Patent Application
20130223086
1. Field of the Invention
The present invention relates to a motor vehicle part comprising a material based on polymer(s) having a surface treatment that makes it possible to improve the surface appearance of the material. The invention also relates to a process for obtaining this part and the use thereof, especially for the manufacture of lighting and/or signaling devices.
2. Description of the Related Art
In the field of technical materials based on polymers, research is often directed towards improving the mechanical properties and/or surface appearance of parts formed from these materials.
In the case of a motor vehicle lighting and/or signaling device, certain parts such as bezels or else trims, essentially fulfill an aesthetic role. Other parts, in particular, mounting plates, reflectors, may play a solely mechanical role or both a mechanical and esthetic role.
By way of example, the role of the reflector is to reflect the light emitted by one or more light sources so that the light beam emitted by the lighting and/or signaling device meets a precise photometry. The bezel must be able to give an aesthetic appearance, shiny or satin-finished for example, which is very homogeneous and durable over time, just like the baseplates and mounting plates, very particularly when they are visible from the outside of the lamp or light.
Irrespective of their function, these parts need to have certain properties, in particular surface properties, whether this is for aesthetic reasons and/or for technical reasons such as a good temperature resistance or a surface appearance that makes it possible not to disturb the reflection of the light emitted by the light and/or lamp.
These parts, which are important elements in a motor vehicle lighting and/or signaling device, may be made of metal or made of a material based on polymer(s), in particular thermosetting or thermoplastic polymers, which have the advantage of lightness and of freedom in the shapes obtained, since they are manufactured by injection-molding techniques.
However, the surface of the parts produced from these materials based on polymer(s) may be modified by numerous factors, including:
1. Surface defects of thermal origin such as deformations, blistering, cracking or other defects. The parts are used in an environment capable of experiencing relatively high temperatures due to the presence of light sources, which generally release heat. A good temperature resistance makes it possible to prevent any deformation (flow) of the part made of the material based on polymer(s). In addition, when these parts are metalized for example by deposition of a reflective metallic layer of aluminum type, the increase in temperature gives rise to a deformation phenomenon of the material leading to blistering at the surface of the metallic layer.
2. Abrasion resistance. The part is liable to be subjected to slight rubbings or abrasions during its transport and its handling leading to the formation of scratches on its surface.
3. Degassing. The increase in temperature mentioned in point 2 of a material based on polymer(s) may also give rise to a phenomenon of extraction of molecules with high vapor pressure (oligomers, additives. etc.) which creates aesthetic defects such as a coloration or dulling of the material, which sometimes leads to unwanted chemical reactions and/or, when the material is in airtight medium, which induces the formation of visible condensates of volatile compounds.
4. Resistance to chemical agents. A material based on polymer(s) is capable of degrading in the presence of various chemical compounds, such as water, oxygen, nitrous oxide, carbon dioxide or any other oxidizing agent, and also certain compounds present in the polymer(s) and capable of entering into reaction with the polymer(s) during degassing.
5. Shine. For certain applications, it is advantageous to have materials which have a shiny surface. However, it sometimes proves difficult to produce depositions that aim to improve this property of the material without modifying the geometry or the texture of the surface of the part.
The present invention therefore relates to a material based on polymer(s) according to the invention comprising a superficial thickness, that is to say a surface thickness, having increased crosslinking. The material based on polymer(s) according to the invention has in particular an improved surface appearance.
In the present application, the term “polymer(s)” is understood to mean polymers that preferably have a Young's modulus at 23° C. of greater than 100 MPa (100 megapascals). These polymers have a particularly advantageous stiffness. Furthermore, they can be shaped by standard processes. Preferably, these polymers have a Young's modulus at 23° C. of between 1000 and 15 000 MPa, more particularly between 2000 and 5000 MPa.
Preferably, these polymers are thermoplastic or thermosetting polymers, alone or as a blend, in particular the polymers selected from the group consisting of polycarbonates (PC), high-temperature polycarbonates (PC-HT), polyamides (PA), acrylonitrile-butadiene-styrene (ABS) copolymers, polybutylene terephthalates (PBT), polyethylene terephthalates (PET), polypropylenes (PP), unsaturated polyesters (UP), polyepoxides (EP), polymethyl methacrylates (PMMA), polysulfones (PSU), polyethersulfones (PES) and polyphenylene sulfides (PPS).
Preferably, the polymer(s) will be selected from the group consisting of polycarbonates (PC), high-temperature polycarbonates (PC-HT), polyamides (PA), acrylonitrile-butadiene-styrene (ABS) copolymers, polybutylene terephthalates (PBT), polypropylenes (PP), unsaturated polyesters (UP-BMC) and polymethyl methacrylates (PMMA).
More preferably, the polymer(s) will be selected from the group consisting of polycarbonates (PC), high-temperature polycarbonates (PC-HT), polyamides (PA), polypropylenes (PP) and methyl polymethacrylates (PMMA).
The expression “based on” is understood to mean a material, comprising, by volume, at least 5% of polymer(s), preferably at least 15%, more preferably at least 20%.
The expression “increased crosslinking” is understood to mean a degree of crosslinking greater than that of the polymer(s) present in the remainder of the material. In general, the degree of crosslinking of the polymer(s) present in the remainder of the material will correspond to the degree of crosslinking obtained under standard polymerization conditions of the polymer(s), that is to say without additional specific treatment of the polymer(s).
For a given set of polymer(s), the degree of crosslinking D may be measured by the solubility of the polymer in a solvent. Since the polymer is soluble in the solvent, the crosslinked portions will themselves be insoluble.
By considering only the mass of the superficial thickness of the polymer:
D=weight of the treated polymer that is insoluble in a solvent/total weight of the polymer.
For example, the degree of crosslinking of polyamide 6,6 (PA-6,6) may be measured as follows:
D=weight of the PA-6,6 which is insoluble in metacresol or formic acid/total weight of PA-6,6.
For PMMA, the degree of crosslinking will be calculated as follows:
D=weight of the PMMA that is insoluble in ethyl acetate/total weight of PMMA.
Advantageously, the degree of crosslinking is 10%, preferably 50%, more preferably 95% greater than that of the polymer(s) present in the remainder of the material.
The crosslinking of the material may also be demonstrated by DSC (differential scanning calorimetry). A comparison of the treated and untreated material demonstrates that the increase in the degree of crosslinking of the material has the effect of making the glass transition temperature “Tg” (endothermic change in heat capacity) disappear. Such a comparison is illustrated in example 6 below.
The motor vehicle part according to the invention may also be characterized by the presence, on the outer surface of the material based on polymer(s), of a thickness having a reduction in the fraction of the free volume of the material.
The free volume is the volume of material not occupied by the polymer(s). The free volume can be measured for example by SAXS (small angle X-Ray scattering). The free volume fraction of a polymer is generally between 0.6 and 0.4. On the other hand, in the material according to the invention, the superficial thickness of the material of the part according to the invention will have a free volume fraction of less than 0.4, preferably between 0.2 and 0.01.
The motor vehicle part according to the invention is capable of being obtained by the process comprising the step that consists in treating the outer surface of the material based on polymer(s) by ion bombardment. This ion bombardment treatment may be a treatment using at least one beam of ions.
Already known in the prior art, in particular from FR-A-2 899 242, is an installation that enables the treatment of an object by ion bombardment.
In the case of the invention, the treatment of the material based on polymer by ion bombardment will make it possible to create a three-dimensional network of polymer(s) at the surface of the material by creating bridges between the macromolecular chains, and on the other hand to graft certain low molecular weight molecules (oligomers or additives) present in the material. Preferably, the ion bombardment treatment will enable a crosslinking resulting from direct bonds between the molecules of polymer(s). A superficial thickness is thus obtained on the material constituting the part, that has increased crosslinking resulting from direct bonds between the molecules of polymer(s).
The ion bombardment treatment may also make it possible to incorporate ions into the material of the motor vehicle part according to the invention in order to treat its surface. In this case it will make it possible to graft certain low molecular weight molecules (oligomers or additives) present in the material.
The ion bombardment treatment is carried out using a device that comprises means of ion bombardment such as for example those described in FR-A-2 899 242: means that form an ion generator and means that form an ion applicator.
The ion applicator customarily comprises means chosen, for example, from electrostatic lenses for forming a beam of ions, a diaphragm, a shutter, a collimator, an ion-beam analyzer and an ion-beam controller.
The ion generator customarily comprises means chosen, for example, from an ionization chamber, an electron cyclotron resonance ion source, an ion accelerator and in certain cases an ion separator.
Ion bombardment is generally carried out under vacuum. For example, FR-A-2 899 242 proposes to house all of the ion bombardment means (ion generator and ion applicator) and also the object to be treated in a vacuum chamber. Evacuation means are connected to this chamber. These evacuation means must make it possible to obtain a relatively high vacuum in the chamber, for example of the order of 10−2 mbar to 10−6 mbar.
Advantageously, the ion bombardment will be carried out by means of ion beams resulting from gases such as helium, neon, krypton, argon, xenon, oxygen or nitrogen, alone or as a mixture. Preferably, oxygen and/or nitrogen, more preferably helium and/or nitrogen, will be used.
Preferably, the ion bombardment will be carried out at a pressure between 1 mbar and 10−5 mbar, preferably between 10−2 mbar and 5×10−4 mbar, transmitting to the material an energy of the order of 0.1 to 100 keV, preferably from 0.3 to 30 keV.
It has been demonstrated that the parts according to the invention have improved properties. Indeed, a better flow resistance at temperature and a better resistance to chemical agents (including resistance to oxidation and to moisture) have been demonstrated for the parts according to the invention. Furthermore, the parts also have a greater shine on the treated surface (see example 1) and are less likely to be subject to the degassing phenomenon (see example 2). It is also possible to modify the color of the material or to make it reflective by virtue of this treatment (see example 1 below) without having to carry out the deposition of a coating such as an aluminization or the deposition of a layer of paint.
These properties originate due to the combination of two phenomena:
Finally, when the part is metalized by deposition of a reflective layer, such as a layer of metal, on the material based on polymer(s), the ion bombardment treatment makes it possible to prevent the blistering phenomenon described above and to prevent the formation of iridescence on the reflective surface. Indeed, a part such as a reflector (or the bezel) must be able to reflect the light achromatically, that is to say without an iridescence or coloration effect, the color of the light beam emitted by a lighting device is a photometric constraint, which is both regulatory and aesthetic.
Advantageously, the thickness having a higher degree of crosslinking or a lower free volume fraction than the remainder of the material is less than 5 μm, preferably less than 2 μm, starting from the outer surface of the material.
The invention also covers a process for treating the surface, in particular the outer surface, of a material based on polymer(s) by ion bombardment. The ion bombardment treatment process is particularly effective for improving the properties of temperature resistance, the properties of resistance to chemical agents and the reflection properties (modification of the reflection coefficient) and/or for modifying the color of a motor vehicle part comprising a material based on polymer(s), in order to reduce the iridescence phenomena of a motor vehicle part comprising a material based on polymer(s) and a reflective layer deposited on the outer surface of the material, preferably a metallic layer, and in order to reduce the degassing phenomena capable of occurring in a motor vehicle part comprising a material based on polymer(s). Some of these properties are demonstrated in the examples that follow.
It will be noted that the degassing phenomenon is particularly reduced when the polymer treated by ion bombardment is a polyamide (see example 2 below) or a polypropylene (see example 5 below).
The improvement in the reflection properties is particularly marked when the polymer treated by ion bombardment is a polypropylene or a polyamide (see example 1 below).
Results that are particularly advantageous in terms of temperature resistance are obtained with high-temperature polycarbonates, treated by ion bombardment. Furthermore, when these high-temperature polycarbonates are metalized using a deposition of a metal layer, significant results are obtained in terms of reduction of the iridescence and blistering phenomena (see example 4 below).
In order to obtain a metalized part, namely a part obtained by depositing a thin metallic layer (for example having a thickness of less than 200 nm) onto a polymer-based part, the results obtained in terms of reduction of the iridescence and blistering phenomena are identical irrespective of the process used, whether the metallization layer was deposited on the material before or after treatment of the part by ion bombardment (see example 4 below). A metalized part is for example a reflector, in which a polymer is coated with a reflective layer via aluminization.
The invention also covers a process for manufacturing a motor vehicle part comprising a material based on polymer(s), comprising the steps consisting in:
The shaping of the material based on polymer(s) according to step 1 of the process may be carried out by any means known in the plastics processing industry, such as for example injection molding, extrusion or thermoforming. The outer surface of the material may optionally be covered by one or more intermediate coatings before coverage by the reflective layer. Preferably, the reflective layer will be a metal layer, such as a layer of aluminum.
The invention also covers:
This process with a step of deposition and a step of treating the material by ion bombardment makes it possible not to decrease the adhesion between the material and the deposited layer, the ion-beam treatment being carried out while the bridges between the material and the deposited layer were produced. The property modifications of the material based on polymer(s) and the advantages described above are retained. This is particularly advantageous for polymers such as PMMA, PC and high-temperature PC. It should be noted that this step of ion bombardment treatment does not necessarily take place directly after the step of depositing the layer, in particular metallic layer, and may be preceded by other treatment steps, for example by a step of depositing a protective layer, such as a varnish.
Preferably, these processes make it possible to obtain motor vehicle parts according to the present invention.
The part according to the invention is particularly suitable for the manufacture of motor vehicle lighting and/or signaling devices, such as lamp bezels, trims, baseplates, mounting plates and reflectors.
Preferably, the part according to the invention is a part of a motor vehicle lighting and/or signaling device, for example a reflector. For example, the reflector of a motor vehicle lamp or a signaling light. This reflector is intended to be associated with a light source, such as LEDs, or incandescent lightbulbs. This may be the reflector of a lamp, for example intended to be associated with LEDs, halogen bulbs or discharge lamps.
The part according to the invention may also be a style part of a motor vehicle lighting and/or signaling device, such as a bezel. The expression “style part” targets a part having at least an aesthetic function. A bezel is a part intended to hide portions of the lighting and/or signaling device, such as wiring, activation mechanisms and attachment means. The part may also be chosen from: trims, baseplates and mounting plates.
The invention also covers a motor vehicle part, this part having an aesthetic, optical, chemical, electrical, thermal and/or mechanical function, this part being subjected to a high thermal stress and comprising a material according to the invention. By way of example, this part may be a bezel (aesthetic function), a reflector (optical function), a detector (chemical function), an electrical insulator (electrical function), a radiator (thermal function) and/or a support part (mechanical function).
Another subject of the invention is an optical module configured to produce a lighting and/or signaling function, comprising a part according to the present invention.
This may be, for example, a module for projecting the image of a light source, such as a module comprising a reflector that concentrates the rays emitted from one focus to a second focus, the reflector being associated with a converging element, such as a converging lens. The converging element is preferably placed in front of the second focus so as to bring the light rays closer. For example, this may be an “elliptical” module (its reflector having a surface corresponding approximately to a surface of an ellipsoid).
Another subject of the invention is a lighting and/or signaling device comprising a motor vehicle part according to the present invention, or an optical module according to the present invention, in particular a lamp, also referred to as a “headlight”, or a signaling light.
Other features and advantages of the invention will be described in the following examples with reference to the figures presented below:
The part is processed by injection molding or by any other means of conversion. This part is inserted into a chamber, equipped with an ion bombardment apparatus, in which a vacuum of between 1 and 10−4 mbar, preferably 10−3 mbar, is produced.
The ion bombardment parameters are the following:
After treatment, the measurements made on the part are the following:
Results:
Conclusion:
It is therefore observed that with the treatment, the color (variation of a and b), the clarity (variation of L) and the shine of the polyamide 6,6 are varied. It will be noted in particular that the shine increases with the amount of energy received by the material.
Bezels of motor vehicle lamps are treated by ion bombardment in the chamber described in example 1 under the following conditions:
Process 1: a single treatment by a beam with helium ions having a mean energy such that each part receives around 1 keV.
Process 2: during a first step, the parts are treated by a beam of helium ions having a mean energy such that each part receives around 5 keV. In a second step, a deposition of aluminum having a thickness of 50-100 nm is applied to each part by PVD (physical vapor deposition) vacuum sputtering before a second deposition of a polysiloxane layer having a thickness of 15-50 nm applied by DC or AC PECVD (plasma enhanced chemical vapor deposition) at 40 kHz (mean frequency, “MF”).
Serial process (metallization): a deposition of aluminum having a thickness of 50-100 nm is applied to each part by PVD (physical vapor deposition) vacuum sputtering before a second deposition of a polysiloxane layer having a thickness of 15-50 nm applied by DC or AC PECVD (plasma enhanced chemical vapor deposition) at 40 kHz (mean frequency, “MF”). There is no treatment by ion bombardment.
The measurements concerning the degassing (also referred to as “fogging”) are carried out according to the following method:
A 2 mm thick sheet of the material to be tested is taken and brought into contact, via convection, with a heat source that may rise up to a temperature of 200° C. A glass slide is placed on top of the sample sheet in order to receive the gases capable of being formed within this sample. The glass slide is itself thermostatically controlled at a temperature of 70° C. to condense the gases formed within the sample.
The sample is subjected, for 20 h, to a temperature determined as a function of its resistance and of the environmental conditions to which the constituent material of the sample is likely to be subjected. These temperatures are indicated in the table below.
The glass slide is then recovered and the transmittance (% T) of this slide is measured by UV-visible spectroscopy at 550 nm, the reference value being given by a clean and blank glass slide. The value of the transmittance is higher when the presence of condensates is low, and therefore when the degassing is low.
Results:
Conclusion:
The ion bombardment treatment therefore makes it possible to reduce the degassing. Indeed, the treated parts (1 and 2) have better transmittance values and therefore a lower degassing than the untreated parts (3 and 4), even though the latter had been subjected to lower temperatures than the treated parts.
A part made of polyamide 6 (PA-6) is inserted into the chamber described in example 1. The ion bombardment parameters are the following:
Result:
After moisture uptake for 7 days at 95% RH (relative humidity) at 60° C., the uptake is 0.5% by weight for the treated PA-6 versus 6% by weight for untreated PA-6. The drop in the Young's modulus and the linear expansion are respectively 20% and 0.5% for the treated PA-6 versus 80% and 2% for untreated PA-6.
The temperature limit for the appearance of degassing is 160° C. for the treated PA-6 versus 110° C. for untreated PA-6.
Coefficient of linear expansion (CLTE, “coefficient of linear thermal expansion”): 4×10−5/° C. versus 7×10−5/° C.?
Finally, the treated PA-6 has an improvement in the tensile strength of +10% relative to the untreated PA-6.
Conclusion:
These results demonstrate that the polyamide 6 treated by ion bombardment have improved mechanical and chemical properties, in particular as regards the moisture resistance, the resistance to stresses and the temperature resistance.
The parts are prepared by injection molding from a copolycarbonate of a blend of bisphenol A (BPA) and bisphenol trimethylcyclohexanone (BPTMC), denoted hereinbelow as BP-TMC-180.
Two processes are carried out on these parts:
Process A:
Step 1: treatment by ion bombardment of helium ions with an energy received by the parts of 5 keV,
Step 2: glow discharge with an air pressure of 5×10−2 to 10−1 mbar over 120 s,
Step 3: deposition of a layer of aluminum having a thickness of from 70 to 100 nm by PVD,
Step 4: deposition by DC or AC PECVD of a polysiloxane layer having a mean thickness of 35 nm from a precursor such as hexamethyldisiloxane (HMDSO).
A control part T1 is also produced with a process A identical to the process A with the exception of step 1, which was not carried out.
Process B:
Step 1: glow discharge with an air pressure of 8×10−2 mbar over 120 s,
Step 2: deposition of a layer of aluminum having a thickness of from 70 to 100 nm by PVD,
Step 3: deposition by DC or AC PECVD of a polysiloxane layer having a mean thickness of 45 nm from a precursor such as HMDSO.
Step 4: treatment by ion bombardment of nitrogen ions with an energy received by the parts of 10 keV.
A control part T2 is also produced with a process B* identical to the process B with the exception of step 4, which was not carried out.
Result:
Conclusion:
The results demonstrate that when the part is metalized, the ion bombardment carried out on high-temperature polycarbonate materials makes it possible to limit the blistering phenomena and the appearance of iridescence. It is also possible to observe that, for the treated polycarbonates, the results are similar, irrespective of the order in which the various steps of the process were carried out.
Parts made of a polypropylene copolymer are treated by ion bombardment in the chamber described in example 1 under the following conditions:
The measurements regarding the degassing are carried out as in example 2.
Result:
Conclusion:
These results demonstrate that when the polypropylene part is treated, it is less sensitive to the degassing phenomenon.
In order to characterize the layer treated by ion bombardment, an analysis by differential scanning calorimetry (DSC) and by Fourier transform infrared (FTIR) spectroscopy is carried out.
Several parts are studied with a view to being compared and samples are taken.
A reference sample is made of untreated PMMA.
The samples are referenced as follows:
Analysis by DSC:
Samples No. 2 to 4 are prepared by extraction in ethyl acetate (true solvent of thermoplastic PMMA). The presence of an insoluble fraction (deposit) is noted in samples 2 to 4. This insoluble fraction is dried then analyzed by DSC in comparison with the dried and also analyzed soluble fraction of the reference sample. The thermogram resulting from the DSC analysis is present in
It is noted that the glass transition temperature (Tg) has disappeared in samples 2 to 4. Furthermore, it was observed that none of the insoluble fractions have melted at the end of the DSC analysis (observation of the content of the capsules).
Analysis by FTIR Spectroscopy:
Samples 2, 3 and 5 were analyzed by FTIR (Fourier transform infrared spectroscopy). The infrared spectrum resulting from this analysis is given in
Tests were carried out in order to determine the effect on the adhesion of the surface of a layer of PMMA treated by an ion beam. Each sample tested was subjected to a beam of ions resulting from helium (He+). The dose of ions received varied from one sample to the next.
The adhesion of the treated layer of these samples was evaluated by measuring the polar component of the surface energy of the treated layer of the corresponding sample. The surface energy specifically comprises a dispersive component and a polar component, and it is this polar component that is correlated to the adhesion of the surface. The higher this polar component, the better the adhesion.
The polar component of the surface energy was calculated by a Zisman type method. The angle that a drop of solvent deposited on the treated surface makes with this surface is measured. By carrying out the measurement for three different solvents of known surface energy, the surface energy of the treated layer, and also its polar and dispersive components, are successfully measured.
The table below gives the results obtained for the various samples.
By considering the polar component of the surface energy of these various treated samples (samples No. 1 to 4) and of that of the untreated sample (No. 5), it is observed that the best adhesion is obtained by the treated sample No. 3. However, this adhesion is very close to that of sample No. 5, namely the control sample without any treatment. For all the other samples, the polar component, and therefore the adhesion is significantly reduced. The greater the deviation from the dose received by sample 3, the worse this adhesion.
These results show that the ion beam treatment at best has no influence on the adhesion of the treated layer, and for precise parameters. For most of the dosages, the ion beam treatment reduces the adhesion.
It follows therefrom that for polymers for which the adhesion is already low, such as PMMA, PC and high-temperature PC, it will be difficult to metalize the surface of the treated material based on polymer(s). Thus, for such materials, when it is desired to both metalize the material and treat it with a beam of ions, it is advantageous to carry out the deposition of the metallic layer on the material based on polymer(s), before carrying out the ion beam treatment.
For example, by considering example 4, even though the processes A and B both make it possible to limit the blistering phenomena and the appearance of iridescence, it may be preferred to choose process B in order to facilitate the step of metallization of the part.
While the system, apparatus, process and method herein described constitute preferred embodiments of this invention, it is to be understood that the invention is not limited to this precise system, apparatus, process and method, and that changes may be made therein without departing from the scope of the invention which is defined in the appended claims.
| Number | Date | Country | Kind |
|---|---|---|---|
| 1057514 | Sep 2010 | FR | national |
This application is the U.S. National Phase application of PCT/EP2011/066177 filed Sep. 19, 2011, which claims priority to French Application No. 1057514 filed Sep. 20, 2010, which applications are incorporated herein by reference and made a part hereof.
| Filing Document | Filing Date | Country | Kind | 371c Date |
|---|---|---|---|---|
| PCT/EP2011/066177 | 9/19/2011 | WO | 00 | 5/15/2013 |
