in tube diameter when an aluminum tube is heated to a temperature increase of at least 10 ° C. during fiber coloring will increase the stretch of fibers wrapped around the tube.

[0078] Ultra high molecular weight polyethylene fibers, such as Dyneema® fibers, have a negative coefficient of thermal expansion. That is, these types of fibers shrink when heated. The coefficient of thermal expansion of the ultrahigh molecular weight polyethylene fiber is about −12 × 10 ⁻⁶ / K. Given this known shrinkage, an expanded structure, such as a metal tube, having a coefficient of thermal expansion substantially opposite to that of the fiber is selected, and the expanded structure becomes less of the fiber during the coloring process when a temperature increase of at least 10 ° C. occurs. It is preferable to cancel or cancel out the shrinkage. For example, aluminum has a coefficient of thermal expansion of 22.2 × 10 ⁻⁶ / K and is therefore of the magnitude necessary to offset the shrinkage of ultra high molecular weight polyethylene fibers during the same heating. Can see. Copper has a coefficient of thermal expansion of 16.6 × 10 ⁻⁶ / K, high-purity iron is 12.0 × 10 ⁻⁶ / K, and cast iron is 10.4 × 10 ⁻⁶ / K. Therefore, it is manufactured from these metals. Structures such as tubes are expected to stretch into ultra high molecular weight polyethylene fibers during the coloring process, where a temperature increase of at least 10 ° C. occurs.

[0079] In various embodiments, the expandable structure includes a tube made of a material having a coefficient of thermal expansion of about 5 x ^10-6 / K to about 30 x ^10-6 / K. In various embodiments, the inflatable structure is a tube made from glass, metal, granite, concrete or quartz. In various embodiments, the metal is selected from the group consisting of aluminum, copper, high purity iron, cast iron, silver, lead, nickel, palladium, and stainless steel. In various embodiments, the expandable structure is a glass, metal, granite, concrete, or quartz tube having an inner diameter of about 20 times the wall thickness. The length of the tube is primarily the size of the autoclave or other system used to apply at least one of heat, pressure, force and vacuum, the scale of the coloring process (for example how many meters of fibers are colored The width of the composite material to be colored, the cost of the tube, and the like.

  [0080] For indirect coating of stretch fibers, a commercial transfer paper impregnated with a dye sublimation colorant with a solid and patterned color may be used as the dye transfer medium. Although these transfer papers are suitable for small scale processes, dye sublimation colorants can be applied directly to tooling mandrels or process equipment by a wide range of coating methods such as gravure coating for manufacturing applications.

  [0081] In various embodiments, a method of transferring a dye to a fiber, blade or composite material comprises: a) winding the fiber, blade or composite material on an inflatable structure; and b) transferring the dye to a transfer medium. Applying a colored transfer medium to the substrate, c) placing the colored transfer medium in contact with the fiber, blade or composite material; and d) applying at least one of heat, external force, external pressure and vacuum pressure. Injecting dye into the fibers, blades or composites to produce colored fibers, blades or composites. The temperature for this process is typically in the range of about 70 ° F. to about 650 ° F., and the pressure is a minimum pressure to keep the material in intimate contact, typically from ambient atmospheric pressure up to 1000 psi. Range. In a preferred embodiment, the temperature of the coloring process is close to, but lower than, the fiber melting point. In various embodiments, the colored transfer medium is a dye transfer paper having a dye on one side. In other embodiments, the autoclave can be used with heat, force, pressure, and / or vacuum. In various embodiments, the expandable structure is expanded at 20 ° C. and preferably 1-30%, more preferably 2-20%, or most preferably 3-10% of the fiber breaking strength before coloring. Includes an adjustable rig that can pre-stretch the fibers. In other embodiments, the expandable structure is a tube, such as glass, metal, granite, concrete or quartz, which gradually expands when the temperature is increased by at least 10 ° C., and the fibers during the coloring process To compensate for fiber shrinkage that may occur due to heating.

  [0082] In various embodiments, a method of transferring a dye to a fiber, blade or composite material comprises: a) applying the dye to a transfer medium to create a dye transfer medium; and b) a dye coated surface of the dye transfer medium. Wrapping the dye transfer medium onto the inflatable structure, leaving the substrate exposed; and c) wrapping the fiber, blade or composite material onto and in contact with the dye transfer medium. And d) applying at least one of heat, external force, external pressure and vacuum pressure to inject the dye into the fiber, blade or composite material to produce a colored fiber, blade or composite material. In various embodiments, the colored transfer medium is a dye transfer paper having a dye on one side. In various embodiments, the autoclave can be used with heating, pressure, and / or vacuum application. In various embodiments, the material to be dyed can be wound directly around the expandable structure (eg, the fibers are wrapped around a metal tube or expandable rig), or alternatively dye transfer The media can be wrapped around the expandable structure, and then the fibers, blades or composites are wrapped around the dye transfer medium and the dye transfer medium is dyed with the expandable structure Be between the composite materials. The temperature for this process is typically in the range of about 70 ° F. to about 650 ° F., and the pressure is a minimum pressure to keep the material in intimate contact, typically from ambient atmospheric pressure up to 1000 psi. Range. In a preferred embodiment, the temperature of the coloring process is close to the melting point of the fiber. In various embodiments, the expandable structure is expanded at 20 ° C. and preferably 1-30%, more preferably 2-20%, or most preferably 3-10% of the fiber breaking strength before coloring. Includes an adjustable rig that can pre-stretch the fibers. In other embodiments, the expandable structure is a tube, such as a metal tube such as aluminum, copper, high purity iron or cast iron, which expands gradually during heating to stretch the fibers during the coloring process and Offsets possible fiber shrinkage.

  [0083] In various embodiments, a method of transferring a dye to a fiber, blade or composite material comprises: a) applying the dye to a transfer medium to make the dye transfer medium; and b) making the dye transfer medium an expandable structure. Wrapping on an object; c) wrapping the fiber, blade or composite material on and in contact with the dye transfer medium and on the expandable structure; and d) adding an additional dye transfer medium to the Winding a dye-coated surface in contact with the fiber, blade or composite material over the fiber, blade or composite material; and e) applying at least one of heat, external force, external pressure and vacuum pressure to apply the dye. Injecting into a fiber, blade or composite material to produce a colored fiber, blade or composite material. In other words, two layers of dye transfer media may be used to sandwich the fiber, blade or composite material to be dyed, all of which are wound in layers around the inflatable structure. The temperature for this process is typically in the range of about 70 ° F. to about 650 ° F., and the pressure is a minimum pressure to keep the material in intimate contact, typically from ambient atmospheric pressure up to 1000 psi. Range. In a preferred embodiment, the temperature of the coloring process is close to, but lower than, the fiber melting point. In various embodiments, the expandable structure is expanded at 20 ° C. and preferably 1-30%, more preferably 2-20%, or most preferably 3-10% of the fiber breaking strength before coloring. Includes an adjustable rig that can pre-stretch the fibers. In other embodiments, the expandable structure is glass, metal, granite, concrete or quartz tube (eg, a metal such as aluminum, copper, high purity iron or cast iron), which increases in temperature by at least 10 ° C. As it is done, it gradually expands to stretch the fiber during the coloring process, offsetting fiber shrinkage that may occur due to heating.

[0084] [Typical Procedure for Coloring Fibers under Tension]
[0085] In an example, tension is provided by differential (and reverse) thermal expansion between the fibers and the expandable structure when both are heated together. Metal is typically a manufacturing material for inflatable structures suitable for use in accordance with the present method, with metal tubes being ideally preferred. In various embodiments, the inflatable structure includes a metal tube having any wall thickness, diameter, and length. In various embodiments, the metal tube comprises aluminum, copper, high purity iron or cast iron. In various embodiments, the inflatable structure includes an aluminum tube having an inner diameter of about 20 times the wall thickness. In various embodiments, the inflatable structure includes a 10 inch inner diameter aluminum tube with a 0.5 inch wall thickness.

  [0086] FIG. 8 illustrates the inflatable structure used in this example. Tubing 890 is an aluminum mandrel having a 0.5 inch wall thickness and a 10 inch inner diameter. The fiber used in this example was Spectra® ultra high molecular weight polyethylene fiber. As mentioned above, ultra high molecular weight polyethylene fiber has a negative coefficient of thermal expansion (CTE), which shrinks the fiber when heated, while aluminum mandrel 890 has a positive coefficient of thermal expansion, which is heated. Inflates the mandrel when The combined effect of Spectra® fiber shrinkage and aluminum mandrel expansion helps to prevent degradation of the fiber's mechanical properties caused by disruption of the elongated polymer chain structure in the fiber.

  [0087] Before applying the dye sublimation transfer paper to the surface of the aluminum mandrel, to clean the mandrel, rub the surface with a solvent wipe impregnated with methyl ethyl ketone (MEK) or other solvent to remove any oil or contamination Material was removed. The MEK is then evaporated using a handheld hot air gun, and the dye sublimation transfer paper faces the dye sublimation side outward for use as a contact surface with the fibers and blades to be colored, and the outer surface of the mandrel. It was strongly wrapped around. Both solid colors and patterned dye sublimation transfer papers are utilized for this study, solid patterns are used when solid colors are transferred to the fibers or blades, and multi-color patterns are used for the fibers or blades. Patterned transfer paper is used when applied along the length. The transfer paper was fixed to the mandrel with tape.

  [0088] Once the transfer paper was secured to the mandrel, the mandrel was attached to a tension control winder using an inflatable core chuck and a fiber or blade spool was attached to the tension control delivery machine. Next, the Spectra® blades or fibers are closely wound with each wrap of the blade in close contact with the colored surface of the transfer paper and preferably overlap adjacent wraps of the blade or fiber. Wrapped on the dye sublimation paper with a predetermined tension. After the Spectra® blade or fiber is fully wound on the mandrel, the second sheet of dye sublimation transfer paper is wound on the fiber or blade layer with the dye sublimation transfer surface facing inward The transfer surface was in intimate contact with the outer surface of the Spectra® fiber or blade, and the paper was fixed with tape to prevent the transfer paper from moving on the mandrel. In this way, each of the dye transfer paper layers was placed so that the dye surface was facing the fibers or blades to be colored, and the fibers or blade layers were sandwiched between the dye transfer paper layers.

  [0089] The outer layer of transfer paper on the mandrel is covered with a 2 mil thick non-porous Teflon film layer so that the colorant gas migrates from the Spectra® fibers or blades during the sublimation process. Prevented. Moreover, the layer of Airweave N-10 was applied as a breather layer. The mandrel was then covered with a layer of Airtech 5 mil nylon vacuum bag sealed to a backing plate with Airtech adhesive tape. An Airtech vacuum tap was inserted under the nylon film vacuum bag. The vacuum tap is shut in place and sealed against the nylon bag film, and a vacuum hose connected to a high volume vacuum pump evacuates air from under the vacuum bag.

  [0090] A 27 inch Hg vacuum was applied to the bagged assembly using a liquid ring vacuum pump to check for leaks in the bag or sealing system.

  [0091] The completed mandrel assembly was maintained under vacuum and placed in an autoclave. Once placed in the autoclave, a vacuum tap on the mandrel was connected to the autoclave's internal vacuum system. The autoclave is pressurized to 5 psi with dry nitrogen to prevent the bag from moving, the vacuum under the bag on the mandrel is opened to the atmosphere to maintain the atmospheric pressure on the sublimation paper during the autoclave heating process, and Spectra® The dye sublimation colorant is prevented from premature sublimation before the fiber reaches a sufficiently high temperature and the colorant is injected into the Spectra® fiber filament. This temperature was close to, but lower than, the fiber melting point and was between about 275-280 ° F.

  [0092] The autoclave temperature is raised to a sublimation transfer temperature of 275-280 ° F. and held at that temperature until the lagging tool and the Spectra® fiber layer reach the transfer temperature. When the Spectra® material reaches the transfer temperature, the autoclave pressure is released while pulling a 28 Hg vacuum under the vacuum bag to prevent damage to the Spectra® filament, and the colorant from the dye transfer paper Sublimation was initiated to facilitate the injection of the colorant into the Spectra® fiber filament. Spectra® fibers were held at an injection temperature of 275-280 ° F. under vacuum for 15 minutes to allow the colorant to be injected into the Spectra® material. At the end of the 15 minute stagnation time, the autoclave was cooled to 150 ° F. while maintaining full vacuum under the mandrel vacuum bag.

  [0094] FIGS. 9 and 10 are plots of the data in Table 1. FIGS. 9 and 10 provide the autoclave dye sublimation injection time, temperature, autoclave pressure, and mandrel pressure schedule under the bag for the coloring cycle.

  [0095] At the end of the injection cycle, the mandrel assembly was removed from the autoclave and the vacuum bag, breather cloth, Teflon film and outer layer of transfer paper were each removed from the aluminum mandrel. The resulting colored Spectra® fibers or blades were examined for coloring characteristics and uniformity.

  [0096] The mandrel was reattached onto a tension control winder using an inflatable core chuck and the fiber or blade was re-wound onto a suitable core. The colored fibers and blades were then subjected to tensile testing in a suitably equipped laboratory.

  [0097] An Instron 5667 universal test load frame controlled by the Instron Blue Hill mechanical test control and data acquisition system was used for testing. A 500 Newton Instron load cell with a set of Instron pneumatic grip fixtures optimized for testing Spectra® fibers was mounted on the load frame and the grip length for the test device was set to 250 mm. . Colored Spectra® fibers and blades were tested to failure at a crosshead speed of 127 mm / min and load and displacement data were collected for each sample test for toughness and modulus calculations. Test results for colored Spectra® blades and fibers were compared to uncolored (ie “as received”) Spectra® fibers and blades using the same test settings and parameters. . The test results of colored and uncolored Spectra® fibers and blades were compared to assess the effect of the coloring process on toughness and modulus.

  [0098] FIG. 11 is a summary of a table of test results for Spectra® material in an “as received” state (ie, prior to the coloring process). FIG. 12 is a plot of toughness versus tensile strain for an uncolored Spectra® material.

  [0099] In comparison, FIG. 13 is a summary of a table of test results for colored Spectra® materials obtained from the process just described. FIG. 14 is a plot of toughness versus tensile strain of a colored Spectra® material from the above coloring process. The material used was a Spectra® fiber 1740 dtex blade.

[00100] [Result]
[00101] The average failure load of a 1740 dtex blade colored with royal blue was measured at 89.1 lbs, which yields a corresponding average strength of 22.78 cN / dtex. The average failure load of the “as received” uncolored 1740 dtex blade as a white gray article was 90.9 lbs, which gives a corresponding average strength of 23.24 cN / dtex. FIG. 11 is compared to FIG. 13 to compare the tabular test results, and FIG. 12 is compared to FIG. 14 to compare the toughness versus strain plots of the colored and uncolored 1740 dtex blade samples. Recalculating the percentage of intensity difference gives 1.1% reduction in the tensile strength of the colored blades when excluding outliers in the test data.

  [00102] From the test results, the toughness of the colored 1740 dtex Spectra® blade is greater than the average toughness of the uncolored material (ie, the white Spectra® 1740 dtex blade tested directly from the factory roll). It is confirmed that it is 1.9% lower. Examination of the data in the table for the failure strength of the colored blade showed an abnormal value of the test # 5 data due to a gripping error that caused initial failure of the test sample. If one outlier in test # 5 of the colored test sample is excluded from the data set, the average break strength of the colored sample increases to 89.8 lbs and the average strength increases to 22.95 cN / dtex. Recalculating the percentage of intensity difference gives 1.1% reduction in the tensile strength of the colored blades when excluding outliers in the test data.

  [00103] The average modulus of the colored 1740 dtex blade is 126.67 cN / dtex, which is actually from the uncolored material, the average modulus of the white 1740 dtex blade (which was 125.07 cN / dtex when tested). Is also slightly higher by 1.2%. While not wishing to be bound by any particular theory, this improvement in the color modulus of the colored blades is that of the fibers of the blade under tension caused during some degree of heat set and color heat and pressure cycles. It can be attributed to alignment. Examining the toughness vs. strain plots of the tensile test results of FIGS. 12 and 14 tends to support the improvement in tensile elongation given as a result of the heat set hypothesis.

  [00104] As can be seen from the plot, the colored blades have a closer, more reproducible load / displacement relationship that is most likely due to heat setting of the blades. Table 2 lists the average strength and average modulus of the “as received” Spectra® fiber blade and the Spectra® fiber blade dyed according to the method described herein.

[Compare with test results of Spectra (registered trademark) 1000 400 denier fiber]
[00106] The average failure load of Spectra® 1000 400 denier (425 dtex) fiber colored with royal blue was 28.23 lbs, which shows a corresponding average toughness of 29.51 cN / dtex. The as-received white uncolored 400 denier (425 dtex) Spectra® 1000 fiber has an average breaking load of 29.94 lbs, which shows a corresponding average strength of 31.29 cN / dtex. Table 3 shows these test results in tabular form.

  [00108] FIGS. 15 and 16 are plots of toughness versus strain for uncolored (FIG. 15) and colored (FIG. 16) 400 denier (425 dtex) Spectra® 1000 fiber samples.

  [00109] Test results show that the toughness of colored 400 denier (425 dtex) Spectra® 1000 fibers is tested directly from the factory roll, uncolored material, white 400 denier (425 dtex) Spectra® 1000 fibers. It is 1.5% lower than the average toughness.

  [00110] The average elastic modulus of colored 400 denier (425 dtex) Spectra® 1000 fibers is 1098.04 cN / dtex, which is the average of uncolored material, white 400 denier (425 dtex) Spectra® 1000 fibers Slightly lower by 1.5% than the elastic modulus (which was 1115.07 cN / dtex when tested). While not wishing to be bound by any particular theory, this reduction in the modulus of the colored blades is due to the disruption of the fiber chain pattern, which reduces the modulus measurement due to non-uniformity of filament bonding. It can be attributed to some extent. Examining the variability of the toughness versus strain plots of the tensile test results of FIGS. 15 and 16 tends to support the idea that the decrease in tensile elongation of the colored fibers is a result of the disruption of fiber chain uniformity. Also, this disruption of fiber chain uniformity can account for a significant portion of the 2.4% reduction in the strength of the colored fiber, which is caused by a decrease in the properties of the Spectra® material as a direct result of coloring. Will reduce the elements of reduced strength.

[Indirect application of multiple colors to blade using printing pattern dye sublimation transfer paper]
[00111] In an exemplary embodiment of multiple colors, a Spectra® 435 denier blade simulated fishing line sample is a dye sublimation transfer sample of a multi-colored “Aqua Blue / Black Stripe / Steelhead Gray” color pattern. Colored using. The coloring process resulted in a fully injected color of the fibers in the blade. The colors and patterns themselves appear to be very suitable as camouflage fishing lines and are probably suitable for other applications where a blue / grey camouflage color pattern is desired. Because of the blade inhomogeneity, non-uniformity and the presence of defects and knots, the blade was used only for color trials and no mechanical test results were recorded for this blade sample.

  [00112] Additional details regarding materials, processes, methods, and manufacturing can be found in US Pat. No. 5,470, issued on Nov. 28, 1995, entitled “COMPOSITE MATERIAL FOR FABRICATION OF SAILS AND OTHER ARTICS”. No. 062, and US Pat. No. 5,333,568 entitled “Material For The FABRICATION OF SAILS” issued on August 2, 1994, and filed June 24, 2011 The title is “WATERPROOF BREATHABLE COMPOSITE MATERIALS FOR FABRICATION OF FLEXIBLE MEMBRANES AND OTHER ARTICS” No. 13 / 168,912, the contents of which are hereby incorporated by reference in their entirety for all purposes.

  [00113] Benefits, other advantages, and solutions to problems have been described above with regard to specific embodiments. However, benefits, benefits, solution to problems, and any element that may result in or make any benefit, advantage or solution important or important to any or all claims Or must be interpreted as essential features or elements. As used herein, the terms “includes”, “including”, “comprises”, “comprising” or any other variant thereof are not limiting. Process, method, article, or device that includes a series of elements is not intended to include only those elements, and is not explicitly described or inherent in such process, method, article, or device Other elements may be included. Further, elements described herein are not required for the practice of the invention unless explicitly described as "essential" or "important".

  [00114] Although Applicants have described Applicants' preferred embodiments of the present invention, it will be understood that the broadest scope of the invention includes modifications such as various shapes, sizes, and materials. Such scope is limited only by the following claims read in conjunction with the above specification. Moreover, many other advantages of Applicant's invention will be apparent to those skilled in the art from the foregoing description and the following claims.

Claims (20)

A method of transferring dye to a fiber, blade or composite material,
Applying a dye to one side of the transfer medium to make a dye transfer medium;
Wrapping the dye transfer medium on an inflatable rig or structure such that the dye side of the dye transfer medium remains exposed;
Wrapping the fiber, blade or composite material onto the dye transfer medium and applying at least one of heat, external force, external pressure and vacuum pressure to inject the dye into the fiber, blade or composite material And making colored fibers, blades or composites.   The method of claim 1, further comprising expanding the expandable rig to pre-stretch the fibers, blades, or composite material prior to the step of applying at least one of heat, external force, external pressure, and vacuum pressure. The method described. The expansion composition comprises a tube having a thermal expansion coefficient between ^{5 × 10 -6 / K~30 × 10} -6 / K, whereby the temperature rise of at least 10 ° C. is added to the process, according to claim 1 the method of.   4. The method of claim 3, wherein the tube comprises glass, metal, granite, concrete or quartz.   The method of claim 4, wherein the metal comprises aluminum, copper, high purity iron, cast iron, lead, nickel, palladium, or stainless steel.   The method of claim 1, wherein the fibers, blades or composite material comprises ultra high molecular weight polyethylene fibers.   The method of claim 1, further comprising cooling the fiber, blade or composite material to a temperature such that the fiber, blade or composite material maintains a desired shape.   The method of claim 1, further comprising curing the dye by applying at least one ultraviolet or electron beam radiation to the fiber, blade, or composite material.   The method of claim 1, further comprising adding a coating to the fiber, blade or composite.   The method of claim 1, further comprising adding a film to the fiber, blade or composite material.   The method of claim 1, further comprising adding a nylon coating and a urethane coating to the fiber, blade or composite material.   The method of claim 1, wherein the composite material is at least one of a nonwoven and a woven material.   The method of claim 1, wherein the transfer medium is at least one of transfer paper, transfer laminate, or transfer film.   The method of claim 1, wherein the dye is applied to the transfer medium in the form of a pattern, graphic or logo, and the colored fibers, blades or composites are respectively injected with a matching pattern, graphic or logo.   The method of claim 1, further comprising the step of applying an additional layer of a dye transfer medium on the fiber, blade or composite prior to the step of applying at least one of heat, external force, external pressure and vacuum pressure. The method described. A method of transferring dye to a fiber,
Applying a dye to one side of the transfer medium to make a dye transfer medium;
Wrapping the dye transfer medium on an inflatable rig so that the dye side of the dye transfer medium remains exposed;
Winding the fiber onto the dye transfer medium;
Pre-stretching the fiber at 20 ° C. to expand the expandable rig to a force of 1-30% of the breaking strength of the fiber;
Applying at least one of heat, external force, external pressure and vacuum pressure to inject the dye into the fibers to produce colored fibers.   The method of claim 16, wherein the fibers comprise ultra high molecular weight polyethylene.   The method of claim 17, wherein the step of applying at least one of heat, external force, external pressure and vacuum pressure comprises heating between 275-280 ° F. A method of transferring dye to a fiber,
Applying a dye to one side of the transfer medium to make a dye transfer medium;
About 20 times the inner diameter of the thermal expansion rate and the wall thickness between the dye transfer medium ^{5 × 10 -6 / K~30 × 10} -6 / K as the dye surface remains exposed in the dye transfer medium Wrapping around a tube having
Winding the fiber around a side tube over the dye transfer medium;
Applying at least one of heat, external force, external pressure and vacuum pressure to inject the dye into the fiber to produce a colored fiber;
A process whereby a temperature increase of at least 10 ° C. is added to the process.   20. The method of claim 19, wherein the fiber comprises ultra high molecular weight polyethylene and the tube comprises aluminum.

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