AU2006322652A1 - Pre-preg and laminate manufacture - Google Patents

Description

WO 2007/065222 PCT/AU2006/001864 Pre-Preg and Laminate Manufacture Field of the invention The invention relates to the manufacture of partially cured resin impregnated papers or non-wovens used for decorative and industrial laminates. 5 The impregnated and optionally coated paper or non-woven, known as a b-stage pre-preg, is subsequently fully cured under pressure in a hot press to form a laminate. The full and final curing of the laminate in a hot press while under pressure enables the b-stage pre-preg to bond with other b-stage pre-pregs, and/or a carrier substrate such as particleboard, fibreboard or oriented strand board. 10 The invention therefore also relates to laminate products manufactured using the partially cured resin impregnated papers or non-wovens formed according to the invention. Any reference herein to a prior document or other prior disclosure is not to be taken as an admission that the content of the document or the disclosure is common 15 general knowledge, either in Australia or elsewhere. Background of the invention The optimal process technology for bringing impregnated papers or non-woven materials used in laminate manufacture to the so-called b-stage includes all of single bath, single bath and coating, and single bath and multiple coating options. "Single 20 bath" also embraces multiple dipping in a single bath or split baths. Papers or non wovens may be developed that only require coating of the resin onto a pretreated surface thereby avoiding the usual first bath saturation. The basic option is to saturate the paper or non-woven in a bath of resin, usually urea formaldehyde (UF) resin, melamine formaldehyde (MF) resin, phenol 25 formaldehyde (PF) resin or any combination of these, before controlling the resin pick up via a set of metering rollers. The resin impregnated paper or non-woven is then WO 2007/065222 PCT/AU2006/001864 2 passed through a set of ovens, each oven or zone set at temperatures that enable the solvent to volatilise and the resin to progress in the degree of cure. The rate of progress of the paper or non-woven through the oven, and the temperature profile, can be carefully controlled to prevent premature skinning of the surface through resin 5 polymerisation in the outer layer. If this occurs, remaining internal water has to force itself out through the skinned film which causes a problem with dusting arising from broken off particles of dried resin, and in some cases also filler particles. This is avoided by having a graduated drying profile over significant drying oven length - the productivity comes from line speed which is limited by the number of drying ovens and 10 their temperatures. It is important to avoid the dusting effect because this would present a significant occupational health and safety issue. Dusting can cover parts of equipment such as safety beams used as breakers if a worker enters a dangerous part of the machine, and a health issue inevitably arises from dust particles in the air. 15 The impregnated paper or non-woven at the end of the impregnation process has a known amount of remaining volatiles and a known degree of cure. This partially dried and partially cured impregnated paper or non-woven is known as a b-stage pre-preg. Among further options in the impregnation process to achieving the desired b stage pre-preg, there is the option to further coat the impregnated paper or non-woven 20 before any partial drying and partial curing takes place, so-called wet-on-wet processing, before partial drying and partial curing in a set of heated ovens, whether gas fired, oil fired or heated by other means. The state of the art is not limited to the abovementioned descriptions, as one skilled in the art would know. Numerous combinations of resin types, resin content, 25 resin additives, additives for specific purposes, such as corundum for improved abrasion resistance, and remaining volatiles and degree of cure are preferred for different strategies in producing the final laminate.

WO 2007/065222 PCT/AU2006/001864 3 There are several aspects in the current method of manufacturing b-stage impregnated papers that are economically disadvantageous. First is the high cost of energy arising from the set of ovens. Second is the large footprint in the form of the long series of drying ovens 5 required to achieve high operating speed. Third is that the gas fired or oil fired drying ovens are always used at maximum operating width, a disadvantage when treating a paper or non-woven at a web width less than the maximum of the drying oven. It is known per se that NIR irradiation, eg applied from halogen-tube radiators, is 10 an effective mechanism for drying or curing a variety of systems: an early disclosure was in US patent 6,436,485 for the purpose of cross-linking and curing the powder in powder coating of thermally sensitive substrates. Other disclosures of interest include WO 2004/106027 [post forming of thermosetting laminates using NIR radiation], and WO 03/000612 [curing adhesive or sealing agents using NIR radiation]. 15 It is an object of the invention to at least in part alleviate the above-mentioned disadvantages. Summary of the invention It has been realised, in accordance with the invention, that NIR irradiation can be usefully applied to the production of pre-pregs with significant process advantages 20 without incurring the skinning and consequent dusting problems that might have been expected to arise with the higher drying and curing rates that can be achieved with NIR irradiation. The invention accordingly provides, in a first aspect, a method of manufacturing a b-stage pre-preg of resin impregnated paper or non-woven, characterised by irradiating 25 a resin impregnated paper or non-woven with NIR radiation to at least partially remove WO 2007/065222 PCT/AU2006/001864 4 solvent by vaporisation of the solvent, and to advance cure of the resin, whereby to produce an at least partially dried and at least partially cured b-stage pre-preg. In its first aspect, the invention further provides apparatus for manufacturing a b stage pre-preg of resin impregnated paper or non-woven, including a resin impregnation 5 station for impregnating a paper or non-woven with resin carried by a solvent, a heating and curing station having irradiation means to irradiate the impregnated paper or non woven with near infra-red (NIR) radiation to at least partially remove the solvent by evaporation of the solvent, and to advance cure of the resin, whereby to produce an at least partially dried and at least partially cured b-stage pre-preg. 10 By "near infra-red" is herein meant the wavelength range between the visible region and 2.5 gm, ie about 0.7 to 2.5gm. It is thought that the skinning and consequent dusting problems that might have been expected to arise with the higher drying and curing rates that can be achieved with NIR irradiation do not arise because NIR radiation does not rely on thermal conduction 15 to the interior as do conventional ovens and infra-red heating systems, but is directed immediately into the whole body of the wet resin to achieve simultaneous drying and curing. As drying occurs, simultaneously the rate of curing increases. A significant facility arising from the invention is the ability, in a preferred embodiment of the invention, to achieve substantially uniform application of the NIR 20 radiation through the impregnated paper or non-woven, an outcome not possible in current state of the art drying equipment. A further advantage is the ability to apply the energy only across the width of the web rather than the width of the drying cabinet. The NIR radiation is thought to cause flash evaporation of the solvent, which is 25 most often water, by agitation of the solvent molecules, and to advance curing as the solvent is driven off by agitating the aminoplast resin molecules. Radiant heat from the NIR apparatus also provides energy to advance the cure of the resin.

WO 2007/065222 PCT/AU2006/001864 5 The invention allows for a considerable reduction in the number of drying ovens required to achieve the desired properties of the partially dried and partially cured b stage pre-preg. NIR irradiation may be employed alone or in conjunction with conventional non-NIR drying/curing ovens to achieve a pre-determined drying and 5 curing program. Typically, the apparatus further includes means for conveying the paper or non woven as an elongated web through the resin impregnation station and the heating and curing station. Preferably, the method includes controlling the amount of the resin outside the 10 body or matrix of the paper or non-woven. For this purpose, metering means may be provided between the resin impregnation station and the heating and curing station. This controlling may comprise substantially removing resin outside the body or matrix of the paper or non-woven. Instead of the usual 40 or 50 metres or more of drying ovens and a line speed of 15 50 m/min, giving a dwell time of approximately one minute, the dwell time using NIR irradiation may be able to be reduced to of the order of seconds or less. The amount of NIR electromagnetic radiation will vary depending on the properties of the paper or non-woven being processed. A black paper will absorb more energy than a white paper or clear overlay paper, and thus the parameters for the 20 individual paper or non-woven need to be taken into consideration. Options to manage the process include controlling the speed at which the impregnated and/or coated paper or non-woven passes through the NIR radiation unit or units, controlling the power output of the NIR unit or units, choice of NIR emitter (eg 800w, 1200w, 1800w, 2500w, 3600w, 4000w and 4400w) and whether the NIR radiation is applied from one side or 25 both sides. In an embodiment, the method may include applying one or more successive thin coats of resin to the at least partially dried and at least partially cured b-stage pre-preg WO 2007/065222 PCT/AU2006/001864 6 produced at the heating and curing station. Such thin coats may be applied at a coverage in the range 2 to 10 g/m 2 , preferably 4 to 8 g/m 2 , most preferably 5 to 6 g/m 2 . In a second aspect, the invention provides apparatus for applying a thin coat or multiple thin coats of resin to an at least partially dried and at least partially cured b 5 stage pre-preg, disposed downstream of a heating and curing station or stations that produced the pre-preg. The resin impregnating the paper or non-woven may be a thermosetting resin component consisting of UF, MF, PF, or any combination of these, whether or not modified with other compatible resin systems. 10 Downstream of the heating and curing station there may be a station for manufacturing a decorative or industrial laminate from one or more of the pre-pregs. Indeed, the invention extends, in a third aspect, to a method of manufacturing a decorative or industrial laminate, characterised by employing one or more b-stage pre preg papers or non-wovens produced according to the first aspect of the invention. 15 Optionally, this method may further employ in the laminate one or more pre-preg papers or non-wovens produced by drying and curing in conventional non-NIR ovens. The final fully cured surface and surface characteristics may be obtained, for example, in a hot press. Brief description of the drawings 20 The invention will now be described, by way of example only, with reference to the accompanying drawings, in which: Figure 1 is a schematic depiction of apparatus for manufacturing a b-stage pre preg of resin impregnated paper or non-woven, according to an embodiment of the invention; 25 Figure 2 shows a modified form of the apparatus depicted in Figure 1, for additionally applying one or more thin coats to the pre-preg; and WO 2007/065222 PCT/AU2006/001864 7 Figure 3 is a diagrammatic plan view of one of the NIR irradiator units. Embodiments of the apparatus The illustrated apparatus includes a resin impregnation station 10, and a heating and curing station 20. An elongated web 5 of paper or non-woven is drawn from a roll 6 5 through the successive stations 10, 20. Resin impregnation station 10 comprises an aqueous or other solvent resin bath 12 in which web 5 is in contact twice with the resin 11 as illustrated to ensure paper saturation, a short contact against a pre-wet roll 13, followed by a longer dip 19. Web 5 then passes to metering means 14 comprising metering rollers 15 that are adjustable to 10 control the amount of resin outside the body or matrix of the paper or non-woven web 5. It is found that best results are achieved downstream if the metering means is set to substantially remove resin outside the body or matrix of the paper and non-woven, i.e. there is left at most only a minimal surface coating of the resin on the paper or non woven. 15 The resin is typically melamine formaldehyde (MF), urea formaldehyde (UF) or phenol formaldehyde (FF) resin, but these may be used in combination, or any other suitable or desired resin may be employed. Downstream of metering rolls 15 the impregnated paper or non-woven 5' optionally contacts a set of smoothing rolls 16 and is then passed into a treatment 20 tunnel 22 of heating and curing station 20. Here, the impregnated paper or non-woven 5' is irradiated from both sides by respective NIR irradiator units 24, 25 for a period typically in the range 0.2 to 1.5 seconds. This irradiation is effective to at least partially remove the resin solvent, typically water, by flash evaporation of the solvent, effected through agitation of the solvent molecules. The NIR radiation is further effective to 25 advance cure of the resin, for example by agitating aminoplast molecules of the resin. The web 5 is moved through the successive units by a web conveying configuration of suitable form. This is not illustrated in detail but components are depicted diagrammatically at some turning points, e.g. at 17.

WO 2007/065222 PCT/AU2006/001864 8 Each NIR irradiator unit 24, 25 conveniently comprises a bank of elongate NIR emitters 26 (Figure 3) preferably arranged in functional blocks 28 of six emitters each. The bank extends as an upper or lower bridge across the web path with the emitters aligned in the direction of web travel. Each block may, for example, extend 120mm 5 laterally of the web, with each emitter, e.g., 250 mm long. With this arrangement, the NIR emitter 26, or at least the emitter blocks 28, that lie outside the impregnated web of paper or non-woven can be turned off, meaning that the radiation is only applied on the web and not significantly outside the web, thereby increasing energy productivity. Examples of different web widths are annotated in Figure 3. 10 The distance from the web to the emitters 26 is adjustable according to other parameters such as type of emitter, web speed and grammage or colour of the paper or non-woven material. In a modified embodiment successive NIR irradiations are effected, either with separate irradiators in the one unit or at separate spaced heating and curing stations. 15 The irradiation is managed so as to convert the impregnated paper or non-woven 5' to an at least partially dried and at least partially cured b-stage pre-preg 5". In a further modification, illustrated in Figure 2, the pre-preg 5" is successively treated by applying one or more thin coats of the resin at coating stations 30, and then partially drying and partially curing the respective coat at further NIR drying and curing 20 stations 20' similar to station 20. Coating stations 30 may apply the coats by spraying (32) or by means of gravure rolls (34), and a thin coat is typically applied to both sides of the pre-preg. The number of thin coats can be as many as is required to obtain a desired amount of final resin uptake and coat weight. A typical individual applied thin coat has a coverage of the order of 2 - 10 g/m 2 , preferably 4 - 8 g/m 2 most preferably 25 5 - 6 g/m 2 . Examples A web of white d6cor paper, of basis weight 80 gsm was impregnated with melamine formaldehyde resin in aqueous solvent, and then partially dried and partially WO 2007/065222 PCT/AU2006/001864 9 cured by being passed twice between 4.4 kw NIR irradiators at 60 m/min. With the NIR irradiators operating at 80% power, the first pass exit temperature was measured as 750C and the final exit temperature about 1020C. The end weight (paper, resin and water) was observed to be 165 gsm including about 11% volatiles. Total residence time 5 between the NIR irradiators was 0.5 seconds. In a second trial, the same grade of MF impregnated white d6cor paper was passed once between similar NIR irradiators at a much slower speed, 37.5 m/min. The exit temperature was measured as about 960C and the end weight (paper, resin and water) 140 gsm. Volatiles comprised about 8%. Residence time between the NIR 10 irradiators was 0.8 seconds. In both trials, no significant skinning or dusting was observed. These trials demonstrate that these trials demonstrate that NIR radiation is an extremely effective method of removing the solvent from the impregnated paper or non woven over a comparatively short distance and with a comparatively short exposure 15 time to the NIR energy source. A conventional set of drying ovens operating at the same or a similar web speed would remove similar amounts of solvent over a distance of 12 - 20 metres with a dwell time of 18 - 30 seconds.

Claims (24)

1. A method of manufacturing a b-stage pre-preg of resin impregnated paper or non-woven, characterised by irradiating a resin impregnated paper or non-woven with near infra-red (NIR) radiation to at least partially remove solvent by evaporation of the 5 solvent, and to advance cure of the resin, whereby to produce an at least partially dried and at least partially cured b-stage pre-preg.

2. A method according to claim 1 wherein the NIR radiation is applied substantially uniformly through the impregnated paper or non-woven.

3. A method according to claim 1 and 2 wherein said paper or non-woven is an 10 elongated web conveyed through a heating and curing station at which said irradiation is effected.

4. A method according to claim 1, 2 or 3, further including controlling the amount of said resin outside the body or matrix of the paper or non-woven.

5. A method according to claim 4 wherein said controlling comprises substantially 15 removing resin outside the body or matrix of the paper or non-woven.

6. A method according to any one of claims 1 to 5 further including applying one or more successive thin coats of resin to the at least partially dried and at least partially cured b-stage pre-preg.

7. A method according to claim 6 where said individual thin coats are applied at a 20 coverage of 2 to 10 g/m 2 .

8. A method according to any one of claims 1 to 7 wherein said evaporation of the solvent is flash evaporation of the solvent by agitation of the solvent molecules.

9. A method according to any one of claims 1 to 8 wherein said advance of resin cure comprises agitating aminoplast molecules of the resin. WO 2007/065222 PCT/AU2006/001864 11

10. A method according to any one of claims 1 to 9 wherein said resin-impregnated paper or non-woven is irradiated with NIR radiation to produce the at least partially dried and at least partially cured b-stage pre-preg, for a time period less than 10 seconds.

11. A method according to any one of claims 1 to 9 wherein said resin-impregnated 5 paper or non-woven is irradiated with NIR radiation, to produce the at least partially dried and at least partially cured b-stage pre-preg, for a time period less than 5 seconds.

12. A method according to any one of claims 1 to 11, wherein the resin-impregnated paper or non-woven is irradiated in conjunction with being heated by conventional non 10 NIR drying/curing ovens, to achieve a pre-determined drying and curing program.

13. A method of manufacturing a decorative or industrial laminate, characterised by employing one or more b-stage pre-preg papers or non-wovens produced according to any one of claims 1 to 12.

14. A method according to claim 13 further employing in the laminate one or more 15 pre-preg papers or non-wovens produced by drying and curing in conventional non-NIR ovens.

15. A method according to claim 14 including fully curing the pre-preg papers or non woven in a hot press.

16. Apparatus for manufacturing a b-stage pre-preg of resin impregnated paper or 20 non-woven, including a resin impregnation station for impregnating a paper or non woven with resin carried by a solvent, and a heating and curing station having irradiation means to irradiate the impregnated paper or non-woven with near infra-red (NIR) radiation to at least partially remove solvent by evaporation of the solvent, and to advance cure of the resin, whereby to produce an at least partially dried and at least 25 partially cured b-stage pre-preg. WO 2007/065222 PCT/AU2006/001864 12

17. Apparatus according to claim 16 wherein said irradiation means is configured for applying the NIR radiation substantially uniformly through the impregnated paper or non-woven.

18. Apparatus according to claim 16 or 17, further including means for conveying 5 said paper or non-woven as an elongated web through said resin impregnation station and said heating and curing station.

19. Apparatus according to claim 18, further including metering means between said stations for controlling the amount of said resin outside the body or matrix of the paper or non-woven. 10

20. Apparatus according to claim 19, wherein said metering means is operable to substantially remove resin outside the body or matrix of the paper or non-woven.

21. Apparatus according to any one of claims 16 to 20, further including means downstream of said heating and curing station for applying one or more successive thin coats of resin to the at least partially dried and at least partially cured b-stage pre-preg 15 of resin impregnated paper or non-woven produced at the heating and curing station.

22. Apparatus for applying a thin coat or multiple thin coats of resin to an at least partially dried and at least partially cured b-stage pre-preg, disposed downstream of a heating and curing station or stations that produced the pre-preg.

23. Apparatus according to claim 22 wherein said heating and curing station or 20 stations effect drying and curing of the resin impregnated paper or non-woven by irradiation with near infra-red (NIR) radiation.

24. Apparatus according to claim 22 or 23, including at least one NIR irradiator unit for at least partially drying and at least partially curing the thin coat or multiple thin coats of resin. 25