Not Applicable.
The invention described herein relates generally to a one-component or a two-component spray gun nozzle tip that dispenses foam in a first spray pattern as well as a second spray pattern after the operator has removed the outermost spray tip.
This invention is particularly suited for in-situ applications of liquid chemicals mixed and dispensed as a spray or a foam and more specifically, to in-situ application of polyurethane foam or froth. In-situ applications for polyurethane foam have continued to increase in recent years extending the application of polyurethane foam beyond its traditional uses in the packaging, insulation and molding fields. For example, polyurethane foam is being used with increasing frequency as a sealant in the building trades for sealing spaces between windows and door frames and the like and as an adhesive for gluing flooring, roof tiles, and the like.
Polyurethane foam for in-situ applications is typically supplied as a “one-component” froth foam or a “two-component” froth foam in portable containers hand carried and dispensed by the operator through either a valve or a gun. However, the chemical reactions producing the polyurethane froth foam in a “one-component” polyurethane foam is significantly different from the chemical reactions producing a polyurethane froth foam in a “two-component” polyurethane foam. Because the reactions are different, the dispensing of the chemicals for a two-component polyurethane foam involves different and additional concepts and concerns than those present in the dispensing apparatus for a “one-component” polyurethane froth foam.
A “one-component” foam generally means that both the resin and the isocyanate used in the foam formulation are supplied in a single pressurized container and dispensed from the container through a valve or a gun attached to the container. When the chemicals leave the valve, a reaction with moisture in the air produces a polyurethane froth or foam. Thus, the design concerns related to an apparatus for dispensing one-component polyurethane foam essentially concerns the operating characteristics of how the one-component polyurethane foam is throttled or metered from the pressurized container. Post drip is a major concern in such applications as well as the dispensing gun not clogging because of reaction of the one component formulation with air (moisture) within the gun. To address or at least partially address such problems, a needle valve seat is typically applied as close to the dispensing point by a metering rod arrangement which can be pulled back for cleaning. While metering can occur at the needle valve seat, the seat is primarily for shut-off to prevent post drip, and depending on gun dimensioning, metering may principally occur at the gun opening.
In contrast, a “two-component” froth foam means that one principal foam component is supplied in one pressurized container, typically the “A” container (i.e., polymeric isocyanate, fluorocarbons, etc.) while the other principal foam component is supplied in a second pressurized container, typically the “B” container (i.e., polyols, catalysts, flame retardants, fluorocarbons, etc.). In a two-component polyurethane foam, the “A” and “B” components form the foam or froth when they are mixed in the gun. Of course, chemical reactions with moisture in the air will also occur with a two-component polyurethane foam after dispensing, but the principal reaction forming the polyurethane foam occurs when the “A” and “B” components are mixed or contact one another in the dispensing gun and/or dispensing gun nozzle. The dispensing apparatus for a two-component polyurethane foam application has to thus address not only the metering design concerns present in a one-component dispensing apparatus, but also the mixing requirements of a two-component polyurethane foam.
Further, a “frothing” characteristic of the foam is enhanced by the pressurized gas employed, e.g., fluorocarbon (or similar) component, which is present in the “A” and “B” components. This fluorocarbon component is a compressed gas which exits in its liquid state under pressure and changes to it gaseous state when the liquid is dispensed into a lower pressure ambient environment, such as when the liquid components exit the gun and enter the nozzle.
While polyurethane foam is well known, the formulation varies considerably depending on application. In particular, while the polyols and isocyanates are typically kept separate in the “B” and “A” containers, other chemicals in the formulation may be placed in either container with the result that the weight or viscosity of the liquids in each container varies as well as the ratios at which the “A” and “B” components are to be mixed. In dispensing gun applications which relate to this invention, the “A” and “B” formulations are such that the mixing ratios are generally kept equal so that the “A” and “B” containers are the same size. However, the weight, more importantly the viscosity, of the liquids in the containers invariably vary from one another. To adjust for viscosity variation between “A” and “B” chemical formulations, the “A” and “B” containers are charged (typically with an inert gas) at different pressures to achieve equal flow rates. The metering valves in a two-component gun, therefore, have to meter different liquids at different pressures at a precise ratio under varying flow rates. For this reason (among others), some dispensing guns have a design where each metering rod/valve is separately adjustable against a separate spring to compensate not only for ratio variations in different formulations but also viscosity variations between the components. The typical two-component dispensing gun in use today can be viewed as two separate one-component dispensing guns in a common housing discharging their components into a mixing chamber or nozzle. This practice, typically leads to operator errors. To counteract this adverse result, the ratio adjustment then has to be “hidden” within the gun, or the design has to be such that the ratio setting is “fixed” in the gun for specific formulations. The gun cost is increased in either event and “fixing” the ratio setting to a specific formulation prevents interchangeability of the dispensing gun.
Another element affecting the operation of a two-component gun is the design of the nozzle. The nozzle is typically a throw away item detachably mounted to the nose of the gun. Nozzle design is important for cross-over and metering considerations in that the nozzle directs the “A” and “B” components to a static mixer within the tip. For example, one gun completely divides the nozzle into two passages by a wall extending from the nozzle nose to the mixer. The wall lessens but does not eliminate the risk of cross-over since the higher pressurized component must travel into the mixer and back to the lower pressure metering valve. Typically nozzles are uniquely designed to orient the aerosol spray in a fan-shaped pattern or a circular pattern, depending on the end geometry of the spray tip. Typically, switching from one spray pattern to the other typically required changing spray tips. When a tip is exchanged, the residual material will solidify and render the nozzle unusable in the future as explained in more detail below.
A still further characteristic distinguishing two-component from one-component gun designs resides in the clogging tendencies of two-component guns. Because the froth foaming reaction commences when the “A” and “B” components contact one another once the gun is used, the static mixer will clog with polyurethane foam or froth formed within the mixer. Therefore the nozzles, which contain the static mixer, are designed as throw away items. In practice, the foam does not instantaneously form within the nozzle upon cessation of metering to the point where the nozzles have to be discarded. Some time must elapse. This is a function of the formulation itself, the design of the static mixer and, all things being equal, the design of the nozzle.
The dispensing gun of the present invention is particularly suited for use in two-component polyurethane foam “kits” typically sold to the building or construction trade. Typically, the kit contains two pressurized “A” and “B” cylinders (130-250 psi), a pair of hoses for connection to the cylinders and a dispensing gun, all of which are packaged in a container constructed to house and carry the components to the site where the foam is to be applied. When the chemicals in the “A” and “B” containers are depleted, the kit is sometimes discarded or the containers can be recycled. The dispensing gun may or may not be replaced. Since the dispensing gun is included in the kit, kit cost considerations dictate that the dispensing gun be relatively inexpensive. Typically, the dispensing gun is made from plastic with minimal usage of machined parts.
The Prior Art dispensing guns are typically “airless” and do not contain provisions for cleaning the gun. That is, a number of dispensing or metering guns or apparatus, particularly those used in high volume foam applications, are equipped or provided with a means or mechanism to introduce air or a solvent for cleaning or clearing the passages in the gun. The use of the term “airless” as used in this patent and the claims hereof means that the dispensing apparatus is not provided with an external, cleaning or purging mechanism.
Within each type of dispensing gun (e.g., one-component dispensing gun, two-component dispensing gun), a metering rod is utilized. The metering rod is a primary shutoff within the dispensing gun that meters or controls dispensing of material. The metering rod is often referred to as a needle or a pin and engages a female type receiver to meter or shutoff flow of chemical (e.g., material, component “A,” component “B,” etc.). In one-component dispensing guns, a single metering rod is included within a dispensing passage. In two-component dispensing guns, a metering rod is included within each dispensing passage associated with component (e.g., material). In an embodiment, two-component dispensing gun includes first dispensing passage and respective metering rod and second dispensing passage and respective metering rod. Upon use of a trigger, metering rod(s) allow material to be dispensed.
Fabrication of metering rods for dispensing guns include various challenges to produce an efficient dispensing gun at a reasonable price point. Typically, metering rods are fabricated incorporating brass, copper, and other materials (e.g., metallic, non-metallic, etc.). Yet, such materials have increased in cost and, in turn, increased cost of manufacturing dispensing guns. Furthermore, dispensing gun requires a secure mating between receiver and metering rod in order to prevent inconsistent metering (e.g., non-uniform dispensing of material, components, or chemical) and incomplete shut off (in a closed position). Inaccuracy between mating surfaces (e.g., receiver and metering rod) is typically overcome by forcing two elements together during initial assembly and allowing the more malleable of the two elements to take set. This technique is referred to as presetting and typically requires lengthy hold time which limits manufacturing of dispensing guns. Overall, presetting increases the possibility of enabling two mating surfaces to have secure connection (e.g., mating) to avoid leakage and/or non-uniform dispensing but adds to the manufacturing time.
Additionally, metallic metering rods are often fabricated with turning or grinding techniques. In particular, during creation of typical metallic metering rod(s), radial micro grooves are present due to such turning or grinding technique. With repeated use over duration of time, these micro grooves cause wear to the more malleable mating surface. In general, micro grooves grind or file away at the mating surface which can cause leakage of chemical/material at the mating surface.
While two-component dispensing guns discussed above function in a commercially acceptable manner, it is becoming increasingly clear as the number of in-situ applications for polyurethane foam increase, that the range or the ability of the dispensing gun to function for all such applications has to be improved. As a general example, metering rods that meter amount of dispensed material need to be fabricated in a manner that prevent uneven dispensing of materials as well as prevent incomplete shutoff.
Further limitations and disadvantages of conventional, traditional, and proposed approaches will become apparent to one of skill in the art, through comparison of such systems and methods with certain embodiments the claimed invention as set forth in the remainder of the present application with reference to the drawings.
In one embodiment of the invention, the invention resides in the combination of an applicator (preferably a spray gun) having a housing and a nozzle which comprises: an expanded rear portion of the nozzle for affixing the nozzle to a front of the applicator (preferably spray gun) employing a fastening means; an egress segment of the nozzle at an opposed end from the expanded rear portion of the nozzle, the egress segment comprising: a nozzle tip, the nozzle tip applying the foam or coating in a first spray pattern; a first nozzle segment rearward along a longitudinal axis of the nozzle tip; a fracture zone rearward along the longitudinal axis of the first nozzle segment; a second nozzle segment rearward along the longitudinal axis of the fracture zone; and an optional static mixer interposed between the second nozzle segment and the expanded rear portion of the nozzle; a terminal end of the fracture zone forming a second nozzle tip when the first nozzle segment is removed from the egress segment of the nozzle along the fracture zone, the second nozzle segment spraying foam in a second spray pattern, the second spray pattern being different from the first spray pattern. As used in this application, the qualifier “different” can mean the same geometric shape, but of a different diametered opening, but could also mean a completely different geometric shape from the first shape.
In one aspect of the invention, the fracture zone is a reduced thickness area between the first and second nozzle segments. In another aspect of the invention, the nozzle will have a first nozzle segment and second nozzle segment, each segment comprising a first polymer and a second polymer. The first polymer and the second polymer are preferably at least partially miscible polymers, having at least one Tg between the Tg of the first polymer and the Tg of the second polymer. In a preferred embodiment of the invention, the first polymer and the second polymer are miscible having a single Tg between the Tg of the first polymer and the Tg of the second polymer.
In yet another aspect of the invention, the first polymer and the second polymer are the same, but of different degrees of crosslinking. Often, the first polymer has a higher degree of crosslinking than the second polymer, which has either a reduced degree of crosslinking or no crosslinking.
In a most preferred embodiment, at least a portion of the spray gun nozzle is a polymer, which comprises a color-changeable additive. The color-changeable additive is often a thermochromatic dye.
In still yet another aspect of the invention, the first polymer is soluble in a solvent, and the second polymer is not soluble in that same solvent.
The invention is also directed toward just a nozzle as hereinabove described.
The invention also comprises a method of forming a fracture zone in a nozzle, wherein the nozzle comprises: an egress segment of the nozzle at an opposed end from the expanded rear portion of the nozzle, the egress segment comprising: a nozzle tip, the nozzle tip applying a coating or spraying a foam in a first spray pattern; a first nozzle segment rearward along a longitudinal axis of the nozzle tip; a fracture zone rearward along the longitudinal axis of the first nozzle segment; a second nozzle segment rearward along the longitudinal axis of the fracture zone; and an optional static mixer interposed between the second nozzle segment and the expanded rear portion of the nozzle (the static mixer preferred when applying foams); a terminal end of the fracture zone forming a second nozzle tip when the first nozzle segment is removed from the egress segment of the nozzle along the fracture zone, the second nozzle segment spraying foam in a second spray pattern, the second spray pattern being different from the first spray pattern, and wherein the steps of forming the fracture zone are selected from at least one of: molding the nozzle to have an area of reduced thickness proximate the fracture zone; molding the nozzle using two polymers adjacent the fracture zone, each of the polymers being at least partially miscible with the other polymer; molding the nozzle using the same or similar polymers on either side of the fracture zone, each of the polymers being crosslinked to a different degree; and molding the nozzle using an overmolded polymer over the egress tip of the nozzle.
When the process includes the step of molding the nozzle to have the area of reduced thickness proximate the fracture zone, a mold is employed having an internal pin inserted along a longitudinal axis of the nozzle at the egress tip. When the process includes the step of molding the nozzle to use two polymers adjacent the fracture zone, the mold will employ two internal mold runners to feed each polymer. When the process includes the step of molding the nozzle using the same or similar polymers on either side of the fracture zone, each of the polymers being crosslinked to a different degree involves either adding different amounts of at least one crosslinking agent to each polymer or exposing each polymer to a different degree of radiation crosslinking. In one embodiment, when the process involves crosslinking, the process includes the step of having a first polymer crosslinked to a higher degree and a second polymer, which has either a reduced degree of crosslinking or no crosslinking. And lastly, when the process includes the step of molding the nozzle using an overmolded polymer, the overmolded polymer and the underlying polymer will be at least partially miscible polymers.
When using overmolding, an essentially circular area in cross-section proximate the fracture zone is preferred and an essentially circular area in cross-section proximate the egress tip. Alternatively, a polygon-shaped area in cross-section (or fan-shaped area) proximate the egress tip may be employed.
The process preferably involves adding a least one thermochromic dye to the nozzle, although two or more thermochromatic dyes may be added for additional visual effects.
These and other advantages and novel features of the claimed invention, as well as details of illustrated embodiments thereof, will be more fully understood from the following description and drawings.
The best mode for carrying out the invention will now be described for the purposes of illustrating the best mode known to the applicant at the time of the filing of this application. The examples are illustrative only and not meant to limit the invention, as measured by the scope and spirit of the claims.
As used in this application, the term “miscible” or “partially miscible” means polymers having blending/bonding characteristics as described later in this application.
As used in this application, the term “different” as used in the context of nozzle egress geometric shapes, means a shape which is not the same in some geometric aspect, e.g., a 3-sided polygon shape as contrasted to a 6-sided polygon shape. Alternatively, it means a “fan” shape as contrasted to a “circular shape”. In yet another aspect, it means the same geometry, except of different dimensions, e.g., a circular shape having a 1 mm internal diameter opening in comparison to a circular shape having a 2 mm internal diameter opening.
As used in this application, the term “fastening means” is illustrated by the various fastening means shown in the Figures, namely the resiliently-biased finger shown in
The Prior Art of
Gun body 12 may be further defined as having integral portions including a longitudinally-extending valve portion 15 to which nozzle 14 is releasably connected and terminating at a longitudinally-extending trigger portion 16, in turn, terminating at longitudinally-extending spring portion (not shown) from which transversely extends handle portion 18. Within gun body housing 12 is a pair of hose openings 22, 23, canted as shown, to which the “A” and “B” hoses (not shown) are attached, respectively, by conventional quick connect couplings or other retaining mechanisms (e.g., friction fitting O-rings). Dispensing gun 10 is also provided with pivotable trigger 20 extending within trigger body portion 16. It should be appreciated that when the operator grasps dispensing gun 10 about handle 18 for finger actuation of trigger 20, that the position of hose openings 22, 23 is such that the kit hoses will drape over the operator's forearm which is preferred over other conventional hose attachment positions on the dispensing gun. Canting hose openings 22, 23 is thus believed to provide some ergonomic benefit while contributing to the improved performance of dispensing gun 10 as described below. While a canted configuration is illustrated, the invention is not limited to that arrangement, and the “A” and “B” hoses may be positioned to enter the gun from the base of handle 18 (not shown).
Referring now to the Prior Art of
As better illustrated in the Prior Art of
In
This problem is solved in the nozzle illustrated in
In switching from a first spray pattern to a second spray pattern, the user will grip forward portion 21 of the nozzle and apply a transverse force to the longitudinal axis of the spray nozzle. This is illustrated in
While the static mixer has been illustrated a circular in cross-section in
As better illustrated in
However, it should be noted that this “fracture” region in the nozzle may be manufactured in several ways. One approach to achieve the desired result is by thinning the walls of the nozzle. Another approach is to employ a first polymer to manufacture the nozzle 14 from location 11 rearward, while a second similar, but not identical polymer could be used to manufacture the nozzle 14 from location 11 forward. The degree of similarity or dissimilarity between the first and second polymers will control the amount of operator force required to “snap” the nozzle as the degree of bonding is controlled at least in part, by the miscibility of the polymers. Another approach involves crosslinking the two polymers (e.g., polyethylene) to different degrees, e.g., 30-40% in region 21 and 50-65% in region 26. When using one of the approaches which employs similar/dissimilar polymers, the manufacture of the nozzle may employ an injection molding die with an internal pin and at least two runner systems, one to mold the plastic from location 11 rearward and a second to mold the plastic from location 11 forward. In an alternative embodiment, the two polymers may be employed sequentially. Similarly, when employing the crosslinking approach, it is possible for example to synthesize the spray nozzle with a polymer which is crosslinked to a first degree and a second polymer added which is crosslinked to a second degree, the first and second degrees being different. Crosslinked polyethylene is a particularly suitable polymer for this approach, using, e.g., either silane crosslinking or radiation crosslinking.
As better illustrated in
When employing either the different polymer approach or the different degrees of crosslinking as the process for synthesizing the tip, it is possible to have both the outer and inner diameters of the tip remain essentially constant. The breaking of the outer tip to expose the inner tip is achieved by chemistry dissimilarities, rather than mechanical separation action.
When employing the approach in which the first and second polymers are different, there is a need for at least some bonding between the two polymers in fracture zone 11. Polymer blends are often used and can be broadly divided into three categories: immiscible polymer blends (heterogeneous polymer blends): compatible polymer blends: and miscible polymer blends (homogeneous polymer blends). If the blend is immiscible, then it is likely made of two polymers and two glass transition temperatures will be observed. Compatible polymer blends are immiscible polymer blends that exhibit macroscopically uniform physical properties. The macroscopically uniform properties are usually caused by sufficiently strong interactions between the component polymers. Miscible polymer blends are polymer blends that have a single-phase structure. In this case, one glass transition temperature will be observed.
Examples of miscible polymer blends include: homopolymer—homopolymer: e.g., (1) polyphenylene oxide (PPO)—polystyrene (PS) where the miscibility of the two polymers is caused by the presence of an aromatic ring in the repeat units of both chains; and (2) polyethylene terephthalate (PET)—polybutylene terephthalate (PBT); and (3) poly(methyl methacrylate) (PMMA)—polyvinylidene fluoride (PVDF). These blends further include: homopolymer—copolymer: e.g., (1) polypropylene (PP)—EPDM; and (2) polycarbonate (PC)—acrylonitrile butadiene styrene (ABS).
In order to make two polymers mix, it is important to make them have less energy when mixed than they would be separate. But most of the time, the two polymers which are targeted to be blended, will not be miscible. This is not fatal, it simply means that a bit more chemistry is involved. One approach is to use copolymers. Polystyrene doesn't blend with many polymers, but if use of a copolymer is made from styrene and p-(hexafluoro-2-hydroxyisopropyl)styrene, blending is a lot easier. Fluorine atoms are very electronegative, and they're going to draw electrons away from all the nearby atoms. This approach leaves the alcohol hydrogen very lacking in electrons, which means it is left with a partial positive charge. It is known that hydrogen will form strong hydrogen bonds with any group with a partial negative charge. This enables the formation of blends of this copolymer with polycarbonates, poly(methyl methacrylate), and poly(vinyl acetate).
In yet another approach, a blend can be created using for example, a random copolymer of styrene and acrylonitrile. This copolymer will blend with poly(methyl methacrylate) (PMMA). However, PMMA will not blend with either polystyrene or polyacrylonitrile. The random copolymer will blend with PMMA because while the styrene segments and the acrylonitrile segments of the random copolymer may not like PMMA, they like each other even less. The styrene segments are non-polar, while the acrylonitrile segments are very polar. So, the styrene segments and the acrylonitrile segments blend into the PMMA to avoid coming into contact with each other.
For making blends in large amounts, one approach is to heat the two polymers together until they are above the glass transition temperatures of both polymers. At this point they can be mixed. This is often done in machines such as extruders.
A few polymer pairs mix. Most don't. But there are also polymer pairs that sometimes mix and sometimes don't. The variables that one can control to make them mix or not mix are usually temperature and composition. A lot of polymer pairs are only miscible when there is a lot more of one polymer than of the other. There will be a range of compositions for which the two polymers won't mix.
The Hildebrand solubility parameter (δ) is but one measure of a numerical estimate of the degree of interaction between materials, and can be a good indication of solubility, particularly for nonpolar materials such as many polymers. There are other metrics which could be employed. Materials with similar values of δ are likely to be miscible. The Hildebrand solubility parameter is the square root of the cohesive energy density:
The cohesive energy density is the amount of energy needed to completely remove unit volume of molecules from their neighbors to infinite separation (an ideal gas). This is equal to the heat of vaporization of the compound divided by its molar volume in the condensed phase. In order for a material to dissolve, these same interactions need to be overcome as the molecules are separated from each other and surrounded by the solvent. Materials with similar solubility parameters will be able to interact with each other, resulting in solvation, miscibility or swelling.
The conventional units for the solubility parameter are (calories per cm3)1/2, or cal1/2 cm−3/2. The SI units are J1/2 m−3/2, equivalent to the pascal1/2 and wherein 1 calorie is equal to 4.184 J.
Another approach to determining miscibility is by use of the Free Energy equation which provides another definition of what miscibility means in terms of thermodynamics; from it the state of miscibility of a polymer pair cannot be obtained.
ΔGM=ΔHM−TΔSM
The most common method to establish polymer miscibility is Differential Scanning calorimetry (DSC), with which determination of the glass transition temperature (Tg) or the depression of the melting temperature allow one to obtain details of the mixing.
Completely miscible blends consist of one homogeneous phase. This type of blend exhibits only one glass transition temperature (Tg), which is between the Tg s of both blend components with a close relation to the blend composition.
The miscibility of homopolymer/copolymer blends has been successfully described by the binary interaction model. The most common specific intermolecular interactions occurring between two different polymer chains are: hydrogen bond, ionic bond and dipole-dipole interactions
The criteria for determining whether or not two polymers are miscible are now well established. One common method used for establishing miscibility in polymer-polymer blends or partial phase mixing in such blends is through determination of the glass transition (or transitions) in the blend versus those of the unblended constituents. A miscible polymer blend will usually exhibit a single glass transition Tg between the Tg's of the components. With cases of limited miscibility, two separate transitions Tg1 and Tg2 between those of the constituents may result, typically depicting two phases, a phase rich in the first component and a second phase rich in the second component. A partially miscible blend of the first and second polymer blends is characterized by more than one glass transition temperature Tg, but at a location between Tg1 and Tg2.
In yet another aspect of the invention, separation between regions 21 and 26 is effected by selective dissolution in a solvent in which the polymer of region 21 is soluble whereas the polymer of region 26 is not. For example, if region 21 is overmolded with polystyrene, then simply dipping the nozzle in acetone will reveal the second geometry, provided that region 26 is either not soluble in acetone, or minimally soluble in acetone.
The overmolding approach enables the manufacturer to use a first geometric shape for the tip which is formed by removal at fracture zone 11 while having a tip with a second geometric shape at the extremity. The second geometric shape may be similar or dissimilar to the first geometric shape, depending on the shape of the cavity of the mold. Therefore, overmolding can be employed to result in a tip which has two circular geometries for the tip, the diameters being different, or the tip could have two geometries which are completely different (e.g., circular at fracture zone 11 and oval or polygon-shaped at exit 17b).
The color-changing aspects of the invention above, use thermochromism which is typically implemented via one of two common approaches: liquid crystals and leuco dyes. Liquid crystals are used in precision applications, as their responses can be engineered to accurate temperatures, but their color range is limited by their principle of operation. Leuco dyes allow wider range of colors to be used, but their response temperatures are more difficult to set with accuracy.
Some liquid crystals are capable of displaying different colors at different temperatures. This change is dependent on selective reflection of certain wavelengths by the crystalline structure of the material, as it changes between the low-temperature crystalline phase, through anisotropic chiral or twisted nematic phase, to the high-temperature isotropic liquid phase. Only the nematic mesophase has thermochromic properties. This restricts the effective temperature range of the material.
The twisted nematic phase has the molecules oriented in layers with regularly changing orientation, which gives them periodic spacing. The light passing through the crystal undergoes Bragg diffraction on these layers, and the wavelength with the greatest constructive interference is reflected back, which is perceived as a spectral color. A change in the crystal temperature can result in a change of spacing between the layers and therefore in the reflected wavelength. The color of the thermochromic liquid crystal can therefore continuously range from non-reflective (black) through the spectral colors to black again, depending on the temperature. Typically, the high temperature state will reflect blue-violet, while the low-temperature state will reflect red-orange. Since blue is a shorter wavelength than red, this indicates that the distance of layer spacing is reduced by heating through the liquid-crystal state.
Some such materials are cholesteryl nonanoate or cyanobiphenyls. Liquid crystals used in dyes and inks often come microencapsulated, in the form of suspension. Liquid crystals are used in applications where the color change has to be accurately defined.
Thermochromic dyes are based on mixtures of leuco dyes with suitable other chemicals, displaying a color change (usually between the colorless leuco form and the colored form) in dependence on temperature. The dyes are rarely applied on materials directly; they are usually in the form of microcapsules with the mixture sealed inside. An illustrative example would include microcapsules with crystal violet lactone, weak acid, and a dissociable salt dissolved in dodecanol; when the solvent is solid, the dye exists in its lactone leuco form, while when the solvent melts, the salt dissociates, the pH inside the microcapsule lowers, the dye becomes protonated, its lactone ring opens, and its absorption spectrum shifts drastically, therefore it becomes deeply violet. In this case the apparent thermochromism is in fact halochromism.
The dyes most commonly used are spirolactones, fluorans, spiropyrans, and fulgides. The weak acids include bisphenol A, parabens, 1,2,3-triazole derivates, and 4-hydroxycoumarin and act as proton donors, changing the dye molecule between its leuco form and its protonated colored form; stronger acids would make the change irreversible.
Leuco dyes have less accurate temperature response than liquid crystals. They are suitable for general indicators of approximate temperature. They are usually used in combination with some other pigment, producing a color change between the color of the base pigment and the color of the pigment combined with the color of the non-leuco form of the leuco dye. Organic leuco dyes are available for temperature ranges between about 23° F. (−5° C.) and about 140° F. (60° C.), in wide range of colors. The color change usually happens in about a 5.4° F. (3° C.) interval.
The size of the microcapsules typically ranges between 3-5 μm (over 10 times larger than regular pigment particles), which requires some adjustments to printing and manufacturing processes.
Thermochromic paints use liquid crystals or leuco dye technology. After absorbing a certain amount of light or heat, the crystalline or molecular structure of the pigment reversibly changes in such a way that it absorbs and emits light at a different wavelength than at lower temperatures.
The thermochromic dyes contained either within or affixed upon either the disposable nozzle or hoses may be configured to change the color of the composition in various ways. For example, in one embodiment, once the composition reaches a selected temperature, the composition may change from a base color to a white color or a clear color. In another embodiment, a pigment or dye that does not change color based on temperature may be present for providing a base color. The thermochromic dyes, on the other hand, can be included in order to change the composition from the base color to at least one other color.
In one particular embodiment, the plurality of thermochromic dyes are configured to cause the cleansing composition to change color over a temperature range of at least about 3° C., such as at least about 5° C., once the composition is heated to a selected temperature. For example, multiple thermochromic dyes may be present within the cleansing composition so that the dyes change color as the composition gradually increases in temperature. For instance, in one embodiment, a first thermochromic dye may be present that changes color at a temperature of from about 23° C. to about 28° C. and a second thermochromic dye may be present that changes color at a temperature of from about 27° C. to about 32° C. If desired, a third thermochromic dye may also be present that changes color at a temperature of from about 31° C. to about 36° C. In this manner, the cleansing composition changes color at the selected temperature and then continues to change color in a stepwise manner as the temperature of the composition continues to increase. It should be understood that the above temperature ranges are for exemplary and illustrative purposes only.
Any thermochromic substance that undergoes a color change at the desired temperature may generally be employed in the present disclosure. For example, liquid crystals may be employed as a thermochromic substance in some embodiments. The wavelength of light (“color”) reflected by liquid crystals depends in part on the pitch of the helical structure of the liquid crystal molecules. Because the length of this pitch varies with temperature, the color of the liquid crystals is also a function of temperature. One particular type of liquid crystal that may be used in the present disclosure is a liquid crystal cholesterol derivative. Exemplary liquid crystal cholesterol derivatives may include alkanoic and aralkanoic acid esters of cholesterol, alkyl esters of cholesterol carbonate, cholesterol chloride, cholesterol bromide, cholesterol acetate, cholesterol oleate, cholesterol caprylate, cholesterol oleyl-carbonate, and so forth. Other suitable liquid crystal compositions are possible and contemplated within the scope of the invention.
In addition to liquid crystals, another suitable thermochromic substance that may be employed in the present disclosure is a composition that includes a proton accepting chromogen (“Lewis base”) and a solvent. The melting point of the solvent controls the temperature at which the chromogen will change color. More specifically, at a temperature below the melting point of the solvent, the chromogen generally possesses a first color (e.g., red). When the solvent is heated to its melting temperature, the chromogen may become protonated or deprotonated, thereby resulting in a shift of the absorption maxima. The nature of the color change depends on a variety of factors, including the type of proton-accepting chromogen utilized and the presence of any additional temperature-insensitive chromogens. Regardless, the color change is typically reversible.
Although not required, the proton-accepting chromogen is typically an organic dye, such as a leuco dye. In solution, the protonated form of the leuco dye predominates at acidic pH levels (e.g., pH of about 4 or less). When the solution is made more alkaline through deprotonation, however, a color change occurs. Of course, the position of this equilibrium may be shifted with temperature when other components are present. Suitable and non-limiting examples of leuco dyes for use in the present disclosure may include, for instance, phthalides; phthalanes; substituted phthalides or phthalanes, such as triphenylmethane phthalides, triphenylmethanes, or diphenylmethanes; acyl-leucomethylene blue compounds; fluoranes; indolylphthalides, spiropyranes; cumarins; and so forth. Exemplary fluoranes include, for instance, 3,3′-dimethoxyfluorane, 3,6-dimethoxyfluorane, 3,6-di-butoxyfluorane, 3-chloro-6-phenylamino-flourane, 3-diethylamino-6-dimethylfluorane, 3-diethylamino-6-methyl-7-chlorofluorane, and 3-diethyl-7,8-benzofluorane, 3,3′-bis-(p-dimethyl-aminophenyl)-7-phenylaminofluorane, 3-diethylamino-6-methyl-7-phenylamino-fluorane, 3-diethylamino-7-phenyl-aminofluorane, and 2-anilino-3-methyl-6-diethylamino-fluorane. Likewise, exemplary phthalides include 3,3′,3″-tris(p-dimethylamino-phenyl)phthalide, 3,3′-bis(p-dimethyl-aminophenyl)phthalide, 3,3-bis(p-diethylamino-phenyl)-6-dimethylamino-phthalide, 3-(4-diethylaminophenyl)-3-(1-ethyl-2-methylindol-3-yl)phthalide, and 3-(4-diethylamino-2-methyl)phenyl-3-(1,2-dimethylindol-3-yl)phthalide.
Although any solvent for the thermochromic dye may generally be employed in the present disclosure, it is typically desired that the solvent have a low volatility. For example, the solvent may have a boiling point of about 150° C. or higher, and in some embodiments, from about 170° C. to 280° C. Likewise, the melting temperature of the solvent is also typically from about 25° C. to about 40° C., and in some embodiments, from about 30° C. to about 37° C. Examples of suitable solvents may include saturated or unsaturated alcohols containing about 6 to 30 carbon atoms, such as octyl alcohol, dodecyl alcohol, lauryl alcohol, cetyl alcohol, myristyl alcohol, stearyl alcohol, behenyl alcohol, geraniol, etc.; esters of saturated or unsaturated alcohols containing about 6 to 30 carbon atoms, such as butyl stearate, methyl stearate, lauryl laurate, lauryl stearate, stearyl laurate, methyl myristate, decyl myristate, lauryl myristate, butyl stearate, lauryl palmitate, decyl palmitate, palmitic acid glyceride, etc.; azomethines, such as benzylideneaniline, benzylidenelaurylamide, o-methoxybenzylidene laurylamine, benzylidene p-toluidine, p-cumylbenzylidene, etc.; amides, such as acetamide, stearamide, etc.; and so forth.
The thermochromic composition may also include a proton-donating agent (also referred to as a “color developer”) to facilitate the reversibility of the color change. Such proton-donating agents may include, for instance, phenols, azoles, organic acids, esters of organic acids, and salts of organic acids. Exemplary phenols may include phenylphenol, bisphenol A, cresol, resorcinol, chlorolucinol, b-naphthol, 1,5-dihydroxynaphthalene, pyrocatechol, pyrogallol, trimer of p-chlorophenol-formaldehyde condensate, etc. Exemplary azoles may include benzotriaoles, such as 5-chlorobenzotriazole, 4-laurylaminosulfobenzotriazole, 5-butylbenzotriazole, dibenzotriazole, 2-oxybenzotriazole, 5-ethoxycarbonylbenzotriazole, etc.; imidazoles, such as oxybenzimidazole, etc.; tetrazoles; and so forth. Exemplary organic acids may include aromatic carboxylic acids, such as salicylic acid, methylenebissalicylic acid, resorcylic acid, gallic acid, benzoic acid, p-oxybenzoic acid, pyromellitic acid, b-naphthoic acid, tannic acid, toluic acid, trimellitic acid, phthalic acid, terephthalic acid, anthranilic acid, etc.; aliphatic carboxylic acids, such as stearic acid, 1,2-hydroxystearic acid, tartaric acid, citric acid, oxalic acid, lauric acid, etc.; and so forth. Exemplary esters may include alkyl esters of aromatic carboxylic acids in which the alkyl moiety has 1 to 6 carbon atoms, such as butyl gallate, ethyl p-hydroxybenzoate, methyl salicylate, etc.
The amount of the proton-accepting chromogen employed may generally vary, but is typically from about 2 wt. % to about 20 wt. %, and in some embodiments, from about 5 to about 15 wt. % of the thermochromic substance. Likewise, the proton-donating agent may constitute from about 5 to about 40 wt. %, and in some embodiments, from about 10 wt. % to about 30 wt. % of the thermochromic substance. In addition, the solvent may constitute from about 50 wt. % to about 95 wt. %, and in some embodiments, from about 65 wt. % to about 85 wt. % of the thermochromic composition.
Regardless of the particular thermochromic substance employed, it may be microencapsulated to enhance the stability of the substance during processing. For example, the thermochromic substance may be mixed with a thermosetting resin according to any conventional method, such as interfacial polymerization, in-situ polymerization, etc. The thermosetting resin may include, for example, polyester resins, polyurethane resins, melamine resins, epoxy resins, diallyl phthalate resins, vinylester resins, and so forth. The resulting mixture may then be granulated and optionally coated with a hydrophilic macromolecular compound, such as alginic acid and salts thereof, carrageenan, pectin, gelatin and the like, semisynthetic macromolecular compounds such as methylcellulose, cationized starch, carboxymethylcellulose, carboxymethylated starch, vinyl polymers (e.g., polyvinyl alcohol), polyvinylpyrrolidone, polyacrylic acid, polyacrylamide, maleic acid copolymers, and so forth. The resulting thermochromic microcapsules typically have a size of from about 1 to about 50 micrometers, and in some embodiments, from about 3 to about 15 micrometers. Various other microencapsulation techniques may also be used.
Thermochromic dyes are commercially available from various sources. In one embodiment, for instance, thermochromic dyes marketed by Chromadic creations, Hamilton, Ontario and sold under the trade name SpectraBurst Thermochromic Polypropylene.
The thermochromic dyes can be present in the composition in an amount sufficient to have a visual effect on the color of the composition. The amount or concentration of the dyes can also be increased or decreased depending upon the desired intensity of any color. In general, the thermochromic dyes may be present in the composition in an amount from about 0.01% by weight to about 9% by weight, such as from about 0.1% by weight to about 3% by weight. For instance, in one particular embodiment, the thermochromic dyes may be present in an amount from about 0.3% to about 1.5% by weight.
As described above, thermochromic dyes typically change from a specific color to clear at a certain temperature, e.g., dark blue below 60° F. (15.6° C.) to transparent or translucent above 60° F. (15.6° C.). If desired, other pigments or dyes can be added to the composition in order to provide a background color that remains constant independent of the temperature of the composition. By adding other pigments or dyes in combination with the thermochromic dyes to the composition, the thermochromic dyes can provide a color change at certain temperatures rather than just a loss of color should the thermochromic dye become clear. For instance, a non-thermochromic pigment, such as a yellow pigment, may be used in conjunction with a plurality of thermochromic dyes, such as a red dye and a blue dye. When all combined together, the cleansing composition may have a dark color. As the composition is increased in temperature, the red thermochromic dye may turn clear changing the color to a green shade (a combination of yellow and blue). As the temperature further increases, the blue thermochromic dye turns clear causing the composition to turn yellow.
It should be understood, that all different sorts of thermochromic dyes and non-thermochromic pigments and dyes may be combined to produce a composition having a desired base color and one that undergoes desired color changes. The color changes, for instance, can be somewhat dramatic and fanciful. For instance, in one embodiment, the composition may change from green to yellow to red.
In an alternative embodiment, however, the composition can contain different thermochromic dyes all having the same color. As the temperature of the composition is increased, however, the shade or intensity of the color can change. For instance, the composition can change from a vibrant blue to a light blue to a clear color. In addition to the above, many alterations and permutations are possible. Any of a variety of colors and shades can be mixed to undergo color changes as a function of temperature.
While the above invention has been described with particularity to spray foam applications, using blowing agents, there is no need to limit the invention to such, and in fact, any coating may be applied, with minor variations known to those having ordinary skill-in-the-art. For instance, polyurethane coatings may be applied to surfaces in the manner described without the need for a static mixer for example. The same applies to many other coatings. For these applications, the invention reduces to: in combination, an applicator having a housing and a nozzle which comprises: an expanded rear portion of the nozzle for affixing the nozzle to a front of the housing employing a fastening means; an egress segment of the nozzle at an opposed end from the expanded rear portion of the nozzle, the egress segment comprising: a nozzle tip at an egress end of the nozzle, the nozzle tip applying a foam or a coating in a first pattern; a first nozzle segment rearward along a longitudinal axis of the nozzle tip; a fracture zone rearward along the longitudinal axis of the first nozzle segment; a second nozzle segment rearward along the longitudinal axis of the fracture zone; and a terminal end of the fracture zone forming a second nozzle tip when the first nozzle segment is removed from the egress segment of the nozzle along the fracture zone, the second nozzle segment applying the foam or the coating in a second pattern, the second pattern being different from the first pattern.
In one embodiment, the fracture zone is a reduced thickness area between the first and second nozzle segments and in which the first nozzle segment and second nozzle segment comprise a first polymer and a second polymer. Often, the first polymer and the second polymer are at least partially miscible polymers, having at least one Tg between the Tg of the first polymer and the Tg of the second polymer. When the first polymer and the second polymer are miscible, they may have a single Tg between the Tg of the first polymer and the Tg of the second polymer. In yet another aspect of the invention, the first polymer and the second polymer are the same, but of different degrees of crosslinking and often, the first polymer has a higher degree of crosslinking than the second polymer, which has either a reduced degree of crosslinking or no crosslinking. In a preferred embodiment, particularly when applying foam to a surface, at least a portion of the spray gun nozzle is a polymer, which comprises a color-changeable additive, often a thermochromatic dye. In yet another embodiment, the first polymer is soluble in a solvent, and the second polymer is not soluble in that same solvent.
While the invention has been described with reference to certain embodiments, it will be understood by those skilled in the art that various changes may be made, and equivalents may be substituted without departing from the scope of the invention. In addition, many modifications may be made to adapt a particular situation or material to the teachings of the invention without departing from its scope. Therefore, it is intended that the invention not be limited to the particular embodiment disclosed, but that the invention will include all embodiments falling within the scope of the appended claims.
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