JP2002505186A - Method and apparatus for depositing a two-component impregnating agent and a coating agent on a carrier - Google Patents

Abstract

A two component mixture based on thermoplastic liquifiable or fluid components is applied as separate layers onto the substrate(1) and the first layer is solidified before applying the second. Both layers are then fluidized and mixed together. Independent claims are made for :- (1) process equipment for applying and crosslinking the two component material including an ultrasonic resonator(16); and (2) use of an ultrasonic resonator for impregnating a fabric strip(1) with a curable polymer. Preferred Features: The softening temperatures of both components differ by ≥ 30 degrees C, preferably ≥ 50 degrees C. The first component is a hardener with a softening point of 100 degrees C and is applied at 135-160 degrees C, preferably 150 degrees C. The second component is a polymer with a softening point of 50 degrees C and is applied at 80-110 degrees C, preferably 90 degrees C. Ultrasonic energy may be applied to the coated or uncoated side to effect mixing.

Description

DETAILED DESCRIPTION OF THE INVENTION

The present invention relates to a method and an apparatus for depositing a two-component impregnant or coating on a carrier. Such methods and devices are often known and common. Such methods are performed, for example, to coat substrates of a wide variety of materials such as plastics, metal plating, tissue or glass fibers. Using fiber materials (tissues, fleeces, wovens) consisting of natural or synthetic fibers or glass fibers, for impregnation of the fiber material, in particular for coagulation and filling, or for impregnation and / or subsequent coating. Two-component agents can be utilized. This makes it possible to impregnate and / or coat sheet materials such as webs or strips and fiber bundles. As such, such carriers to be coated and / or impregnated can be of any geometric shape. In the context of the present invention, it is to be understood that mixtures having several components are also two-component compounds. This is the case with some crosslinkable polymers, or when various curing agents are utilized in one system. Also, a two-component system is, for example, a thermoplastically curable or solvent-containing drying system in which the system comprises at least one polymerizable polymer or prepolymer and a suitable curing agent system or crosslinker. It should also be understood that

[0002] In the production of circuit boards, in particular for the coating of fibrous materials for the production of so-called prepregs, the most diverse forms of coating methods or coating devices are known. It can be seen that, in particular, epoxy resins have been tried and tested, as described in detail in US Pat. No. 5,478,599 and EP 476 752 as coating and / or impregnating agents. Such epoxy resins are available, for example, from Shell Chemical Company from Epon.
Resin (Epon Resin) 1031 is available.

As a second component of such a two-component system, a suitable curing agent is used. This includes
Amine, acid, phenol and anhydride belong. For example, Shell International Company
Novolac hardeners, such as those available under the name Epicur DX-175, are especially frequently utilized.

[0004] Furthermore, it is also often the case that cure accelerators are used to accelerate the curability / crosslinking and / or lower the curing temperature. As is known from the literature mentioned above, the polymer resin becomes liquid at a given temperature and, when in the liquid state, is deposited and allowed to penetrate as deeply into the substrate as possible, for example by impregnation. Polymer formulation. This also applies to the case where the temperature of the curing agent to be liquefied by heating and then adhered is set.

[0005] As can be inferred from US Pat. No. 5,478,599, the deposition temperature ranges from 50 ° C. to 250 ° C., preferably from 100 ° C. to 200 ° C., depending on the setting of the resin and the curing agent. Can be selected with.

[0006] The coated and impregnated carrier is then heated by elevated ambient temperature (eg, hot air) or infrared radiation. Thereby, the polymer is heated at 80 ° C. to 25 ° C.
It cures at a temperature of 0 ° C., preferably 100 ° C. to 200 ° C., to such an extent that no gelation occurs. The coated carrier, in particular the fibrous material impregnated with the polymer, can then be subjected to a curing treatment, for example, in a drying tower.

To harden or liquefy the polymer or hardener, most conventional extruders are used, which extrude heated components via nozzles, dies, coating equipment and other means of application. Is deposited on the carrier. Such attachment means are described, for example, in U.S. Pat. No. 5,478,599, U.S. Pat. No. 4,327,130, U.S. Pat. No. 4,063.531 or EP 476 752;
681 and German patent A1-41 19 538 or British patent A1
No. 2,171,934.

The known methods and devices have various difficulties when applied in practice. Primarily,
In particular, problems arise when two-component impregnating agents and coatings are applied. Usually, the two-component agent is supplied in a separate conduit and is mixed in the mixing head just before application on the carrier. For this reason, each time the application process is interrupted, the mixing system tends to harden in the application head. As a result, the work may be interrupted. Further, the curing agent and the polymer have different viscosities at the same temperature in principle. If both components are guided in the deposition head, the temperature will be equal.
This makes it impossible to set the desired optimum viscosity state of the two components. Optimizing the viscosity is one important method parameter in order to be able to achieve impregnation, in particular penetration into the carrier or placement without bubbles on the surface of the carrier.

Problems often accompany impregnation, especially when trying to ensure that the two components fully penetrate the carrier at high deposition rates to ensure homogeneous impregnation.

[0010] It is an object of the present invention to improve the known method and apparatus and avoid its known disadvantages. In particular, there is provided a method and apparatus for a two-component agent that allows for bubble-free and complete surface penetration and wetting of the carrier material. Furthermore, 2
After the two components have been deposited, the curing conditions are controlled and varied to an extent that can be freely determined for the method and equipment.

According to the invention, the two components are preferably deposited on the carrier one after the other in a separate layer in which one component is located on the other component, but mixed on the carrier. These goals are achieved by discontinuing before curing.

According to the invention, by mixing the two components on a carrier, different requirements are achieved in a systematic and optimal way. As a result of thorough mixing on the carrier, the point at which curing begins can be accurately determined. Thus, the system must be set up to avoid such curing when premixing in the deposition head while reacting simultaneously with mixing. Thus, the two components can be separately applied. However, in certain applications, it is also possible to deposit the two roughly premixed components and only then to thoroughly mix them on the carrier.

Furthermore, mixing on the carrier will ensure that the two components are in particular intimate contact with the surface of the carrier and penetrate rapidly and deeply during impregnation.

Further, when the two components are deposited separately, the temperature and viscosity of the two components can be optimized. Thus, according to the invention, there is provided a two-component impregnant or coating for a thermoplastically liquefiable or liquid component. This liquefaction is mostly performed by heating within the above-mentioned temperature range.

Thereafter, the two components, one above the other, are deposited on a carrier as separate layers. In this way, separate attached components can be arranged with specially set attachment parameters for each attached component. When the fiber material is impregnated, the attached components penetrate into the fiber material.

Prior to depositing the second layer, it is preferred that at least the first of the deposited layers be solidified. This is easily done in an optimal way to solidify the layer by cooling. This prevents the second adhesion layer from mixing with the first layer and, at the same time, prevents the start of the curing step.

Also, in principle, after the second layer has solidified, it cools and at the same time hardens. However, this is not an essential method condition. Thereafter, one or more solidified layers are again liquefied and mixed together. This is advantageously done by supplying thermal energy, for example in the form of an infrared ray of the radiator. The components can be mixed in an optimally simple manner by supplying ultrasonic energy. At the same time, heat is generated in the layer by the ultrasonic resonator, which contributes to liquefaction. Instead of an ultrasonic resonator, a resonator having another vibration frequency, such as an electromagnetic resonator, can be used as the mixing head.

[0018] Suitable ultrasonic resonators for generating ultrasonic energy have been used for many years for the most diverse applications. Thus, resonators have been used for welding, cleaning or separating and sieving the components. Suitable resonators are commercially available, for example, from the company Telsonic of Bronschoffen, Switzerland. The power required depends on the amount of binary agent deposited, transport speed, carrier thickness and material weight, and possible pre-liquefaction of the components. The required power can be easily determined by the experimental method of bringing the coated carrier into contact with the resonator by the time of the method. By slowly increasing the power, the point at which the two components mix optimally can be determined. Further, according to the impregnating method and the apparatus, it is possible to know how much power of the ultrasonic resonator is used to optimally impregnate the carrier with the two components.

Achieving a particularly high density and absence of bubbles during impregnation when the curing agent and polymer are deposited on one side of the material and then subjected to ultrasonic energy (collision) from the deposition side Can be. In this way, the two components in the material web are:
And is optimally introduced on the side of the material web located opposite the wrapped bubble outlet of the ultrasonic resonator.

When the two components are applied, the desired optimum temperature for the components can be set, and thus the viscosity can be controlled. This is particularly advantageous when the two components have different liquefaction temperatures. In this way, for example, a curing agent with a higher melting temperature can be applied first. After adhering and penetrating into the carrier, the curing agent cools and solidifies. Thus, for example, if a polymer component with a lower melting temperature is deposited, the curing agent with a higher melting temperature remains solid. When the two components are deposited one on top of the other, no thorough mixing takes place. Curing takes place in the next step, preferably in the field of ultrasonic energy, by liquefaction and thorough mixing. In practice, it has been found to be good when the softening temperatures of the two components differ by at least 30 ° C, preferably by at least 50 ° C.

Heating the two components before applying the ultrasonic energy can accelerate the liquefaction and mixing process. In practice, this has been found when heating and curing the curing agent and polymer to a temperature substantially above the softening temperature and testing and testing. This is, in particular,
It is effective when impregnating a material web. Experiments and tests have shown that curing agents that soften at about 90 ° C. significantly liquefy when heated to 135 ° C. to 160 ° C., preferably 150 ° C. This is also true for polymers having a softening temperature of about 70 ° C. to 80 ° C., and preferably heated to 90 ° C. to 110 ° C., and thus fully liquefy. The curing agent and the polymer
This liquefaction according to the method of the invention and with the apparatus according to the invention is not necessarily important, since there is no mixing and therefore there is no need to worry about premature curing due to high temperatures.

Heating the web after application of the ultrasonic energy allows the curing to be accelerated and controlled in the process. Of course, ultrasonic resonators can be used very commonly with thermoplastic, solvent-containing heat-reactive impregnants or heat-reactive impregnants that can be cured in another way, It is not limited to only two-component systems. In this case, the resonator
It does not function as a mixing head, but merely "liquefies" the two-component means and pushes it tightly into the web material and only expels bubbles.

Hereinafter, the present invention will be described in more detail with reference to the accompanying drawings by way of example embodiments. According to FIG. 1, in a first method step A, a substrate 1 is made available (
Be prepared). In method step B, a first layer 2 of a two-component impregnant or coating is applied to the carrier 1. In method step C, the layer 2 is cooled and solidifies before the second layer 3 of the second component of the two-component agent is deposited on the first layer 2.

In method step D, the two layers 2, 3 are thoroughly mixed with one another, resulting in a cured layer 4 consisting of a two-component impregnant or coating. This allows the layer 4 to completely or partially penetrate into the carrier.

According to FIG. 2, a material web 5 of fiberglass fiber structure is guided as a carrier 1 to an impregnation and coating device 6. In this way, the material web 5 is initially
Travel around. The roller is provided with a conventional wide slot nozzle 8. A novolak curing agent heated to about 150 ° C. by an extruder 9 (Epical D from Shell International Chemical Company)
X-175). This liquefied hardener penetrates the material web 5, which in a further course of the method is guided over the cooling device 10. The cooling device 10 cools the curing agent applied as the first layer 2,
The hardener solidifies. It is also possible to omit the cooling means 10 depending on the ambient temperature and the length of the path.

As the material travels behind the cooling device 10, the material web 5
And a roller 12 to be guided to a second wide slot nozzle 13. The wide slot nozzle 13 is supplied with an epoxy resin (Epon resin 1031 from Shell Chemical Company) heated to about 90 ° C. by a second extruder 14. This resin deposited as the second component 3 forms a separate layer on the first layer 2 of the cooled and solidified hardener. The very fluid resin is not only deposited on the surface of the first layer 2, but also forms a separate second layer on the already solidified first layer 3. This is done even if the resin penetrates into the open cavities of the material web 5. This is ensured by the fact that the liquefaction temperature of the polymer deposited as the second component 3 is significantly lower than that of the first layer 2. Thus, the two layers cannot be mixed and the polymerization process upon deposition has not yet begun.

An infrared heating means 15 for heating the material web 5 and the two layers 2, 3 is connected behind the second wide slot nozzle 13. The material web 5 and the two layers are then subjected to ultrasonic energy (impact) in such a way that the components of the two layers are sufficiently mixed with each other and the material web 5 is evenly filled with the two-component agent. ) A resonator 16 is provided.

After the resonator 16, two rollers 1 arranged at a configurable distance from each other
7, 18 are provided. These rollers control and set the thickness of the impregnated material web 5. In a further step, the material web is guided to the heating device 20 so that the degree of cure of the binary mixture can be controlled in a defined manner. To do this,
In particular, infrared radiators are suitable.

FIG. 3 shows a material web 5 used as a carrier 1 in various method steps A to D, according to the embodiment according to FIG. This allows
In step B, the hardener penetrates the material web 5. In step C,
Epoxy resin supplied from the wide slot nozzle 13 as the second layer 3 is attached to the curing agent.

In step D, the layers 2, 3 (hardener and epoxy resin) are mixed and the material web 5 is evenly impregnated with the two-component impregnant and coating. As in the result of FIG. 4, the resonators 16 according to FIG. 2 are arranged over the entire width of the material web 5 so that the material web 5 is provided with ultrasonic energy over its entire width. Hit. Since the material web according to the embodiment of FIG. 2 is coated on its upper side with the two-component layers 2, 3, the application of ultrasonic waves by means of the resonator 16 ensures complete mixing and heating of the layers 2, 4. Not only does this have an effect, but at the same time it is ensured that the two-component agent completely penetrates the material web 5. According to the example of the embodiment according to FIG. 6, after passing through the first ultrasonic resonator 16 a, in a manner that is completely absorbed by the material of the carrier 1, One can understand how the two-component impregnants or coatings, which remain on the top side of the carrier, are mixed and "liquefied" via ultrasonic energy. The second resonator 16b further improves the uniformity and complete mixing of the material in the carrier 1.

In the embodiment of FIG. 5 in which the fiber bundle 22 is used as a carrier, the fiber bundle is first guided around the rollers 23, whereby the two-component agent is heated in the heated impregnated gutter 24. Dipped in the first component. Thereafter, the fiber bundle 22 travels above the second roller 19, where the attached impregnant is cooled and hardened. The fiber bundle 22 is then passed through the two rollers 26, 27 to a second impregnated gutter 25
Through which the two-component impregnating agent and the second component of the coating are deposited. The fiber bundle 22 is guided to the resonator 16 via two further rollers 28, 29. Also in this case, the two components of the two-component agent, which are applied sequentially, form separate layers. In particular, these components are not arranged in a plane or parallel like a substrate with a larger surface, for example in the material web 5 (FIG. 2). However, since the components are deposited sequentially and the second component is applied only when the first component has cooled and solidified, there is a separate layer that extends unevenly within the fiber bundle 22. Resonator 16 applies high ultrasonic energy to fiber bundle 22 such that the two components are heated, liquefied, and thoroughly mixed simultaneously. This complete mixing can also be performed in two steps with the same resonators 16a and 16b as in FIG. As resonator 16, an electromagnetic resonator or vibrator driven in another way can also be used as a mixing head. However, in such a vibrating device, a sufficient heat source (eg by radiator and / or hot air or electric heating) is provided in front of the mixing head to sufficiently liquefy the two-component agent in front of the vibrating head. Must be provided.

If only one component of the impregnating agent has to be used, of course, the first impregnation trough 24 remains unused. The device can thereby be used not only for two-component saturants but also for one-component saturants.

[Brief description of the drawings]

FIG. 1 is a schematic view of a process of a coating method having features of the present invention.

FIG. 2 is a schematic diagram of an apparatus for impregnating a web of glass fiber material and producing a prepreg with features of the present invention.

3 is a view of the material web according to FIG. 2, showing the various steps of the method in an enlarged cutaway view.

FIG. 4 is a schematic view of a material web with a resonator.

FIG. 5 is a schematic view of an apparatus for impregnating a fiber bundle.

FIG. 6 is a diagram of a modified embodiment of the device with two resonators.

──────────────────────────────────────────────────続 き Continuation of front page (81) Designated country EP (AT, BE, CH, CY, DE, DK, ES, FI, FR, GB, GR, IE, IT, LU, MC, NL, PT, SE ), OA (BF, BJ, CF, CG, CI, CM, GA, GN, GW, ML, MR, NE, SN, TD, TG), AP (GH, GM, KE, LS, MW, SD, SZ, UG, ZW), EA (AM, AZ, BY, KG, KZ, MD, RU, TJ, TM), AL, AM, AT, AU, AZ, BA, BB, BG, BR, BY, CA, CH, CN, CU, CZ, DE, DK, EE, ES, FI, GB, GE, GH, GM, HR, HU, ID, IL, IS, JP, KE, KG, KP , KR, KZ, LC, LK, LR, LS, LT, LU, LV, MD, MG, MK, MN, MW, MX, NO, NZ, PL, PT, RO, RU, SD, SE, SG, SI, SK, SL, TJ, TM, TR, TT, UA, UG, US, UZ, VN, YU, ZWF Term (Reference) 4D075 AB01 AB32 AB54 AE06 BB13Z BB37Z CA47 DA03 DB01 DB31 EA17 EA27 EC37 4F042 AA22 AA23 DB00 DB18

Claims (21)

[Claims] 1. In a method of depositing a two-component impregnant or coating on a carrier, the two components are preferably such that one component is after the other and one component is the other. A method comprising depositing on a carrier in a separate layer to overlie the components, mixing only when on the carrier, and then curing. 2. The method according to claim 1, wherein (a) making available a two-component impregnating or coating material having a thermoplastically liquefiable component, ie a liquid component; and (b) two components. (C) depositing at least a first layer of the deposited layer and a second layer as a separate layer with one component overlying the other component; Prior to solidifying; and (d) thereafter, the one or more solidified layers are again liquefied and mixed. 3. The method according to claim 1, wherein the two layers are mixed by ultrasonic energy. 4. A two-component impregnant having a polymer which crosslinks under the influence of a hardening agent, in particular according to one of claims 1 to 3, having a large surface or binding products, in particular a material. In a method of impregnating a web or fiber bundle, a curing agent and a polymer are applied to at least one side of a product, and then the curing agent and the polymer are subjected to an ultrasonic energy field to crosslink and cure. The method characterized by the above. 5. The method according to claim 4, wherein (a) a liquid polymer, that is, a polymer and / or a liquid curing agent that can be thermoplastically liquefied at a preset high liquefaction temperature, (B) that a polymer and / or curing agent in a softened state at least at its liquefaction temperature is deposited on the product; and (c) Cooling at least the initially deposited component to below its liquefaction temperature before depositing the second component; and (d) subjecting the two components to a field of ultrasonic energy, Cross-linking and curing. 6. The method according to claim 5, wherein (a) making the thermoplastically softenable polymer available as a component at a first liquefaction temperature; and (b) first liquefaction temperature. And the second liquefaction temperature is different, making available a thermoplastically softenable curing agent at the second liquefaction temperature; and (c) first, the component having the higher liquefaction temperature Heating to the liquefaction temperature and depositing on the product, and then again cooling and solidifying; (d) then heating the second component having the lower liquefaction temperature to this liquefaction temperature and depositing Depositing at a temperature below the liquefaction temperature of the first component applied; and (e) subsequently exposing the first and second components to a field of ultrasonic energy. . 7. The method according to any one of claims 4 to 6, wherein the product is heated before applying the ultrasonic energy and after depositing the two components. 8. The method according to claim 7, wherein the product is heated by radiant heat. 9. The method according to claim 4, wherein the respective softening temperatures differ by at least 30 ° C., preferably by at least 50 ° C.
A method comprising making two components available. 10. The method according to any one of claims 4 to 9, wherein about 10
A softener having a softening temperature of 0 ° C., as a first component, 135 ° C. to 160 ° C.,
Preferably, a polymer deposited at about 150 ° C. and having a softening temperature of about 50 ° C. as a second component is deposited at 80 ° C. to 110 ° C., preferably at about 90 ° C. . 11. The method according to any one of claims 4 to 10, wherein the product is coated on one side with a polymer and a curing agent, and then the coated side is exposed to ultrasonic energy. The method. 12. The method according to claim 11, wherein the non-coated side of the product is subsequently subjected to ultrasonic energy. 13. The method according to claim 4, wherein the product is subjected to a heat treatment after the ultrasonic treatment. 14. The method according to claim 13, wherein the product is heated with radiant heat. 15. The method according to claim 4, wherein the thickness of the impregnated product after sonication is set to a presettable measurement value. 16. An apparatus for adhering and cross-linking a two-component impregnant or coating comprising a polymer in which a two-component agent cross-links under the influence of a curing agent, the carrier comprising: An apparatus characterized in that it is equipped with an ultrasonic resonator (16, 16a, 16b) for applying ultrasonic energy to the impregnating agent or coating material deposited on (1, 5, 23). 17. The device according to claim 16, wherein the ultrasonic resonator (16, 1;
A mechanism (15) for heating the impregnating agent or coating agent attached in front of 6a, 16b)
A device characterized by being equipped with: 18. The device according to claim 16, further comprising a mechanism (20) for heating the impregnating or coating material behind the ultrasonic resonator. 19. The device according to claim 16, wherein a layer of the first component (2) liquefied by supplying heat is applied to the carrier (1, 5, 23).
) On the first component (7, 8, 9, 24), the second component (3) on the first component (12, 13, 14, 25), and the carrier ( 15, 22)
An ultrasonic resonator (16, 16a, 16b) for completely mixing the upper two layers. 20. Apparatus according to claim 17, wherein the heating mechanism comprises an radiator emitting infrared energy. 21. A method using an ultrasonic resonator for impregnating a web of material with a curable polymer.