WO1995011091A1 - Method and apparatus for spraying viscous adhesives - Google Patents

Method and apparatus for spraying viscous adhesives Download PDF

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Publication number
WO1995011091A1
WO1995011091A1 PCT/US1994/012086 US9412086W WO9511091A1 WO 1995011091 A1 WO1995011091 A1 WO 1995011091A1 US 9412086 W US9412086 W US 9412086W WO 9511091 A1 WO9511091 A1 WO 9511091A1
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WO
WIPO (PCT)
Prior art keywords
adhesive
mixer
adhesive composition
inlet
virgin
Prior art date
Application number
PCT/US1994/012086
Other languages
French (fr)
Inventor
James W. Messerly
James C. Smith
Laurence B. Saidman
Original Assignee
Nordson Corporation
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Nordson Corporation filed Critical Nordson Corporation
Priority to AU10413/95A priority Critical patent/AU1041395A/en
Publication of WO1995011091A1 publication Critical patent/WO1995011091A1/en

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Classifications

    • BPERFORMING OPERATIONS; TRANSPORTING
    • B05SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05DPROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D1/00Processes for applying liquids or other fluent materials
    • B05D1/02Processes for applying liquids or other fluent materials performed by spraying
    • B05D1/025Processes for applying liquids or other fluent materials performed by spraying using gas close to its critical state
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B05SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05BSPRAYING APPARATUS; ATOMISING APPARATUS; NOZZLES
    • B05B12/00Arrangements for controlling delivery; Arrangements for controlling the spray area
    • B05B12/08Arrangements for controlling delivery; Arrangements for controlling the spray area responsive to condition of liquid or other fluent material to be discharged, of ambient medium or of target ; responsive to condition of spray devices or of supply means, e.g. pipes, pumps or their drive means
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B05SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05BSPRAYING APPARATUS; ATOMISING APPARATUS; NOZZLES
    • B05B12/00Arrangements for controlling delivery; Arrangements for controlling the spray area
    • B05B12/14Arrangements for controlling delivery; Arrangements for controlling the spray area for supplying a selected one of a plurality of liquids or other fluent materials or several in selected proportions to a spray apparatus, e.g. to a single spray outlet
    • B05B12/1418Arrangements for controlling delivery; Arrangements for controlling the spray area for supplying a selected one of a plurality of liquids or other fluent materials or several in selected proportions to a spray apparatus, e.g. to a single spray outlet for supplying several liquids or other fluent materials in selected proportions to a single spray outlet
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B05SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05BSPRAYING APPARATUS; ATOMISING APPARATUS; NOZZLES
    • B05B7/00Spraying apparatus for discharge of liquids or other fluent materials from two or more sources, e.g. of liquid and air, of powder and gas
    • B05B7/24Spraying apparatus for discharge of liquids or other fluent materials from two or more sources, e.g. of liquid and air, of powder and gas with means, e.g. a container, for supplying liquid or other fluent material to a discharge device
    • B05B7/26Apparatus in which liquids or other fluent materials from different sources are brought together before entering the discharge device
    • B05B7/28Apparatus in which liquids or other fluent materials from different sources are brought together before entering the discharge device in which one liquid or other fluent material is fed or drawn through an orifice into a stream of a carrying fluid
    • B05B7/32Apparatus in which liquids or other fluent materials from different sources are brought together before entering the discharge device in which one liquid or other fluent material is fed or drawn through an orifice into a stream of a carrying fluid the fed liquid or other fluent material being under pressure
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B05SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05DPROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D2401/00Form of the coating product, e.g. solution, water dispersion, powders or the like
    • B05D2401/90Form of the coating product, e.g. solution, water dispersion, powders or the like at least one component of the composition being in supercritical state or close to supercritical state

Definitions

  • This invention relates to a method and apparatus for dispensing viscous adhesives, and, more particularly, to a method and apparatus for dynamically mixing adhesives having a relatively high solids content with supercritical carbon dioxide as a fluid diluent to form an adhesive composition which can be sprayed at comparatively low pressures.
  • Adhesives have been utilized for decades to bind a wide variety of materials together, and new applications for adhesives are being developed on a continuing basis. Compared to mechanical fastening devices, adhesives are capable of distributing stresses over wider surface areas and provide superior strength-to-weight ratios and dimensional stability for a variety of finished products.
  • a large portion of the adhesives utilized in industrial and commercial applications contain organic solvents and/or nonaqueous diluents which function to reduce the viscosity of the adhesives to facilitate their application.
  • a variety of application methods are employed in industry, such as brushing, rolling, dipping and the like, but spraying of adhesive in atomized droplets is often the most desirable particularly when adhering materials such as paper, cardboard, wood, leather, plastic, cloth and rubber.
  • a growing concern with the application of adhesives containing organic solvents or nonaqueous diluents, particularly when employing the spraying method of application is the environmental hazards occasioned by the release of organic solvent vapors to atmosphere during the application procedure. The escaping solvents can contaminate the surrounding atmosphere and create injury to the personnel involved in the application operation. Additionally, since most solvents react with oxidants, pollution problems of toxicity, odor and smog may be created.
  • a batch type system and a continuous supply system are disclosed in Patent 5,066,522, and one or the other is employed depending upon the requirements of the particular application.
  • the effectiveness of each of these systems in spraying an acceptable coating or layer of viscous adhesive onto a substrate is dependent, at least in part, on the effectiveness with which the virgin adhesive and supercritical carbon dioxide are intermixed to form an adhesive composition wherein the supercritical carbon dioxide is dissolved or dispersed in solution with the adhesive.
  • the supercritical carbon dioxide and adhesive are combined within a static mixer located at a position downstream from the sources of both materials. It has been found that static mixers are ineffective in obtaining complete admixture of the supercritical carbon dioxide and adhesive especially when the virgin adhesive has a high solids content, i.e. on the order of at least about 20% to 30% solids.
  • the dynamic mixer breaks down the carbon gel of the rubber so that the supercritical carbon dioxide becomes mixed in and penetrates the interstices of the rubber before the heptane solvent component of the rubber dissolves into the supercritical carbon dioxide. This produces a homogenous mixture of supercritical carbon dioxide and rubber adhesive which is a sprayable composition.
  • this invention is predicated upon the concept of providing an apparatus for spraying viscous adhesive in which virgin adhesive and a supercritical fluid diluent, such as supercritical carbon dioxide, are thoroughly and substantially completely intermixed by a dynamic mixing device.
  • the mixing device comprises a housing having a hollow interior formed with a first inlet for the supercritical carbon dioxide, a second inlet for adhesive which is located near the first inlet, and, an outlet spaced from the two inlets.
  • a wire brush is placed within the housing interior, with its bristles preferably located in the space between the two inlets and the outlet. The opposite end or handle portion of the brush is connected to an air motor or other rotational device.
  • the motor is operative to rotate the wire brush within the mixer housing so that in the course of passage from the inlets to the outlet of the housing the supercritical carbon dioxide and adhesive are intermixed to form an adhesive composition in which the supercritical carbon dioxide is substantially completely dissolved or dispersed in the adhesive to produce a sprayable composition. It is contemplated that paddles or other movable mixing elements could be utilized in place of the wire brush described above, provided that the adhesive undergoes sufficient agitation and shearing to enable the supercritical carbon dioxide to dissolve or disperse in solution within the adhesive.
  • a recirculation loop is preferably provided for continuously recir-culating the adhesive composition from the outlet of the mixer, to the adhesive dispenser and then back to the second inlet of the mixer for combination with additional supercritical carbon dioxide.
  • the recirculation loop is also connected to a source of virgin adhesive which selectively supplies additional adhesive to the loop as the spraying operation proceeds.
  • a capacitance sensor is incorporated in the loop to provide a measurement of the capacitance of the adhesive composition which is indicative of the relative proportion or ratio of supercritical fluid and virgin adhesive within the adhesive composition. The capacitance of the adhesive composition is monitored to ensure it remains within a predetermined level to achieve optimum spraying conditions.
  • adheresive composition refers to adhesives having a relatively high solids content, i.e. on the order of at least about 10% to 40% by volume, wherein a portion of the solvent component within the adhesive is replaced with a fluid diluent such as supercritical fluid to reduce solvent emissions.
  • supercritical fluid as used herein is intended to refer to a gas in a supercritical state above its critical pressure and critical temperature, wherein the gas has a density approaching that of a liquid material. It is also contemplated that liquified gases could be utilized in forming adhesive compositions, and it should therefore be understood that the term “liquified gas” may be utilized interchangeably with the term “supercritical fluid” in the foregoing description.
  • a number of compounds in a supercritical or liquified state can be intermixed with the virgin adhesive to produce an adhesive composition for spraying by the apparatus of this invention.
  • These compounds include carbon dioxide, ammonia, water, nitrogen oxide (N 2 0) , methane, ethane, ethylene, propane, pentane, methanol, ethanol, isopropanol. isobutanol, chlorotrifluoro ethane, monofluoromethane and others.
  • supercritical carbon dioxide is employed because of its nontoxic nature and because its critical temperature and critical pressure of 85" F. and 1070 psi, respectively, are well within the operating ranges of standard airless spraying systems including the apparatus 10 of this invention.
  • the apparatus 10 comprises a supercritical carbon dioxide supply 12, a supply of virgin adhesive 14, a recirculation loop 16, an adhesive dispenser 18, and a dynamic mixer 20. These components of apparatus 10 are described individually below, and then their collective operation in forming and spraying an adhesive composition containing supercritical carbon dioxide is explained.
  • the supercritical carbon dioxide supply 12 comprises a tank 22, containing liquified carbon dioxide, which is connected by a line 24 to a filter 26.
  • the liquified carbon dioxide passes through filter 26, and then through a line 28 into a pump 30.
  • the pump 30 increases the pressure of the liquified carbon dioxide to a level above its supercritical pressure, e.g. preferably in the range of about 1200 to 1600 psi.
  • the pump 30 is preferably a Haskell pump Model No. DSF35 commercially available from The Haskell Company of Burbank, California.
  • the pressurized, liquified carbon dioxide is discharged from pump 30 through line 32 into a heater 34, preferably of the type sold by Nordson Corporation of Westlake, Ohio, under the model No. NH4.
  • the heater 34 is effective to raise the temperature of the liquified carbon dioxide to a level at least above the super-critical temperature of carbon dioxide, and preferably in the range of about 110 to 125 ⁇ F.
  • a relief valve 36 is connected to the heater 34 to act as a pressure release within the supercritical carbon dioxide supply 12, if required.
  • the liquified carbon dioxide is converted to supercritical carbon dioxide upon discharge from the heater 34.
  • the supercritical carbon dioxide is transmitted through a line 38 to a valve 40 which controls the flow of supercritical carbon dioxide into a supply line 42 connected to mixer 20.
  • the supply line 42 includes a one-way valve 44 to prevent flow of material from the mixer 20 in a direction toward the valve 40.
  • the valve 40 is connected by a line 41 to a controller 120 which operates the valve 40 in the same manner as the computer and pulse generator circuit of U.S. Patent No. 5,215,253 to Saidman et al., owned by the assignee of this invention, the disclosure of which is incorporated by reference in its entirety herein.
  • the controller 40 employs a standard PID (proportional, integral, derivative) control algorithm to control the opening and closing of valve 40, and, hence, the quantity of supercritical carbon dioxide entering the recirculation loop 16.
  • the mixer 20 comprises a housing 46, formed with an interior 48, having a first inlet 50 connected to the supply line 42, a second inlet 52 connected to one end of recirculation loop 16, and, an outlet 54 connected to the opposite end of recirculation loop 16.
  • the housing interior 48 receives a wire brush 56 having bristles 58 and a stem portion or handle 60.
  • the bristles 58 of wire brush 56 are preferably located within the housing interior 48 in the space between the second inlet 52 and the outlet 54, and, as depicted in the Fig. , such bristles 58 extend across substantially the entire cross section of the housing interior 48.
  • the handle 60 of wire brush 56 is rotatably carried by an internal bronze bearing 62 and an external bronze bearing 64 as depicted in the Fig. A portion of the handle 60 between the bearing 62, 64 receives a packing 66 preferably formed of tetrafluoroethylene or similar material capable of creating a seal along the brush handle 60 to prevent the escape of adhesive or supercritical carbon dioxide from the housing interior 48.
  • the outermost end of handle 60 is connected by a coupler 68 to the output of a variable speed motor 70.
  • the motor 70 is effective to rotate the wire brush within the housing interior 48 at a speed in the range of about 2,000 to 2,500 revolutions per minute which is monitored by a tachometer 71.
  • the tachometer 71 sends a signal representative of the motor speed via a line 77 to a motor control 73, which, in turn, controls the operation of motor 70 as required.
  • the recirculation loop 16 comprises a line 72 connected to the outlet 54 of mixer 20 which, in turn, is connected to a capacitance cell 74 e.g. a capacitance sensing circuit of the type disclosed in U.S. Patent No. 5,215,253 to Saidman et al., noted above.
  • the capacitance cell 74 is effective to sense the capacitance of the material flowing therethrough, which, in turn, can be correlated to the relative proportion of supercritical carbon dioxide within such material.
  • a meter 76 or other measurement device is connected to the capacitance cell 74 to provide a reading or indication of the capacitance of the material flowing through the recirculation loop 16 during operation of apparatus 10.
  • the capacitance cell 74 is connected by a line 75 to the controller 120 for purposes explained in more detail below. The detailed construction and operation of the capacitance cell 74 forms no part of this invention of itself, and is therefore not discussed herein.
  • a line 78 extends downstream from the capacitance cell 74 and is connected by a branch line 80 to the adhesive dispenser.
  • the dispenser 18 is a spray gun of the type sold by Nordson Corporation of Westlake, Ohio, under Model No. A7A.
  • the dispenser or spray gun 18 is a recirculating type gun which discharges material through a recirculation line 82 back into the line 78 in the event the gun 18 is not operating.
  • a regulating valve 84 is located within line 78 between the branch line 80 and recirculation line 82 to divide the flow of material so that a desired amount of material is always circulating in the recirculating loop 16.
  • a back pressure regulator 86 is connected to line 78 downstream from the regulating valve 84 to maintain the pressure of the material within line 78 at a substantially constant level for supply to the dispenser or spray gun 18.
  • a pressure monitoring device 88 is also connected to line 78, between the shut off valve 84 and back pressure regulator 86, to provide an indication of the pressure level within line 78.
  • the back pressure regulator is connected by a line 90 to a heater 92 preferably of the type sold by Nordson Corporation of Westlake, Ohio, under Model No. NH4.
  • the purpose of the heater 92 is to maintain the temperature of the material within recirculation loop 16 at a level in excess of the critical temperature of supercritical carbon dioxide and, preferably, at a temperature in the range of about 110 to 120° F.
  • virgin adhesive is transmitted from the adhesive source 14 into recirculation loop 16 through an adhesive pump 94 which may be, for example, a Nordson Rhino (R> Model pump.
  • the virgin adhesive is discharged from pump 94 through a line 96, which carries a shut off valve 97, directly into line 90 of the recirculation loop 16. Additionally, the adhesive pump 94 is connected by a line 95 to the controller 120 for purposes discussed below.
  • a one ⁇ way valve 98 is positioned in line 90 upstream from pump 94 to block the flow of virgin adhesive in a direction toward the pressure regulator 86.
  • a pressure monitoring device 99 is connected to line 90 between the one-way valve 98 and pressure regulator 86 to monitor the pressure within line 90 at that location. Controller 120 is connected to this pressure monitoring device 99 via a line 101 as will be described below.
  • the heater 92 is connected by a line 100 to a high pressure pump 102, preferably of the type sold by Nordson Corporation of Westlake, Ohio, under Model HP.
  • a high pressure pump 102 preferably of the type sold by Nordson Corporation of Westlake, Ohio, under Model HP.
  • an accumulator 104 is connected by a line 106 to line 100 at a location between the heater 92 and high pressure pump 102.
  • the accumulator 104 is also commercially available from The Parker Hannifin Corporation, of Hillsborough, North Carolina, under Model No. BD05A214.
  • the purpose of accumulator 104 is to dampen or smooth out any pressure fluctuations which may be present at the input to high pressure pump 102, which could be created, for example, when the adhesive dispenser or gun 18 is opened and/or when additional virgin adhesive is introduced into the recirculation loop 16 from pump 94.
  • the high pressure pump 102 is connected by a line 108 to a filter 110, preferably of the type sold by Nordson Corporation of Westlake, Ohio, under Model No. 109765.
  • Filter 110 is connected by a line 112 to the second inlet 52 of mixer 20 thus completing the recirculation loop 16. Operation of System
  • the method of operation of the apparatus 10 proceeds as follows. Initially, liquified carbon dioxide from tank 22 passes through the carbon dioxide supply 12 described above, where it is raised to sufficient temperature and pressure to form supercritical carbon dioxide downstream from the heater 34. The supercritical carbon dioxide is discharged from valve 40 through line 42 and past the one-way valve 44 into the first inlet 50 of the mixer 20.
  • virgin adhesive from pump 94 is introduced into the recirculation loop 16 by line 96 where it is heated to a temperature of about 120° F. , and then directed by high pressure pump 102 through filter 110 into the second inlet 52 of mixer 20.
  • the virgin adhesive supplied by the pump 94 is highly viscous, and may have a solids content of 30% or higher.
  • the mixer 20 is equipped with a dynamic mixing device, such as schematically shown in the Fig.
  • the dynamic mixing device comprises a wire brush 56 having bristles 58 which are located between the second inlet 52 and the outlet 54 of the mixer housing 46.
  • the supercritical carbon dioxide and virgin adhesive are introduced into the housing interior 48 through inlets 50, 52, respectively, where they come into contact with the bristles 58 of the wire brush 56.
  • the motor 70 is operative to rotate the wire brush 56, and, hence, the bristles 58, at speeds in the range of about 2,000 to 2,500 rpm. It has been found to be necessary that the wire brush 56 be rotated at least at a predetermined minimum speed. As noted above, the speed of motor 70 is monitored by tachometer 71 and controlled by the control 73 in response to a signal from tachometer 71. This control arrangement ensures that the motor speed remains above the predetermined minimum.
  • the viscous adhesive is exposed to high, dynamic shear stresses and agitation in the course of movement from the second inlet 52 to the outlet 54 of mixer 20.
  • This enables the supercritical carbon dioxide to thoroughly intermix with the virgin adhesive, so that it substantially completely disperses into solution therewith.
  • An adhesive composition is thus formed within mixer 20 comprising virgin adhesive and supercritical carbon dioxide which acts as a diluent to replace a substantial portion of the solvent content of the virgin adhesive.
  • the adhesive composition is discharged through the outlet 54 of mixer 20 and enters the recirculation loop 16 for transmission to the dispenser 18.
  • the relative proportion of supercritical carbon dioxide and virgin adhesive within the adhesive composition is monitored by the capacitance cell 74.
  • the cell 74 provides a measurement of the capacitance of the adhesive composition moving therethrough which can be correlated to its supercritical carbon dioxide content. If capacitance cell 74 sends a signal to controller 120 via line 75 representative of a capacitance reading which is too low, controller 120 sends a signal through line 95 to turn on the pump 94 so that adhesive is added to the loop until the capacitance rises up into the acceptable range.
  • controller 120 If the capacitance cell 74 sends a signal to controller 120 representative of a capacitance level which is too low, the PID loop function of controller 120 opens valve 40 to allow supercritical carbon dioxide into the recirculation loop 16 until the capacitance reading therein drops down into the acceptable range.
  • a further control function provided herein involves a measurement of pressure within the recirculation loop 16.
  • the pressure signal from pressure monitor 99 provides a continuous signal to controller 120. If the pressure drops below a minimum pressure setting, the signal through line 101 from pressure monitor 99 representative of such pressure level causes the controller 120 to turn on pump 94 so that additional adhesive is pumped into the recirculation loop 16 until the pressure climbs above the minimum setting.
  • the apparatus 10 of this invention is essentially continuous in operation, depending upon the requirements of a particular application. It is contemplated that upon initial start up of apparatus 10, the adhesive composition will be circulated within recirculation loop 16 for a period of time in order to ensure that sufficient supercritical carbon dioxide is present within the adhesive composition. Once the proper ratio of the components within the adhesive formulation is obtained, the spray gun 18 can be operated to spray adhesive composition onto a particular substrate. As the quantity of the adhesive composition within the loop 16 starts to become depleted, the flow of additional supercritical carbon dioxide and virgin adhesive into the recirculation loop 16 and mixer 20 is controlled by operation of the valve 40 and pump 94 as described above. Example

Abstract

A method and apparatus for spraying adhesive compositions having a high solids content comprises a source of supercritical fluid diluent (22) such as supercritical carbon dioxide, a source of virgin adhesive (14), an adhesive dispenser (18) and a mixer (20) communicating with each source (14, 22) of material and with the dispenser (18). The mixer (20) includes a dynamic mixing element which agitates the viscous adhesive material allowing (56) the supercritical carbon dioxide to be effectively dispersed into the adhesive, thus forming an adhesive composition with a high solids content having a relatively low viscosity suitable for spray application of the adhesive.

Description

METHOD AND APPARATUS FOR SPRAYING VISCOUS ADHESIVES
Field of the Invention
This invention relates to a method and apparatus for dispensing viscous adhesives, and, more particularly, to a method and apparatus for dynamically mixing adhesives having a relatively high solids content with supercritical carbon dioxide as a fluid diluent to form an adhesive composition which can be sprayed at comparatively low pressures. Background of the invention
Adhesives have been utilized for decades to bind a wide variety of materials together, and new applications for adhesives are being developed on a continuing basis. Compared to mechanical fastening devices, adhesives are capable of distributing stresses over wider surface areas and provide superior strength-to-weight ratios and dimensional stability for a variety of finished products.
A large portion of the adhesives utilized in industrial and commercial applications contain organic solvents and/or nonaqueous diluents which function to reduce the viscosity of the adhesives to facilitate their application. A variety of application methods are employed in industry, such as brushing, rolling, dipping and the like, but spraying of adhesive in atomized droplets is often the most desirable particularly when adhering materials such as paper, cardboard, wood, leather, plastic, cloth and rubber. A growing concern with the application of adhesives containing organic solvents or nonaqueous diluents, particularly when employing the spraying method of application, is the environmental hazards occasioned by the release of organic solvent vapors to atmosphere during the application procedure. The escaping solvents can contaminate the surrounding atmosphere and create injury to the personnel involved in the application operation. Additionally, since most solvents react with oxidants, pollution problems of toxicity, odor and smog may be created.
While it may be possible to simply reduce the organic solvent and/or nonaqueous diluent content of certain adhesives, such a reduction generally increases the viscosity of the resulting adhesive composition to such an extent that it can no longer be sprayed using conventional techniques, i.e. air spray, airless spray and air-assisted, airless spray. Even if such highly viscous adhesive compositions are capable of being sprayed, the pressure required to convey and transmit the adhesive through an adhesive dispenser to obtain successful atomization is very high. In some cases, even at high application pressures, the adhesive layer resulting from spraying viscous adhesive compositions does not have enough solvent present to allow for sufficient flow out of the adhesive where a continuous, uniform adhesive coating is desired. These problems have been addressed in U.S. Patent No. 5,066,522 to Cole, et al., in which it is suggested that at least a portion of the organic solvents and/or nonaqueous diluents in conventional adhesive compositions be replaced with a supercritical fluid as a diluent. As discussed in Patent 5,066,522, supercritical carbon dioxide has been found to be an acceptable replacement for a substantial portion of the organic solvents or nonaqueous diluents currently utilized in many adhesive compositions. The presence of supercritical carbon dioxide in solution with the adhesive reduces the environmental hazards created by the escape of solvents, enhances curing of the adhesive for certain types of adhesive materials, and often avoids the formation of "cobwebs" or elongated, thin strands of adhesive which may be produced during spraying operations with conventional adhesive formulations. The problem of cobwebs is eliminated because of the explosive atomization created when the supercritical carbon dioxide is released from solution upon exposure of the pressurized solution to atmosphere.
A batch type system and a continuous supply system are disclosed in Patent 5,066,522, and one or the other is employed depending upon the requirements of the particular application. The effectiveness of each of these systems in spraying an acceptable coating or layer of viscous adhesive onto a substrate is dependent, at least in part, on the effectiveness with which the virgin adhesive and supercritical carbon dioxide are intermixed to form an adhesive composition wherein the supercritical carbon dioxide is dissolved or dispersed in solution with the adhesive. In both the batch type and continuous supply systems disclosed in Patent 5,066,522, the supercritical carbon dioxide and adhesive are combined within a static mixer located at a position downstream from the sources of both materials. It has been found that static mixers are ineffective in obtaining complete admixture of the supercritical carbon dioxide and adhesive especially when the virgin adhesive has a high solids content, i.e. on the order of at least about 20% to 30% solids.
The problem with static mixers is particularly evident when attempting to spray rubber-based cements, especially when carbon gels are present. These types of adhesives contain "bound rubbers" which means that the rubber and solvent components of the adhesive form a suspension or dispersion as opposed to a solution. Most bound rubber adhesives use heptane as a solvent to reduce their viscosity. When these types of adhesives are passed through a static mixer with supercritical carbon dioxide, the heptane preferentially dissolves into the supercritical carbon dioxide, leaving the rubber component. The result is pockets of highly solvated supercritical carbon dioxide in a thick, high viscosity rubber, which cannot be effectively sprayed. Summary of the Invention
It is therefore among the objectives of this invention to provide a method and apparatus for spraying highly viscous adhesives, such as bound rubber adhesives, which produces an adhesive composition which is readily sprayable at comparatively low pressure, and which is simple in construction and operation. These objectives are accomplished in an apparatus for spraying adhesive compositions having a high solids content comprising a source of fluid diluent such as supercritical carbon dioxide, a source of virgin adhesive, an adhesive dispenser and a mixer communicating with each source of material and with the dispenser. The mixer includes a dynamic mixing element which agitates the viscous adhesive material allowing the supercritical carbon dioxide to be dissolved or dispersed into solution with the adhesive material, thus forming an adhesive composition having a high solids content and relatively low viscosity.
In the case of bound rubber adhesives, the dynamic mixer breaks down the carbon gel of the rubber so that the supercritical carbon dioxide becomes mixed in and penetrates the interstices of the rubber before the heptane solvent component of the rubber dissolves into the supercritical carbon dioxide. This produces a homogenous mixture of supercritical carbon dioxide and rubber adhesive which is a sprayable composition.
More generally, this invention is predicated upon the concept of providing an apparatus for spraying viscous adhesive in which virgin adhesive and a supercritical fluid diluent, such as supercritical carbon dioxide, are thoroughly and substantially completely intermixed by a dynamic mixing device. In the presently preferred embodiment, the mixing device comprises a housing having a hollow interior formed with a first inlet for the supercritical carbon dioxide, a second inlet for adhesive which is located near the first inlet, and, an outlet spaced from the two inlets. A wire brush is placed within the housing interior, with its bristles preferably located in the space between the two inlets and the outlet. The opposite end or handle portion of the brush is connected to an air motor or other rotational device. The motor is operative to rotate the wire brush within the mixer housing so that in the course of passage from the inlets to the outlet of the housing the supercritical carbon dioxide and adhesive are intermixed to form an adhesive composition in which the supercritical carbon dioxide is substantially completely dissolved or dispersed in the adhesive to produce a sprayable composition. It is contemplated that paddles or other movable mixing elements could be utilized in place of the wire brush described above, provided that the adhesive undergoes sufficient agitation and shearing to enable the supercritical carbon dioxide to dissolve or disperse in solution within the adhesive. In another aspect of this invention, a recirculation loop is preferably provided for continuously recir-culating the adhesive composition from the outlet of the mixer, to the adhesive dispenser and then back to the second inlet of the mixer for combination with additional supercritical carbon dioxide. The recirculation loop is also connected to a source of virgin adhesive which selectively supplies additional adhesive to the loop as the spraying operation proceeds. A capacitance sensor is incorporated in the loop to provide a measurement of the capacitance of the adhesive composition which is indicative of the relative proportion or ratio of supercritical fluid and virgin adhesive within the adhesive composition. The capacitance of the adhesive composition is monitored to ensure it remains within a predetermined level to achieve optimum spraying conditions. Description of the Drawings The structure, operation and advantages of the presently preferred embodiment of this invention will become further apparent upon consideration of the following description, taken in conjunction with the accompanying Fig. which is a schematic depiction of the adhesive spraying system of this invention. Detailed Description of the Invention
For purposes of the present discussion, the term "adhesive composition" refers to adhesives having a relatively high solids content, i.e. on the order of at least about 10% to 40% by volume, wherein a portion of the solvent component within the adhesive is replaced with a fluid diluent such as supercritical fluid to reduce solvent emissions. The term "supercritical fluid" as used herein is intended to refer to a gas in a supercritical state above its critical pressure and critical temperature, wherein the gas has a density approaching that of a liquid material. It is also contemplated that liquified gases could be utilized in forming adhesive compositions, and it should therefore be understood that the term "liquified gas" may be utilized interchangeably with the term "supercritical fluid" in the foregoing description.
A number of compounds in a supercritical or liquified state can be intermixed with the virgin adhesive to produce an adhesive composition for spraying by the apparatus of this invention. These compounds include carbon dioxide, ammonia, water, nitrogen oxide (N20) , methane, ethane, ethylene, propane, pentane, methanol, ethanol, isopropanol. isobutanol, chlorotrifluoro ethane, monofluoromethane and others. For purposes of the present discussion, supercritical carbon dioxide is employed because of its nontoxic nature and because its critical temperature and critical pressure of 85" F. and 1070 psi, respectively, are well within the operating ranges of standard airless spraying systems including the apparatus 10 of this invention. System Construction Referring now to the Fig. , the apparatus 10 comprises a supercritical carbon dioxide supply 12, a supply of virgin adhesive 14, a recirculation loop 16, an adhesive dispenser 18, and a dynamic mixer 20. These components of apparatus 10 are described individually below, and then their collective operation in forming and spraying an adhesive composition containing supercritical carbon dioxide is explained.
The supercritical carbon dioxide supply 12 comprises a tank 22, containing liquified carbon dioxide, which is connected by a line 24 to a filter 26. The liquified carbon dioxide passes through filter 26, and then through a line 28 into a pump 30. The pump 30 increases the pressure of the liquified carbon dioxide to a level above its supercritical pressure, e.g. preferably in the range of about 1200 to 1600 psi. The pump 30 is preferably a Haskell pump Model No. DSF35 commercially available from The Haskell Company of Burbank, California. The pressurized, liquified carbon dioxide is discharged from pump 30 through line 32 into a heater 34, preferably of the type sold by Nordson Corporation of Westlake, Ohio, under the model No. NH4. The heater 34 is effective to raise the temperature of the liquified carbon dioxide to a level at least above the super-critical temperature of carbon dioxide, and preferably in the range of about 110 to 125β F. A relief valve 36 is connected to the heater 34 to act as a pressure release within the supercritical carbon dioxide supply 12, if required.
Having been pressurized and heated above the supercritical levels, the liquified carbon dioxide is converted to supercritical carbon dioxide upon discharge from the heater 34. The supercritical carbon dioxide is transmitted through a line 38 to a valve 40 which controls the flow of supercritical carbon dioxide into a supply line 42 connected to mixer 20. Preferably, the supply line 42 includes a one-way valve 44 to prevent flow of material from the mixer 20 in a direction toward the valve 40. The valve 40 is connected by a line 41 to a controller 120 which operates the valve 40 in the same manner as the computer and pulse generator circuit of U.S. Patent No. 5,215,253 to Saidman et al., owned by the assignee of this invention, the disclosure of which is incorporated by reference in its entirety herein. As discussed in detail in Patent No. 5,215,253, and as mentioned below in connection with an explanation of the operation of apparatus 10, the controller 40 employs a standard PID (proportional, integral, derivative) control algorithm to control the opening and closing of valve 40, and, hence, the quantity of supercritical carbon dioxide entering the recirculation loop 16. In the presently preferred embodiment, the mixer 20 comprises a housing 46, formed with an interior 48, having a first inlet 50 connected to the supply line 42, a second inlet 52 connected to one end of recirculation loop 16, and, an outlet 54 connected to the opposite end of recirculation loop 16. The housing interior 48 receives a wire brush 56 having bristles 58 and a stem portion or handle 60. The bristles 58 of wire brush 56 are preferably located within the housing interior 48 in the space between the second inlet 52 and the outlet 54, and, as depicted in the Fig. , such bristles 58 extend across substantially the entire cross section of the housing interior 48. The handle 60 of wire brush 56 is rotatably carried by an internal bronze bearing 62 and an external bronze bearing 64 as depicted in the Fig. A portion of the handle 60 between the bearing 62, 64 receives a packing 66 preferably formed of tetrafluoroethylene or similar material capable of creating a seal along the brush handle 60 to prevent the escape of adhesive or supercritical carbon dioxide from the housing interior 48. The outermost end of handle 60 is connected by a coupler 68 to the output of a variable speed motor 70. The motor 70 is effective to rotate the wire brush within the housing interior 48 at a speed in the range of about 2,000 to 2,500 revolutions per minute which is monitored by a tachometer 71. In order to ensure that the motor speed is maintained within the desired range or at least above a minimum speed, the tachometer 71 sends a signal representative of the motor speed via a line 77 to a motor control 73, which, in turn, controls the operation of motor 70 as required.
In the presently preferred embodiment, the recirculation loop 16 comprises a line 72 connected to the outlet 54 of mixer 20 which, in turn, is connected to a capacitance cell 74 e.g. a capacitance sensing circuit of the type disclosed in U.S. Patent No. 5,215,253 to Saidman et al., noted above. As discussed in Patent 5,215,253, the capacitance cell 74 is effective to sense the capacitance of the material flowing therethrough, which, in turn, can be correlated to the relative proportion of supercritical carbon dioxide within such material. A meter 76 or other measurement device is connected to the capacitance cell 74 to provide a reading or indication of the capacitance of the material flowing through the recirculation loop 16 during operation of apparatus 10. The capacitance cell 74 is connected by a line 75 to the controller 120 for purposes explained in more detail below. The detailed construction and operation of the capacitance cell 74 forms no part of this invention of itself, and is therefore not discussed herein.
A line 78 extends downstream from the capacitance cell 74 and is connected by a branch line 80 to the adhesive dispenser. In the preferred embodiment, the dispenser 18 is a spray gun of the type sold by Nordson Corporation of Westlake, Ohio, under Model No. A7A. The dispenser or spray gun 18 is a recirculating type gun which discharges material through a recirculation line 82 back into the line 78 in the event the gun 18 is not operating. Preferably, a regulating valve 84 is located within line 78 between the branch line 80 and recirculation line 82 to divide the flow of material so that a desired amount of material is always circulating in the recirculating loop 16.
A back pressure regulator 86 is connected to line 78 downstream from the regulating valve 84 to maintain the pressure of the material within line 78 at a substantially constant level for supply to the dispenser or spray gun 18. A pressure monitoring device 88 is also connected to line 78, between the shut off valve 84 and back pressure regulator 86, to provide an indication of the pressure level within line 78.
The back pressure regulator is connected by a line 90 to a heater 92 preferably of the type sold by Nordson Corporation of Westlake, Ohio, under Model No. NH4. The purpose of the heater 92 is to maintain the temperature of the material within recirculation loop 16 at a level in excess of the critical temperature of supercritical carbon dioxide and, preferably, at a temperature in the range of about 110 to 120° F. As depicted at the top of the Fig. , virgin adhesive is transmitted from the adhesive source 14 into recirculation loop 16 through an adhesive pump 94 which may be, for example, a Nordson Rhino (R> Model pump. The virgin adhesive is discharged from pump 94 through a line 96, which carries a shut off valve 97, directly into line 90 of the recirculation loop 16. Additionally, the adhesive pump 94 is connected by a line 95 to the controller 120 for purposes discussed below. In order to ensure that the virgin adhesive from pump 94 is transmitted to the heater 92, a one¬ way valve 98 is positioned in line 90 upstream from pump 94 to block the flow of virgin adhesive in a direction toward the pressure regulator 86. A pressure monitoring device 99 is connected to line 90 between the one-way valve 98 and pressure regulator 86 to monitor the pressure within line 90 at that location. Controller 120 is connected to this pressure monitoring device 99 via a line 101 as will be described below.
The heater 92 is connected by a line 100 to a high pressure pump 102, preferably of the type sold by Nordson Corporation of Westlake, Ohio, under Model HP. As depicted in the Fig. , an accumulator 104 is connected by a line 106 to line 100 at a location between the heater 92 and high pressure pump 102. The accumulator 104 is also commercially available from The Parker Hannifin Corporation, of Hillsborough, North Carolina, under Model No. BD05A214. The purpose of accumulator 104 is to dampen or smooth out any pressure fluctuations which may be present at the input to high pressure pump 102, which could be created, for example, when the adhesive dispenser or gun 18 is opened and/or when additional virgin adhesive is introduced into the recirculation loop 16 from pump 94.
The high pressure pump 102, in turn, is connected by a line 108 to a filter 110, preferably of the type sold by Nordson Corporation of Westlake, Ohio, under Model No. 109765. Filter 110, in turn, is connected by a line 112 to the second inlet 52 of mixer 20 thus completing the recirculation loop 16. Operation of System
The method of operation of the apparatus 10 proceeds as follows. Initially, liquified carbon dioxide from tank 22 passes through the carbon dioxide supply 12 described above, where it is raised to sufficient temperature and pressure to form supercritical carbon dioxide downstream from the heater 34. The supercritical carbon dioxide is discharged from valve 40 through line 42 and past the one-way valve 44 into the first inlet 50 of the mixer 20.
During initial start up of the apparatus 10, virgin adhesive from pump 94 is introduced into the recirculation loop 16 by line 96 where it is heated to a temperature of about 120° F. , and then directed by high pressure pump 102 through filter 110 into the second inlet 52 of mixer 20. The virgin adhesive supplied by the pump 94 is highly viscous, and may have a solids content of 30% or higher. In order to thoroughly intermix the supercritical carbon dioxide with such viscous adhesive, the mixer 20 is equipped with a dynamic mixing device, such as schematically shown in the Fig. As noted above, the dynamic mixing device comprises a wire brush 56 having bristles 58 which are located between the second inlet 52 and the outlet 54 of the mixer housing 46. The supercritical carbon dioxide and virgin adhesive are introduced into the housing interior 48 through inlets 50, 52, respectively, where they come into contact with the bristles 58 of the wire brush 56. Preferably, the motor 70 is operative to rotate the wire brush 56, and, hence, the bristles 58, at speeds in the range of about 2,000 to 2,500 rpm. It has been found to be necessary that the wire brush 56 be rotated at least at a predetermined minimum speed. As noted above, the speed of motor 70 is monitored by tachometer 71 and controlled by the control 73 in response to a signal from tachometer 71. This control arrangement ensures that the motor speed remains above the predetermined minimum. As a result, the viscous adhesive is exposed to high, dynamic shear stresses and agitation in the course of movement from the second inlet 52 to the outlet 54 of mixer 20. This enables the supercritical carbon dioxide to thoroughly intermix with the virgin adhesive, so that it substantially completely disperses into solution therewith. An adhesive composition is thus formed within mixer 20 comprising virgin adhesive and supercritical carbon dioxide which acts as a diluent to replace a substantial portion of the solvent content of the virgin adhesive.
The adhesive composition is discharged through the outlet 54 of mixer 20 and enters the recirculation loop 16 for transmission to the dispenser 18. In order to ensure that the adhesive composition has an appropriate ratio of virgin adhesive and supercritical carbon dioxide suitable for spraying, the relative proportion of supercritical carbon dioxide and virgin adhesive within the adhesive composition is monitored by the capacitance cell 74. The cell 74 provides a measurement of the capacitance of the adhesive composition moving therethrough which can be correlated to its supercritical carbon dioxide content. If capacitance cell 74 sends a signal to controller 120 via line 75 representative of a capacitance reading which is too low, controller 120 sends a signal through line 95 to turn on the pump 94 so that adhesive is added to the loop until the capacitance rises up into the acceptable range. If the capacitance cell 74 sends a signal to controller 120 representative of a capacitance level which is too low, the PID loop function of controller 120 opens valve 40 to allow supercritical carbon dioxide into the recirculation loop 16 until the capacitance reading therein drops down into the acceptable range.
A further control function provided herein involves a measurement of pressure within the recirculation loop 16. The pressure signal from pressure monitor 99 provides a continuous signal to controller 120. If the pressure drops below a minimum pressure setting, the signal through line 101 from pressure monitor 99 representative of such pressure level causes the controller 120 to turn on pump 94 so that additional adhesive is pumped into the recirculation loop 16 until the pressure climbs above the minimum setting.
The apparatus 10 of this invention is essentially continuous in operation, depending upon the requirements of a particular application. It is contemplated that upon initial start up of apparatus 10, the adhesive composition will be circulated within recirculation loop 16 for a period of time in order to ensure that sufficient supercritical carbon dioxide is present within the adhesive composition. Once the proper ratio of the components within the adhesive formulation is obtained, the spray gun 18 can be operated to spray adhesive composition onto a particular substrate. As the quantity of the adhesive composition within the loop 16 starts to become depleted, the flow of additional supercritical carbon dioxide and virgin adhesive into the recirculation loop 16 and mixer 20 is controlled by operation of the valve 40 and pump 94 as described above. Example
Acceptable spraying of a viscous rubber- based adhesive is obtained with an apparatus 10 of the type described above operating with the following parameters: Solids content of adhesive composition 30% Pressure in recirculating loop 1200 to 1600 psi
Temperature in recirculating loop 120° F. Capacitance of formulation 54 to 55 pF
Temperature of supercritical carbon dioxide at inlet 50 112 to 114° F. Temperature at capacitance cell 115 to 120" F.
Temperature at heater 92 outlet 118 to 121" F.
Mixer speed 2000 to 2500 rpm
Under the above-identified operating conditions, a suitable spray pattern of adhesive is obtained.
While the invention has been described with reference to a preferred embodiment, it will be understood by those skilled in the art that various changes may be made and equivalents may be substituted for elements thereof 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 the essential scope thereof. Therefore, it is intended that the invention not be limited to the particular embodiment disclosed as the best mode contemplated for carrying out this invention, but that the invention will include all embodiments falling within the scope of the appended claims.

Claims

What is claimed is:
1 Apparatus for spraying adhesive compositions, comprising: first supply means for supplying a fluid diluent; second supply means for supplying virgin adhesive; a mixer having at least one inlet for receiving the fluid diluent and virgin adhesive, and an outlet, said mixer including means for dynamically intermixing the fluid diluent and virgin adhesive so that the fluid diluent is substantially dispersed in solution with the virgin adhesive to form an adhesive composition; an adhesive dispenser communicating with said mixer for spraying the adhesive composition onto a substrate.
2 The apparatus of claim 1 in which said mixer includes a housing having an interior which is formed with said inlet and said outlet, said means for dynamically intermixing comprising: a mixing member located within said interior of such housing; means for rotating said mixing member.
3 The apparatus of claim 2 in which said mixing member is a wire brush.
4 The apparatus of claim 3 in which said inlet and said outlet of said mixer housing are spaced from one another, said wire brush being positioned in said space between said inlet and outlet and having bristles which at least partially span the cross section of said housing interior.
5 The apparatus of claim 2 in which said means for rotating said mixing member is a motor. 6 The apparatus of claim 2 in which said mixer housing is formed with an inlet for said -fluid diluent and a separate inlet for said virgin adhesive.
7 The apparatus of claim 1 in which said fluid diluent is selected from the group consisting of supercritical carbon dioxide and liquified carbon dioxide.
8 Apparatus for spraying adhesive compositions, comprising: first supply means for supplying supercritical carbon dioxide; second supply mens for supplying virgin adhesive; a mixer having a first inlet connected to said first supply means, a second inlet and an outlet, said mixer including means for dynamically intermixing the supercritical carbon dioxide and virgin adhesive so that the supercritical carbon dioxide is substantially dispersed in solution with the virgin adhesive to form an adhesive composition; an adhesive dispenser; a recirculation loop connected to said second inlet of said mixer, to said outlet of said mixer, to said second supply means and to said adhesive dispenser, said recirculation loop being effective to transmit adhesive composition from said outlet of said mixer to said adhesive dispenser for spraying onto a substrate, said recirculation loop transmitting virgin adhesive from said second supply means to said mixer for intermixing with said supercritical carbon dioxide to form additional adhesive composition.
9 The apparatus of claim 8 in which said mixer includes a housing having an interior which is formed with said inlet and said outlet, said means for dynamically intermixing comprising: a wire brush located within said interior of such housing; means for rotating said wire brush.
10 The apparatus of claim 9 in which said inlet and outlet of said mixer housing are spaced from one another, said wire brush being positioned in said space between said inlet and outlet and having bristles which at least partially span the cross section of said housing interior. 11 The apparatus of claim 9 in which said means for rotating said wire brush is a motor.
12 The method of spraying adhesive compositions, comprising: transmitting virgin adhesive and supercritical fluid into a mixer; dynamically intermixing the adhesive and supercritical fluid within the mixer interior by operation of a movable mixing element to cause the supercritical fluid to disperse in solution within the adhesive thus forming an adhesive composition; transmitting the adhesive composition to a dispenser for spraying onto a substrate.
13 The method of claim 12 in which said step of dynamically intermixing the adhesive and supercritical fluid comprises rotating a mixing member within the interior of the mixer in the course of passage of the adhesive and supercritical fluid from at least one inlet in the mixer to its outlet.
14 The method of claim 12 in which said step of dynamically intermixing the adhesive and supercritical fluid comprises rotating a mixing member at a predetermined, minimum speed within the interior of the mixer in the course of passage of the adhesive and supercritical fluid from at least one inlet in the mixer to its outlet.
15 The method of claim 12 further including the step of recirculating the adhesive composition which is not discharged from the dispenser through a recirculation loop to the mixer.
16 The method of claim 15 in which said step of recirculating the adhesive composition further comprises: sensing the capacitance of the adhesive composition within the recirculation loop; adding supercritical carbon dioxide into the recirculation loop in the event the capacitance of the adhesive composition is above a predetermined level.
17 The method of claim 15 in which said step of recirculating the adhesive composition further comprises: sensing the capacitance of the adhesive composition within the recirculation loop; adding virgin adhesive into the recirculation loop in the event the capacitance of the adhesive composition is below a predetermined level.
18 The method of claim 15 in which said step of recirculating the adhesive composition further comprises: sensing the pressure of the adhesive composition within the recirculation loop; adding virgin adhesive into the recirculation loop in the event the pressure of the adhesive composition is below a predetermined level.
19 The method of spraying adhesive containing bound rubber, comprising: transmitting virgin bound rubber adhesive and supercritical fluid into a mixer; dynamically intermixing the adhesive and supercritical fluid within the mixer interior by operation of a movable mixing element to form a sprayable adhesive composition; transmitting the sprayable adhesive composition to a dispenser for spraying onto a substrate.
PCT/US1994/012086 1993-10-20 1994-10-19 Method and apparatus for spraying viscous adhesives WO1995011091A1 (en)

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Families Citing this family (21)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5688879A (en) * 1992-03-27 1997-11-18 The University Of North Carolina At Chapel Hill Method of making fluoropolymers
DE69334213T2 (en) * 1992-03-27 2009-06-18 University Of North Carolina At Chapel Hill Process for the preparation of fluoropolymers
US5863612A (en) * 1992-03-27 1999-01-26 University North Carolina--Chapel Hill Method of making fluoropolymers
US6344243B1 (en) 1997-05-30 2002-02-05 Micell Technologies, Inc. Surface treatment
US6287640B1 (en) 1997-05-30 2001-09-11 Micell Technologies, Inc. Surface treatment of substrates with compounds that bind thereto
US6165560A (en) * 1997-05-30 2000-12-26 Micell Technologies Surface treatment
CA2291146C (en) * 1997-05-30 2008-09-09 Micell Technologies Surface treatment
US6444772B1 (en) * 1998-10-28 2002-09-03 Nitto Denko Corporation Supercritical fluid pressure sensitive adhesive polymers and their preparation
DE69905756T2 (en) 1998-12-03 2004-02-19 Nordson Corp., Westlake SYSTEM FOR APPLYING HOT-MELT MATERIALS WITH A HIGH-TEMPERATURE-RESISTANT PRESSURE CONTROL AND A HEATED, RECIRCULATING DISTRIBUTOR
DE19922018A1 (en) * 1999-05-12 2000-12-07 Fraunhofer Ges Forschung Multi-component adhesive and device for gluing with such a multi-component adhesive
US6802903B2 (en) * 2001-09-25 2004-10-12 Becton, Dickinson And Company Apparatus for applying adhesive to tubing
AU2003215357A1 (en) * 2002-02-22 2003-09-09 Terrasimco Inc. Bladder-based apparatus and method for dispensing coatings
US6832699B2 (en) * 2002-02-22 2004-12-21 Terrasimco Inc. Direct pressure apparatus and method for dispensing coatings
US7178742B2 (en) * 2003-05-06 2007-02-20 Lear Corporation Fluid delivery system for spray applicator
JP4505851B2 (en) * 2003-11-21 2010-07-21 株式会社サンツール Bubble hot melt application equipment
US20080271991A1 (en) * 2005-04-15 2008-11-06 Advanced Technology Materials , Inc. Apparatus and Method for Supercritical Fluid Removal or Deposition Processes
US20070267512A1 (en) * 2006-05-18 2007-11-22 Carl Raabe System for uniform cold-spray application of high-solid content emulsified asphalts
EP2099571A1 (en) * 2007-01-09 2009-09-16 Nordson Corporation Closed-loop bubble elimination system and methods for applying a conformal coating material to a substrate
WO2011117998A1 (en) * 2010-03-25 2011-09-29 日本たばこ産業株式会社 Machine for producing low-ignition-propensity web, method for producing same, and method for producing low-ignition-propensity wrapping paper used in cigarettes
WO2013140814A1 (en) * 2012-03-22 2013-09-26 株式会社安川電機 Coating application device
US10988645B1 (en) 2018-01-10 2021-04-27 Wilsonart Llc Non-flammable contact adhesive

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2084038A (en) * 1980-09-11 1982-04-07 Matsuoka Mitsutoshi Apparatus for preparing dispersions
US5215253A (en) * 1990-08-30 1993-06-01 Nordson Corporation Method and apparatus for forming and dispersing single and multiple phase coating material containing fluid diluent

Family Cites Families (64)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US328134A (en) * 1885-10-13 Gas-scrubber
US1511765A (en) * 1921-08-02 1924-10-14 Marc L Latham Solution meter
US1483225A (en) * 1922-04-29 1924-02-12 Hammett Harry Rice Liquid meter
US1585255A (en) * 1923-03-03 1926-05-18 Mcfadden William David Water meter for irrigation heads
US2592481A (en) * 1948-06-18 1952-04-08 Arthur M Spencer Fiber beater for the liberation of cellulose fibers
US2862511A (en) * 1956-03-20 1958-12-02 Arthur R Forsberg Apparatus for liquid treatment of granular material
US3229077A (en) * 1962-01-22 1966-01-11 Performance Measurement Compan Fluid blending apparatus using digital computing means
GB1141963A (en) * 1966-04-05 1969-02-05 Avery Hardoll Ltd Improvements in and relating to liquid dispensing apparatus
US3651989A (en) * 1970-03-24 1972-03-28 Milton D Westrich Liquid metering system
US3764069A (en) * 1971-07-30 1973-10-09 Nordson Corp Method and apparatus for spraying
US3777935A (en) * 1971-10-19 1973-12-11 Storey W Pulse capture unit and apparatus for controlling the blending of two flowable substances
US3751644A (en) * 1972-02-22 1973-08-07 Sun Oil Co Automatic blending control system
US3921901A (en) * 1974-05-28 1975-11-25 Resource Planning Associates I Atomization of liquid fuels
US4019653A (en) * 1975-08-22 1977-04-26 Graco Inc. Automatic proportioning paint spray system
US3967634A (en) * 1975-11-06 1976-07-06 Graco Inc. Flow ratio control system
US4116364A (en) * 1976-02-02 1978-09-26 Binks Manufacturing Company Dispensing system for low stability fluids
US4265858A (en) * 1976-03-31 1981-05-05 Nordson Corporation Metering and mixing apparatus for multiple component
US4046287A (en) * 1976-05-10 1977-09-06 Graco Inc. Automatic metering and dispensing system
US4059466A (en) * 1976-08-02 1977-11-22 Nordson Corporation Hot melt thermoplastic adhesive foam system
US4059714A (en) * 1976-08-02 1977-11-22 Nordson Corporation Hot melt thermoplastic adhesive foam system
US4156754A (en) * 1977-04-27 1979-05-29 Nordson Corporation Method of making foamed thermoplastic adhesive materials and adhesive process therefor
US4259402A (en) * 1977-04-27 1981-03-31 Nordson Corporation Bonding with foamed hot melt adhesives
US4247581A (en) * 1977-10-14 1981-01-27 Nordson Corporation Method of coating with film-forming solids
US4200207A (en) * 1978-02-01 1980-04-29 Nordson Corporation Hot melt adhesive foam pump system
US4193745A (en) * 1978-03-09 1980-03-18 Nordson Corporation Gear pump with means for dispersing gas into liquid
US4423161A (en) * 1979-02-28 1983-12-27 Nordson Corporation Apparatus and method for dispensing foamable compositions
US4301119A (en) * 1979-02-28 1981-11-17 Nordson Corporation Apparatus and method for dispensing foamable compositions
US4371096A (en) * 1979-04-16 1983-02-01 Nordson Corporation Control apparatus for pressurized gas/liquid systems
US4288741A (en) * 1979-05-18 1981-09-08 Auburn International, Inc. Electrical measurement of fluid void fraction for fluid having capacitive and resistive conductive components
US4350266A (en) * 1979-06-08 1982-09-21 Binks Manufacturing Company Pumping system for unstable fluids
US4505406A (en) * 1979-07-19 1985-03-19 Nordson Corporation Method and apparatus for dispensing liquid compositions
US4505957A (en) * 1979-07-19 1985-03-19 Nordson Corporation Coating by atomization of high (i.e., about 70-99% by weight) solids film-forming compositions
US4527712A (en) * 1979-07-19 1985-07-09 Nordson Corporation Method and apparatus for dispensing liquid compositions
US4705461A (en) * 1979-09-19 1987-11-10 Seeger Corporation Two-component metering pump
US4505405A (en) * 1980-07-24 1985-03-19 Graco Inc. Proportional pumping system
US4405063A (en) * 1981-02-27 1983-09-20 Nordson Corporation Method and apparatus for controlling the density of dispensed hot melt thermoplastic adhesive foam
DE3140485A1 (en) * 1981-10-12 1983-04-28 Jagenberg-Werke AG, 4000 Düsseldorf DEVICE FOR DELIVERING VERY SMALL LIQUID QUANTITIES
US4516725A (en) * 1982-09-30 1985-05-14 501 Binks Manufacturing Co. Dual component pumping system
US4553701A (en) * 1982-10-22 1985-11-19 Nordson Corporation Foam generating nozzle
US4632314A (en) * 1982-10-22 1986-12-30 Nordson Corporation Adhesive foam generating nozzle
US4630774A (en) * 1982-10-22 1986-12-23 Nordson Corporation Foam generating nozzle
US4734451A (en) * 1983-09-01 1988-03-29 Battelle Memorial Institute Supercritical fluid molecular spray thin films and fine powders
US4522789A (en) * 1983-09-06 1985-06-11 Graco Inc. Plural component mixing and dispensing system
US4779762A (en) * 1984-05-30 1988-10-25 Nordson Corporation Method and apparatus for controlling the gas content of dispensed hot melt thermoplastic adhesive foam
US4654802A (en) * 1984-06-07 1987-03-31 Halliburton Company Cement metering system
US4601645A (en) * 1985-02-04 1986-07-22 Nordson Corporation Gear pump-liquid gas mixer with improved gas introduction
US4778631A (en) * 1985-10-02 1988-10-18 Nordson Corporation Method and apparatus for foaming high viscosity polymer materials
US4717582A (en) * 1986-05-22 1988-01-05 The Dow Chemical Company Method and apparatus for controlling the density of a foam
US5057342A (en) * 1987-12-21 1991-10-15 Union Carbide Chemicals And Plastics Technology Corporation Methods and apparatus for obtaining a feathered spray when spraying liquids by airless techniques
ES2043640T3 (en) * 1987-12-21 1994-01-01 Union Carbide Corp SUPERCRITICAL FLUIDS AS THINNERS IN THE APPLICATION BY LIQUID SPRAY OF COATINGS.
US5141156A (en) * 1987-12-21 1992-08-25 Union Carbide Chemicals & Plastics Technology Corporation Methods and apparatus for obtaining a feathered spray when spraying liquids by airless techniques
US5066522A (en) * 1988-07-14 1991-11-19 Union Carbide Chemicals And Plastics Technology Corporation Supercritical fluids as diluents in liquid spray applications of adhesives
US5106650A (en) * 1988-07-14 1992-04-21 Union Carbide Chemicals & Plastics Technology Corporation Electrostatic liquid spray application of coating with supercritical fluids as diluents and spraying from an orifice
US5108799A (en) * 1988-07-14 1992-04-28 Union Carbide Chemicals & Plastics Technology Corporation Liquid spray application of coatings with supercritical fluids as diluents and spraying from an orifice
US5203843A (en) * 1988-07-14 1993-04-20 Union Carbide Chemicals & Plastics Technology Corporation Liquid spray application of coatings with supercritical fluids as diluents and spraying from an orifice
ES2045280T3 (en) * 1988-07-14 1994-01-16 Union Carbide Corp APPLICATION OF COATINGS BY ELCTROSTATIC SPRAY OF LIOQUIDS WITH SUPERCRITICAL FLUIDS AS THINNERS AND SPRAYING FROM A HOLE.
US4882107A (en) * 1988-11-23 1989-11-21 Union Carbide Chemicals And Plastics Company Inc. Mold release coating process and apparatus using a supercritical fluid
DE69003711T2 (en) * 1989-03-22 1994-01-27 Union Carbide Chem Plastic Precursor coating compositions.
ES2042110T3 (en) * 1989-03-22 1993-12-01 Union Carbide Chemicals And Plastics Company, Inc. PRE-COURSE COMPOSITIONS FOR COATING.
US5088443A (en) * 1989-10-04 1992-02-18 Nordson Corporation Method and apparatus for spraying a liquid coating containing supercritical fluid or liquified gas
US5106659A (en) * 1989-10-04 1992-04-21 Nordson Corporation Method and apparatus for spraying a liquid coating containing supercritical fluid or liquified gas
US5098194A (en) * 1990-06-27 1992-03-24 Union Carbide Chemicals & Plastics Technology Corporation Semi-continuous method and apparatus for forming a heated and pressurized mixture of fluids in a predetermined proportion
US5058805A (en) * 1990-07-12 1991-10-22 Brunswick Corporation Paint spraying system
US5197800A (en) * 1991-06-28 1993-03-30 Nordson Corporation Method for forming coating material formulations substantially comprised of a saturated resin rich phase

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2084038A (en) * 1980-09-11 1982-04-07 Matsuoka Mitsutoshi Apparatus for preparing dispersions
US5215253A (en) * 1990-08-30 1993-06-01 Nordson Corporation Method and apparatus for forming and dispersing single and multiple phase coating material containing fluid diluent

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