比利时专利BE1019810A3 TWO COMPONENTS THERMOHARDER-RUBBER OBJECT.

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公开号:BE1019810A3
申请号:E2012/0113
申请日:2012-02-27
公开日:2012-12-04
发明作者:Rik Gielen
申请人:B & P Products；
IPC主号:

专利说明:

Two-component thermoset rubber object
SCOPE OF THE INVENTION
The present invention relates to articles which must offer sufficient mechanical strength but, in addition, to certain of their surfaces also shock-absorbing or sealing. must offer properties and / or have a closing function. More particularly, the invention relates to machine or structural parts, such as, for example, from pneumatic or hydraulic systems, where elastic seals are provided between the rigid parts to separate the contents of the whole, or the condition thereof, from the environment of the whole.
BACKGROUND OF THE INVENTION
Many parts are expected to have considerable mechanical properties, but they are also expected to close or seal well on certain contact surfaces with other parts, for example in order to keep the contents of the systems under pressure and / or leakage From the contents to the environment. Such components can be found, for example, in hydraulic or pneumatic systems, in particular: devcheitiisch: process technology, in vehicles, but also in more everyday household; garden and kitchen objects or appliances such as washing machines, vacuum cleaners, hand blenders and kitchen robots.
Due to the mechanical requirements, these parts are often made of metal. A separate rubber component is then usually provided for the seal, which is then applied between the surfaces with which two components come into contact with each other. To keep the rubber parts in place, recesses are sometimes provided in the contact surfaces. The rubber parts may also be glued to one of the contact surfaces for the same reason.
This mounting technique means that at the time of mounting an additional part, in this case the rubber part, must be provided. This additional part must be exactly in the prescribed location for correct assembly. Such extra parts increase the complexity and difficulty of the assembly, as well as the risk of problems and / or failures. Additional parts require their own supply chain, may be lost or missing, and may be mounted incorrectly. In each of these cases this leads to problems with the assembly itself or endangers the proper functioning of the whole.
To circumvent this problem, objects were designed in which a rubber part is integrated with a rigid part in one and the same object. For example, JP 02103110 A describes how injection molding first injects a quantity of a rubber composition into the cavity of a movable core mold, and before hardening the rubber a thermosetting resin is injected into the still-free resin via a second nozzle space in the mold, thereby pressing the core in another position, after which the thermosetting resin is cured and the rubber is vulcanized at the same time. According to JP 02103110 A, this method provides a very tight connection between the two materials of the molded article, making the article suitable for oil seals in the engines of motorcycles. Also JP 63264322 A, JP 59202928 A and JP57084834 A describe similar articles made by introducing a thermosetting resin and a rubber composition to be vulcanized in a casting or compression mold after which. At the same time the resin is cured and the rubber is vulcanized. The problem with these two-component articles thus produced is that this production method cannot ensure precise dimensions of the two parts, because distortion of the free surface of the first ...
component introduced during the introduction of the second component. The intermediate surface between the two parts is therefore not precisely defined.
Because of the different mechanical properties of the two parts, this leads to problems. For example: the deformation characteristics of an elastic part will not be exactly predictable because its dimensions are not precisely determined. .
JP 2007-011047 describes how spin-casting or centrifugal molding produces a two-part rubber sheet. In a first step, the mold is partially, but at least 80%, filled with a first Polyurethane composition for a more elastic rubber with an α value of 0.85, which is then cured at 130 ° C. Then, in a second step, the mold is filled with a second polyurethane composition for a rubber with a higher hardness and a lower surface friction, and cured.
The end product is a rubber knife of 2 mm thick with the elasticity of the first rubber but on one side thanks to the harder rubber layer of about 0.1 mm and the low frictional resistance of the second rubber, which is very suitable as a scraping knife due to this combination of properties (“Cleaning bladé”) in electrical photography or dry photocopy technique. JP 2007-011047 states that the thickness of the surface layer is of little importance, as long as it is present and is not thicker than 20% of the total leaf thickness, and this every To be able to maintain the elasticity of the main layer, the dimensions of the two components are precisely guaranteed on this interface in this technique too.
WO 2008/003279 describes a component for a vacuum pump that consists of a thermoset part and a silicone rubber part in contact with the thermoset part. The parts were injection molded in successive steps. The process comprises a first step in which the thermoset is cast into a mold, after which the mold is adjusted to receive the injection of silicone rubber: Between two successive injection molding steps, a process step can be provided in which the temperature of the thermoset part is adjusted, and also a deburring process step can be switched.
However, WO 2008/003279 does not describe under which conditions the curing of the silicone rubber must take place. It is known to those skilled in the art that silicone rubber is very often vulcanized at room temperature, which is generally known as room temperature tempering (RXV). When cooling the thermoset part to room temperature, before the rubber composition is injected. , there is a risk that due to thermal shrinkage there will be a play between the thermoset part and the mold in which it sits. As a result, when injecting the rubber composition, some of that composition may leak into the space created by that play and vulcanize therein. As a result, the rubber part is deformed, it deviates from the intended dimensions, and the thermoset part is marred with rubber stains or a rubber layer on those surfaces where the rubber has no function. Moreover, this means an additional consumption of raw material.
Due to the lack of precisely guaranteed dimensions of the contact surface between the two components that make up the objects of the prior art, there remains a need for a method which gives a higher precision of the dimensions of the different parts in the manufacture of objects that consist of a rigid thermoset part and an integrated elastic rubber part.
The present invention has for its object to provide for the avoidance or at least alleviation of the problems described above and / or general improvements.
SUMMARY OF THE INVENTION
According to the invention there is provided a multi-part shaped article as well as a method for its manufacture, as defined in any of the appended claims.
The invention provides a molded article comprising a rigid member and a resilient member, the rigid member comprising a thermoset and providing mechanical support to the resilient member, the resilient member comprising vulcanized rubber and being suitable for a closing and / or shock-absorbing function to be filled, characterized in that the article is manufactured according to a method comprising a preforming step in which the thermoset is preformed in a first form and subsequently cured to form the rigid part, wherein the. curing of the thermoset is carried out at a temperature in the range of 150 to 230 ° C, after which the first shape is adjusted and / or the cured, rigid, part. is transferred to a second mold, and thereafter by injection molding, transfer molding, compression molding and / or pressing the rubber is formed and subsequently vulcanized to form the resilient part, and this while the rubber is in contact with the thermoset of the rigid part, wherein the vulcanization is carried out at a temperature in the range of 150 to 230 ° C.
We have found that in this way the dimensions of the two parts of the object can be guaranteed very precisely, also those of the intermediate surface that arises between the two or more different parts or components of the multi-part object. This advantage is brought about by the fact that the first thermoset material is cured while still in its first form, which guarantees very precise dimensions of the first part. The formation of the rubber part then happens in a room whose dimensions are also precisely known. , which is formed by the second and / or modified form and the cured rigid part with its precise dimensions, so that also the vulcanized rubber part has precisely guaranteed dimensions. This offers the advantage that the behavior of the rubber part can be predicted very precisely, which is of great importance in many applications, such as providing a good seal under well-defined stress conditions: Both the curing of the thermoset and the vulcanization of allowing the rubber to take place in the temperature range 150-230 ° C, any shrinkage of the cured rigid part relative to the mold remains minimal because the cured rigid part fills the first form as well as possible, so that possible leakage of the rubber composition between the mold and the cured rigid part is kept as small as possible or even avoided. Under these conditions it is also possible to ensure that both the rigid part and the rubber part are given exactly guaranteed dimensions. In this way it is also avoided that more rubber composition would be used than is necessary to form the resilient part, or that the object would have to be subjected to an after-treatment to remove the rubber caused by the leak. Such additional steps are usually complex and time-consuming, and generally fail to achieve the desired view of one. restore unpolluted thermoset surface.
In another embodiment, the invention provides a method for manufacturing a molded article, characterized in that the method comprises a preforming step in which the thermoset is preformed in a first form and subsequently cured at least partially to form the rigid part, after which the first mold is adjusted and / or the hardened rigid part is transferred to a second mold, and wherein by injection molding, transfer molding, press molding and / or pressing the rubber is formed and then vulcanized to form the resilient part, and this while the rubber is in contact with the thermoset of the rigid part.
DETAILED DESCRIPTION
The cured thermoset which forms the rigid part in the article according to the present invention preferably has at least one characteristic, and possibly all characteristics, from the list consisting of • a Rockwell hardness as measured according to the standard test method ASTM D-785 with a Rockwell tester, from at least M60 to M140, preferably at least M70, and more preferably M75 or even at least M80, and optionally at most M130, preferably at most M125, and more preferably at most M120, Brinell hardness HB measured according to ISO 6506-1: 2005 as HBS 10/100 of at least 1.6, preferably of at least 2.6, more preferably an HBW 10/3000 of at least 15, preferably at least 35, and even more preferably of at least 70, more preferably at least 90, even more preferably at least 110, preferably at least 120, and in addition at least 140, preferably at least 150, more preferably at least 200, even more preferably at least 250 , moreover preferably at least 300, more preferably at least 350, even more preferably at least 500, and even more preferably at least 800, a tensile strength, as measured on a sample made by injection molding according to ISO 527, preferably from 10 to 400, more preferably from 20 to 300, even more preferably from 30 to 200, even more preferably from 40 to 100, even more preferably from 60.0 to 70.0 MPa, • an elongation at break (elongation at break ) as measured on a sample made by injection molding according to ISO 527, of at most 1000%, preferably at most 0.900%, more preferably at most 0.800%, even more preferably at most 0.700%, and at even more preferably at most highest 0.600%, • an E-modulus or Young's Elasticity Modulus at room temperature (at about 23 ° C, or in other tests in the range of. .
20-25 ° C) as measured by the standard test method ASTM D-638 of at least 2 to 30 GPa, preferably at least 3 and more preferably at least 4 and even 5 GPa, even more preferably at least 6 , or 7, or even 8 GPa, and thereby possibly at most 25 GPa, preferably at most 20 ..... · - GPa, but moreover preferably at most 18 GPa or even at most 16.0 GPa, • a flexural modulus as measured on a sample made by ISO 178 injection molding, of at most 30 GPa, preferably at most 25 GPa, even more preferably at most 20 GPa, furthermore preferably at most 19 or even only 18 GPa, and possibly at least 10 GPa, preferably at least 14 GPa, even more preferably at least 16.0 GPa, • a notch impact value determined by the Charpy notch impact test at 23 ° C, as measured on a non-notched sample made by injection molding according to ISO 179 / 1eU , preferably from 0.50-12.00 J / cm 2, more preferably from 0.70-9.00 J / cm cm 2, more preferably from 0.90-7.00 J / cm 2, in addition. more preferred. 1.00-4.00 J / cm2, • ·· ... a notch impact value determined with the Charpy notch impact test at 23 ° C, as measured on a notched sample made by injection molding according to ISO 179 / 1eA, preferably from 0.100 - 1000 J / cm2, more preferably from 0.200 - 0.700 J / cm2, more preferably from 0.300 - 500 J / cm2, even more preferably from 0.350 - 0.450 J / cm2, • an electrical Volumetric Resistance (Electrical
Volumetry Resistivity) as measured according to standard IEC 60093, preferably from 1.00 e + 6 to 1.00 e + 16 ohm-cm, more preferably 1.00 e + 9 to 1.00 e + 16 ohm-cm, more preferably 1.00 e + 12 to 1.00 e + 16 ohm-cm, even more preferably from 1.00 e + 15 to 1.00 e + 16 ohm-cm, a dielectric constant as measured at a frequency of approximately 100 Hz according to standard IEC 60250, preferably from 1.50 to 10.00, more preferably from 3.00 to 8.00, more preferably from 4.00 to 7.00, even more preferably from 6.00 to 6.50.
The vulcanized rubber that forms the elastic or resilient part of the article according to the present invention preferably has at least one feature, and possibly all features, from the list consisting of a glass transition temperature Tg of at most 25 ° C, preferably of at most 0 ° C, more preferably at most -25 ° C, even more preferably at most -50 ° C, more preferably at most -60 ° C, and even more preferably at most -7 ° C ( cis-1,4-polyisoprene = natural rubber), even more preferably at most-90 ° C (polybutadiene), • an E-modulus or Young's Elasticity module at room temperature (about 23 ° C, or in the range of 20-25 ° C) as measured according to the standard test method ASTM D-412 of preferably at most 5 x 10'-5 GPa, more preferably at most 5 x 10'3 to 1 GPa; even more preferably 1 x 10 12 to 0.5 GPa, a shore A hardness measured according to the standard test method ASTM D-2240 of at least 20 to 100, preferably at least 30 to 90, more preferably at least 40 and even more preferably at least 50, and optionally at most 80, preferably at most 70, a tensile strength at room temperature (about 23 ° G, or in the range of 20-25 ° C) as measured according to the standard test method ASTM D-412 of at most 7 to 20 MPa, preferably at most 12 to 17 MPa.
Preferably, the thermoset in the article of the present invention is selected from the list consisting of a phenolic resin or a phenolic formaldehyde (PF) resin, in which optionally substituted phenols such as cresol and / or aldehydes other than formaldehyde are incorporated, and wherein novolac resin or bakelite but preferably resole resin is selected, a melamine formaldehyde (MPF) resin, a cellulose resin, a bis-maleimide resin, an epoxy resin, preferably based on bisphenol A, a polyester resin, a polyimide resin, a polyurethane resin, a silicone resin, urea or urea-formaldehyde resin, melamine or melamine-formaldehyde resin, and mixtures thereof, where useful supplemented with a hardener, such as with an epoxy resin, in which case the hardener may be an amine or an acid anhydride.
Epoxy EP 3535, Melopas MP 180/181/182/183, Ralupol UP 804/4385/4806, all from Raschig and Vyncolit 2923W Black, 4523XB Black, 4421XB Black, X613 Black, Green, X655 / X620 / X680 black, green from Vyncolit.
In an embodiment of the present invention, the thermosetting member is preferably reinforced with fibers, preferably fibers selected from the list consisting of glass fiber (GF), carbon fiber, cellulose fiber, and mixtures thereof. The fibers bring the advantage that the brittleness of the rigid part is reduced, and its strength is increased. This is especially the case with phenol resins, which are preferably with glass fibers and / or. mineral fibers are strengthened.
In an embodiment of the article according to the present invention, the rigid part further comprises at least one element selected from the list consisting of a filler, an organic peroxide, an agent for promoting release from the mold (mold release agent), and a curing promoter, wherein the filler is preferably selected from the list consisting of graphite, graphite powder, wood powder, wood flour, talc powder, sand, a silicate, clay, and other mineral fillers such as calcium carbonate, and mixtures thereof.
In another embodiment of the article according to the present invention, the rubber is selected from the list consisting of natural rubber, polyisoprene, preferably at least 50% consisting of cis-polyisoprene, styrene butadiene rubber, butadiene rubber, ethylene propylene rubber, nitrile rubber, chloroprene rubber, butyl rubber, silicone rubber, polynorbornene rubber, poly urethane rubber, fluorocarbon rubber, polyacrylate rubber, fluorosilicone rubber, epichlorohydrin rubber, chlorosulfonated rubber, hydrated nitrile rubber and mixtures thereof.
The most common way to vulcanize rubber, applicable to most diene rubbers, such as natural rubber, styrene butadiene rubber, ethylene propylene rubber and nitrile rubber, is sulfur vulcanization, whereby the rubber is heated with sulfur, usually in the presence of organic vulcanization accelerators to to save both time and resources. Diene rubbers can also be vulcanized with sulfur chloride or with a thiuramic disulfide or bis-morpholine disulfide. Butyl rubber can be vulcanized with quinone dioxide or phenols, Vulcanization with peroxides can be used almost universally and is mainly used with ethylene propylene rubber and silicone rubber. Chloroprene rubber does not vulcanize with sulfur but with zinc oxide or a thiourea. Acrylate rubbers containing a cataloged co-monomer are vulcanized with polyamines and fluororubbers with a mixture of a metal oxide and an amine.
In yet another embodiment of the article according to the present invention, the rubber is vulcanized with sulfur or with peroxides.
In the embodiment according to the present invention wherein the rubber is vulcanized with sulfur, the rubber comprises at most 35% weight of sulfur, preferably at most 25%, more preferably at most 15%, even more preferably at most 10%, more preferably at most 8% or even only 6% weight, and optionally the rubber comprises at least 0.5% weight of sulfur, preferably 1% weight, and more preferably 1.2% weight, based on the weight of rubber which "is present in the resilient member.
In an embodiment of the article according to the present invention, the resilient part further comprises at least one element selected from a vulcanization accelerator, a catalyst, a filler, in addition to the rubber, the filler being preferably selected from the list already mentioned above. has been displayed.
In another embodiment, the object of the present invention is selected from the list consisting of a pump housing, a pump housing, a valve cover for an internal combustion engine, an oil sump, a brake cylinder, an electrical component, such as a base for a relay, preferably a watertight relays, parts for general electrical applications with watertight requirements, such as with a pond pump, a part from a hydraulic and / or pneumatic application, such as a valve housing, etc ....
The inventors have further established that with some thermosets, a certain thermal shrinkage can occur upon cooling after curing of the thermoset. Especially with such thermosets, it is preferred by the inventors that the rigid portion is still sufficiently warm when the rubber composition is introduced into the cavity provided by the second form or by the adapted first form.
In the method according to the present invention, therefore, in an embodiment in which the curing of the thermoset is carried out at a temperature in the range of 150 to 230 ° C and in which the vulcanization is carried out at a temperature in the range of 150 to 230 ° C at the start of vulcanization of the rubber, the hardened rigid part. preferably a temperature not lower than at most 50 degrees Celsius below the vulcanization temperature of the rubber, more preferably not lower than at most 30 degrees Celsius, even more preferably at most 25 degrees Celsius, and furthermore preferably at most 20 degrees Celsius, more preferably at most 15 degrees Celsius, even more preferably at most 10 degrees below, even more preferably not lower than at most 5 degrees below, more preferably not lower than at most 2 degrees below, and at the most preferably not lower than the vulcanization temperature of the rubber.
This offers the advantage that the rigid part still properly or closely fills the portion of the modified or the second shape intended for it at the time the rubber composition is introduced, such that no or substantially no amount of the rubber composition would slip between the mold and the rigid part to which it is not intended to flow, also with thermoset materials that are characterized by a certain thermal shrinkage.
In a further embodiment according to the present invention, the vulcanization of the rubber is carried out at a temperature not lower than at most 50 degrees Celsius below the curing temperature of the thermoset, more preferably not lower than at most 3 degrees Celsius, at even more preferably at most 25 degrees Celsius, and furthermore preferably at most 20 degrees Celsius, more preferably at most 15 degrees Celsius, even more preferably at most 10 degrees below, even more preferably not lower than at most 5 degrees below, at more preferably not lower than at most 2 degrees below, and most preferably not lower than the curing temperature of the thermoset.
This offers the advantage that the rigid part still properly or closely fills the portion of the adapted or second form intended for it to be introduced into the rubber composition such that no or substantially no amount of the rubber composition could slip between the mold and the rigid part to which it is not intended to flow, also with thermoset materials that are marked.
due to a certain thermal shrinkage.
In an embodiment of the method according to the present invention, the rubber is applied in the modified or second mold in a composition which further comprises at least one element selected from sulfur, a sulfur-containing component, a vulcanization accelerator, a catalyst, a filler , wherein preferably the filler is selected from the list given earlier in this document.
In a further embodiment of the method according to the present invention, the vulcanization is carried out at a temperature in the range of 160 to 210 ° C, preferably of 170 to 200 ° C and more preferably of 175 to 195 ° C.
In yet a further embodiment of the method according to the present invention, the curing of the thermoset is carried out at a temperature in the range of 155 to 210 ° C, preferably from 160 to 200 ° C and more preferably from 165 to 195 ° C .
In another embodiment of the method according to the present invention, the temperature of the rigid part is changed by heating or cooling before it is brought into contact with the rubber composition. This reduces the risk that the rubber composition would prematurely vulcanize before it filled up the space in the mold. This additional step is preferably used if a thermoset is selected which is characterized by no or little thermal shrinkage, or if the second form is adapted to tightly enclose the rigid part, at the adjusted temperature, at those places or surfaces that are not intended to come into contact with the rubber compound.
In a further embodiment of the method according to the present invention, the curing and / or the vulcanization is further driven by an additional thermal treatment by exposure of the object to a specific temperature as prescribed in one of the preceding claims during a period of at least 4 hours , preferably at least 8 hours, even more preferably 12 hours, in addition at least 18 hours, preferably at least 24 hours, even more preferably 36 hours, even more preferably at least 48 hours, or even at least 72 hours .
In a further embodiment of the method according to the present invention, the method further comprises deburring at least one side of at least one part of the object selected from the rigid part and the resilient part, or from both parts.
In a further embodiment of the method according to the present invention, the method comprises subjecting the object to a mechanical operation selected from the list consisting of drilling, milling, turning on a lathe, and thread pulling, or a combination thereof.
In a further embodiment of the method according to the present invention, the method further comprises subjecting the article to a surface treatment selected from the list consisting of labeling, lacquering, painting, printing, metallizing such as metal vapor deposition, and rough sanding, for example, to make at least one of the surfaces a rougher look, or a combination thereof.
In a further embodiment of the method according to the present invention, the method further comprises introducing into the object of an insert, for example a bolt or other metal component, for example an electrical contact point, and this insertion can be done even before the thermoset in the first mold is introduced, or before or after the vulcanization of the rubber, and whatever may happen before or after deburring, or before or after the mechanical processing, or before or after the surface treatment. "
In yet a further embodiment of the method according to the present invention, the method further comprises introducing the article into a composite article.
Now that this invention has been fully described, those skilled in the art will realize that the invention can be implemented with a wide range of parameters within what is claimed, without therefore departing from the spirit and scope of the invention. As understood by those skilled in the art, the general invention as defined by the claims includes other preferred embodiments that are not specifically mentioned;

权利要求:
Claims (21)
[1]
A molded article comprising a rigid member and a resilient member, the rigid member comprising a thermoset and providing mechanical support to the resilient member, the resilient member comprising vulcanized rubber and being adapted to perform a sealing and / or shock-absorbing function characterized in that the article is manufactured according to a method comprising a preforming step in which the thermoset is preformed in a first shape and then cured to form the rigid part, wherein the curing of the thermoset is carried out at a temperature in the range of 150 to 230 ° C, after which the first mold is adjusted and / or the hardened rigid part is transferred to a second mold, after which the rubber is formed by injection molding, transfer molding, press molding and / or pressing and subsequently vulcanized around the resilient part to form, and this while the rubber is in contact with the thermoset of the rigid part, w the vulcanization is carried out at a temperature in the range of 150 to 230 ° C.
[2]
The article of claim 1 wherein the cured thermoset has at least one feature from the list consisting of • a Rockwell hardness as measured according to the standard test method ASTM D-785 with a Rockwell tester, of at least M60 to M140, preferably at least M70, and more preferably M75 or even at least M80, and optionally at most M130, preferably at most M125, and more preferably at most M120, a Brinell hardness HB measured according to ISO 6506-1: 2005 as HBS 10/100 of at least 1.6, preferably of at least 2.6, more preferably an HBW 10/3000 of at least 15, preferably of at least 35, even more preferably of at least 70, more preferably of at least 90, even more preferably at least 110, preferably at least 120, and in addition at least 140, preferably at least 150, more preferably at least 200, even more preferably at least 250, furthermore preferably at least 300, more preferably at least 35 0, even more preferably at least 500, and even more preferably at least 800, a tensile strength, as measured on a sample made by injection molding according to ISO 527, preferably from 10 to 400, more preferably from 20 to 300, even more preferably from 30 to 200, even more preferably from 40 to 100, even more preferably from 60.0 to 70.0 MPa, an elongation at break as measured on a sample made by injection molding according to ISO 527, of at most 1000%, preferably at most 0.900%, more preferably at most 0.800%, even more preferably at most 0.700%, and at even more preferably at most 0.600%, • an E-modulus or Young's Elasticity modulus at room temperature (at about 23 ° C, or in other tests in the range of 20-25 ° C) as measured by the standard test method ASTM D-638 of at least 2 to 30 GPa, preferably at least 3 and more preferably at least 4 and even 5 GPa, even more so have at least 6, or 7, or even 8 GPa, and possibly at most 25 GPa, preferably at most 20 GPa, but moreover preferably at most 18 Gpa or even at most 16.0 GPa, a flexural modulus such as measured on a sample made by injection molding according to ISO 178, of at most 30 GPa, preferably at most 25 GPa, even more preferably at most 20 GPa, furthermore preferably at most 19 or even only 18 GPa, and possibly at least 10 Gpa, preferably at least 14 GPa, even more preferably at least 16.0 GPa, • a notch impact value determined with the Charpy notch impact test at · 23 ° C, as measured on a non-notched sample made by injection holes according to ISO 179 / 1eU, preferably from 0.50-12.00 J / cm 2, more preferably from 0.70-9.00 J / cm 2, more preferably from 0.90-7.00 J / cm 2, even more preferably from 1.00-4.00 J / cm 2, · '·· - · -' · one notch impact value determined with the notch impact test of charpy 'at 23 ° C, as measured by to a notched sample made by injection holes according to ISO 179 / 1eA, preferably from 0.100 - 1000 J / cm2. more preferably from 0.200 - 0.700 J / cm 2, more preferably from 0.300 - 500 J / cm 2; even more preferably from 0.350 - 0.450 J / cm 2, • an electrical Volumetric Resistance (Electrical Volumetry Resistivity) as measured according to standard IEC 60093, preferably from 1.00 e + 6 to 1.00 e + 16 ohm-cm, more preferably 1.00 e +9 to 1.00 e + 16 ohm-cm, more preferably 1.00 e + 12 to 1.00 e + 16 ohm-cm, even more preferably from 1.00 e + 15 to 1.00 e + 16 ohm-cm, • a dielectric constant such as measured at a frequency of about 100Hz according to IEC 60250 standard, preferably from 1.50 to 10.00, more preferably from 3.00 to 8.00, more preferably From 4.00 to 7.00, even more preferably from 6.10 to 6.50.
[3]
The article according to claim 1 or 2, wherein the vulcanized rubber has at least one feature from the list consisting of • a glass transition temperature Tg of at most 25 ° C, preferably of at most 15 ° C, even more preferably at highest; 0 ° C, in addition not more than -10 ° C, preferably not more than -25 ° G, even more preferably not more than -40 ° C, even more additionally not more than -50 ° C, even more preferably -60 ° C , and even more preferably at most -70 ° C, w · an E-modulus or Ypung's Elasticity modgius at room temperature (about 23 ° C, or in the range of 20-25 ° C) as measured according to the standard test method ASTM D -412 of preferably at most 5 x 10'4 to 5 GPa, more preferably at most 5 x 10'3 to 1 GPa, even more preferably 1x10'2 to 0.5 GPa, a tensile strength at room temperature (about 23 ° C, or in the range of 20-25 ° C) as measured by the standard test method ASTM D-412 of at most 7 to 20 MPa, preferably at most 12 to 17 MPa.
[4]
The article of any one of the preceding claims wherein the thermoset is selected from the list consisting of a phenolic resin or a phenol-formaldehyde (PF) resin, in which optionally substituted phenols such as cresol and / or aldehydes other than formaldehyde are incorporated, and wherein novolac resin or bakelite but preferably resole resin is selected, a melamine formaldehyde (MPF) resin, a cellulose resin, a bis-maleimide resin, an epoxy resin, preferably based on bisphenol A, a polyester resin, a polyimide resin, a polyurethane resin, a silicone resin, urea or urea-formaldehyde resin, melamine or melamine-formaldehyde resin, and mixtures thereof, where useful supplemented with a hardener, such as with an epoxy resin, in which case the hardener may be an amine or an acid anhydride .
[5]
The article of any one of the preceding claims wherein the thermoset is reinforced with fibers, preferably selected from the list consisting of glass fiber (GF), carbon fiber, cellulose fiber, and mixtures thereof.
[6]
The article of any one of the preceding claims wherein the rigid portion further comprises at least one element selected from, the list consisting of a filler, an organic peroxide, an agent to promote release from the mold (mold release agent), and a curing promoter, also referred to as a catalyst, wherein the filler is preferably selected from the list consisting of graphite, graphite powder, wood powder, wood flour, talcum powder, sand, a silicate, clay, and other mineral fillers such as calcium carbonate, and mixtures thereof . ·; - ··· -
[7]
The article of any one of the preceding claims wherein the rubber is selected from the list consisting of natural rubber, polyisoprene, preferably at least 50% consisting of cis-polyisoprene, styrene butadiene rubber, butadiene rubber, ethylene propylene rubber, nitrile rubber, chloroprene rubber, butyl rubber, silicone rubber, polynorbornene rubber, poly urethane rubber, fluorocarbon rubber, polyacrylate rubber, fluorosilicone rubber, epichlorohydrin rubber, chlorosulfonated rubber, hydrated nitrile rubber and mixtures thereof.
[8]
The article of any one of the preceding claims wherein the rubber is vulcanized with sulfur or with peroxides.
[9]
The product according to the preceding claim wherein the rubber is vulcanized with sulfur, and wherein the rubber contains at most 35% weight of sulfur, preferably at most 25%, more preferably at most 15%, even more preferably at most 10%, with more; preferably at the most: 8% or even only 6% weight, and optionally the rubber containing at least, 0-5% weight of sulfur, preferably 1% weight, and more preferably 1.2% weight, based on the weight of rubber present in the resilient part ·
[10]
The article according to any one of the preceding claims, wherein the resilient part further comprises at least one element selected from a vulcanization accelerator, a catalyst, a filler, in addition to the rubber, the filler preferably being selected from the list in claim 6 .
[11]
The article of any one of the preceding claims selected from the list consisting of a pump housing, a pump housing, a valve cover for an internal combustion engine, an oil sump, a brake cylinder, an electrical component, such as a base for a relay, preferably a watertight relays, parts for general electrical applications with watertight requirements, such as with a pond pump, a part from a hydraulic and / or pneumatic application, such as a valve housing.
[12]
A method of manufacturing a molded article according to any one of the preceding claims, characterized in that the method comprises a preforming step in which the thermoset becomes. y. Pre-formed in a first form and then at least partially cured to form the rigid part, after which the first form is adjusted and / or the hardened rigid part is transferred to a second form, and by injection molding, transfer molding, compression molding and / or pressing the rubber is formed and then vulcanized to form the resilient member, and this while the rubber is in contact with the rigid thermoset; part, wherein the curing of the thermoset is carried out at a temperature in the range of 150 to 230 ° C and in which the vulcanization is carried out at a temperature in the range of 150 to 230 ° C, preferably while the cured rigid part is a temperature has no lower than at most 50 degrees Celsius below the vulcanization temperature of the rubber, more preferably no lower than at most 30 degrees Celsius, even more preferably at most 25 degrees Celsius, and furthermore preferably at most 20 degrees Celsius, more preferably at most 15 degrees Celsius,. .. and even more preferably not more than 10 degrees Celsius below, more preferably not lower than not more than 5 degrees Celsius below, more preferably not lower than not more than 2 degrees Celsius below, and most preferably not lower than the vulcanization temperature of the rubber.
[13]
The method of claim 12 wherein the rubber in the modified form is applied in a composition further comprising at least one element selected from sulfur, a sulfur-containing component, a vulcanization accelerator, a catalyst, a filler, preferably the filler is selected from the list of claim 6.
[14]
The method according to claim 12 or 13, wherein the vulcanization is carried out at a temperature in the range of 160 to 210 ° C, preferably from 170 to 200 ° C and more preferably from 175 to 195 ° C.
[15]
The method of any one of claims 12-14 wherein the curing of the thermoset is carried out at a temperature in the range 155 to 210 ° C, preferably from 160 to 200 ° C and more preferably from 165 to 195 ° C.
[16]
The method according to any of claims 12-14 wherein the curing and / or the vulcanization is further driven by an additional thermal treatment by exposure of the article to a certain temperature as prescribed in any one of the preceding claims during a period of at least 4 hours, preferably at least 8 hours, even more preferably 12 hours, in addition at least 18 hours, preferably at least 24 hours, even more preferably 36 hours, even more preferably at least 48 hours, or even at least 72 hour.
[17]
The method according to any of claims 12-16 further comprising deburring at least one side of at least one part of the object selected from the rigid part and the resilient part, or from both parts.
[18]
The method of any one of claims 12-17 further comprising subjecting the article to a mechanical operation selected from the list consisting of drilling, milling, turning on a lathe, and thread drawing, or a combination thereof.
[19]
The method of any one of claims 12-18 further comprising subjecting the article to a surface treatment selected from the list consisting of labeling, lacquering, painting, printing, metallizing such as metal vapor deposition, and rough sanding, e.g. to make at least one of the surfaces a rougher look, or a combination thereof.
[20]
The method according to any of claims 12-19 further comprising inserting into the object an insert, for example a bolt or other metal part, and this inserting can take place before the thermoset in the first form is introduced, or before or after the vulcanization of the rubber, and whatever may happen before or after deburring, or before or after the mechanical processing, or before or after the surface treatment.
[21]
The method of any one of claims 12-18 further comprising introducing the article into a composite article.

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法律状态:

优先权:

申请号 | 申请日 | 专利标题

BE201100138|2011-02-28|

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