Composite sheets of polyarylene sulfide resin.

0001The invention relates to composite films made of polyarylene sulfides and a process for their production. The composite films according to the invention are notable for particularly good adhesion and are suitable for electronic components and for the production of membranes.

0002The treatment of PAS molding compositions with HF salts or HF-containing acids is known from JP-A 62/142786. For some applications, particularly as a membrane and for weather protection, the ions remaining in the molding compositions after treatment are a nuisance.

0003From EP-A 182 379 it is known to obtain improved metal adhesion by laser treatment of PAS surfaces and ion etching if, in particular, the known additives TiO₂, SiO₂, CaCO₃ and / or CaSO₄ are used as suitable fillers. The process is very complex.

0004According to US Pat. No. 4,486,463, good adhesion of copper to PAS molding compositions is known to be achieved if amorphous surfaces are treated with sulfuric acid / sodium dichromate solutions. The removal of the remaining residual solvents on the PAS surfaces is complex.

0005From EP-A 103 148 it is known to achieve improved metal adhesion through physical aging of PAS surfaces. Disadvantages are long cycle times (more than 10 days) and not always satisfactory liability.

0006From JP-A 57/187327 it is known that PAS surfaces (preferably film surfaces) improve their adhesion properties to metals by corona discharge or plasma treatment. Here, too, the process itself is quite complex.

0007Compound films of polyarylene sulfide molded parts or films with other thermoplastics are known in principle. In many cases, however, they do not adhere sufficiently to one another, which leads to delamination of the composite over time.

0008There has been no shortage of attempts to improve this liability. Additives and adhesives can be added between the two films (a) and (b) (or in the case of multilayer films at all points which are important for the polyarylene sulfide film adhesion). The process has the disadvantage that the profile of properties of the highly heat-resistant polyarylene sulfide moldings is limited by the heat resistance of the adhesives in the area of ​​use. Furthermore, there are often undesirable outgassing and film contamination in the manufacture of the composites.

0009The invention relates to composite films<ul id="ul0001" list-style="none"><li>(a) Films with a thickness of 1 to 1500 microns made of polyarylene sulfides, which may contain conventional additives, fillers and reinforcing agents and</li><li>(b) Films with a thickness of 2 to 3000 µm from other thermoplastics.</li></ul>

0010Another object of the invention is a process for the production of composite films, characterized in that a preferably amorphous polyarylene sulfide film (a) is produced by a known process with a thickness of 1 to 1500 microns on the surface with aprotic organic liquids at temperatures of 10 ° C to the melting temperature of the polyarylene sulfide used, preferably from 10 ° C to 80 ° C, is treated in particular at 20 to 30 ° C and during and / or after this treatment, the film with a second film made of other thermoplastics using pressures of 1 to 500 bar, optionally with heating to temperatures of 10 ° C to 10 ° C above it Melting temperature and / or glass temperature is brought together.

0011Aprotic organic liquids such as N-alkylactams such as N-methylcaprolactam, N-methylpyrrolidone and 2-methyltetrahydrofuran are used to treat the surface of the polyarylene sulfide film.

0012The contact times of these liquids with the preferably amorphous PAS surface are less than 10 minutes, preferably less than 1 minute and in particular from 0.1 to 30 seconds.

0013Amorphous PAS surfaces with particularly high roughness are preferably obtained.

0014After drying or wiping off the liquid residues from the surfaces, a mask is then optionally applied to the PAS surface according to known methods and covers those PAS regions which should not have good adhesion with other thermoplastics.

0015If necessary, more than one film made of other thermoplastics can also be brought into contact with the polyarylene sulfide films. According to the invention, the polyarylene sulfide film (a) can be treated on one side or on both sides with the aprotic liquids, in order then to apply other thermoplastic films on one side or on both sides.

0016In a special embodiment of the invention, polyarylene sulfide-containing moldings can be coated (tiled) instead of the film of component (a) according to the invention with films from other thermoplastics (b).

0017Another embodiment of the invention is the lamination of molded parts made of other thermoplastics (b) with foils (a).

0018The present invention thus also relates to a process for the lamination of molded parts made of polymers (b) with polyarylene sulfide-containing films (a) with a thickness of 1 to 1500 µm, characterized in that a polyarylene sulfide film (a), produced per se known process with a thickness of 1 to 1500 μm on the surface with aprotic organic liquids at temperatures from 10 ° C. to the melting temperature of the polyarylene sulfide used, preferably from 10 ° C. to 80 ° C., in particular at 20 to 30 ° C., and during and / or after this treatment the film with the molding made of thermoplastics b) using pressures of 1 to 500 bar, if appropriate with heating to temperatures from 10 ° C to 100 ° C above their melting temperature and / or glass temperature.

0019The invention further relates to the laminated moldings produced by this process.

0020The present invention also relates to a process for the lamination of molded parts made of polyarylene sulfides (a) with foils made of other thermoplastics (b) with a thickness of 2 to 3000 µm, characterized in that the molded part (a) is first coated with aprotic on the surface to be laminated organic liquids at temperatures from 10 ° C to the melting temperature of the polyarylene sulfide used, preferably from 10 ° C to 80 ° C, is treated in particular at 20 to 30 ° C and during and / or after this treatment, the molding with the film made of thermoplastics b) using pressures of 1 to 500 bar, optionally with heating to temperatures of 10 ° C to 100 ° C above it Melting temperature and / or glass temperature is brought together.

0021Another object of the invention are the laminated molded parts made of PAS produced by this method.

0022In the first process step, the PAS molding compositions are processed into films in known manner on known processing machines. In this case, an essentially amorphous PAS outer layer of the molded part (film) is produced by spraying into relatively low-temperature tools or by extrusion with rapid cooling at the extrusion exit point. It is also possible to use PAS molding compositions which crystallize only very poorly and therefore generally already have an amorphous molding covering layer. Such PAS molding compositions are, for example, branched or their crystallization is prevented by additives or by impurities.

0023In general, the PAS-containing molding compounds used with preference have glass transition temperatures of more than 85 ° C. and a heat resistance, determined according to Vicat B, of more than 230 ° C., in particular more than 260 ° C. In the case of partially crystalline PAS with glass transition temperatures below 230 ° C., a preferred Vicat B temperature of above 230 ° C. can be achieved by means of fillers and by crystallization formers.

0024Polyarylene sulfides (PAS), preferably polyphenylene sulfide (PPS), which are suitable according to the invention are known, for example, from EP-A 171 021, US Pat. No. 3,354,129. You can use structural elements of formulas (I) - (IV)<chemistry id="chem0001" num="0001"><img file="EP0448822A2_D0001.tif" /></chemistry> in the<dl id="dl0001"><dt>R</dt><dd>for C₁-C₄-alkyl, C₆-C₁₀-aryl and</dd><dt>n</dt><dd>for 0, 1, 2,</dd></dl> stands, contain.

0025The PAS can be linear or branched. Their properties can be varied by special end groups. Mixtures of any composition of the different PAS are possible.

0026The PAS can contain up to 60% by weight of known additives, fillers and reinforcing agents, for example inorganic fillers such as glass fibers.

0027Small admixtures of other polymers, preferably up to 5 parts by weight per 100 parts by weight of PAS, can also be added to the PAS-containing molding compositions.

0028Polyphenylene sulfide (PPS) is preferably used.

0029PAS-containing molding compounds are known and are commercially available, for example, under the trade names FORTRON®, SUPEC®, RYTON®, TEDUR®.

0030A major advantage of the invention is that it is simple to carry out without increasing the cycle time in the manufacture of the composite. Special technical equipment is not required - the surface treatment can, for example. by spraying or immersing in the liquid.

0031Other thermoplastics (b) in the sense of the invention are known amorphous or partially crystalline polymers with molecular weights M._w from 10,000 to 300,000 g / mol. Preferred are polymers which have a glass transition temperature of more than 80 ° C or which, as partially crystalline polymers, have a melting temperature of more than 100 ° C, preferably more than 120 ° C and less than 400 ° C.

0032Such polymers are known and commercially available. For example, polycarbonates, polyamides, polyolefins, polysulfones, polyketones, thermoplastic vinyl polymers such as polymethylacrylic acid esters or homopolymers of vinyl aromatics, copolymers of vinyl aromatics or graft polymers of vinyl monomers on rubbers, polyethers, polyimides, thermoplastic polyurethanes, aromatic polyesters (carbonates) and liquid-crystalline.

0033The films according to the invention can be used in the production of electrical components such as printed circuit boards, chips, etc.

Examples

0034<ul id="ul0002" list-style="none"><li>I) Polyarylene sulfide molding compositions: The following PAS-containing molding compounds were used:<ul id="ul0003" list-style="none"><li>a) PAS, produced in accordance with US Pat. No. 3,354,129 with branch addition;</li><li>b) PAS according to EP-A 142 024, Example 2;</li><li>c) PAS according to US-A 4,286,018, Example 10;</li><li>d) PAS according to US-A 3,354,129.</li></ul></li><li>II) other thermoplastics:<ul id="ul0004" list-style="none"><li>a) bisphenol-A polycarbonate with a relative viscosity - measured in methylene chloride at 25 ° C. and a concentration of 0.5 g / dl polymer - of 1.28;</li><li>b) Polymethyl methacrylate V 811 - Rohm &amp; Haas;</li><li>c) polycaprolactam with a relative solution viscosity of 3.0 - measured as a 0.5% by weight solution in m-cresol;</li><li>d) polyethylene terephthalate with an intrinsic viscosity of 0.72, measured in phenol / o-dichlorobenzene weight ratio 1: 1 at 25 ° C;</li><li>e) polybutylene terephthalate with an intrinsic viscosity of 1.21, measured in phenol / o-dichlorobenzene (weight ratio 1: 1) at 25 ° C;</li><li>f) poly (2,6-dimethyl-1,4-phenylene) ether with a relative viscosity of 1.62, measured in chloroform at 25 ° C., 0.5% by weight solution;</li><li>g) Aromatic polyester carbonate based on bisphenol A with an ester content of 80% by weight (isophthalic acid: terephthalic acid = 1: 1) with a relative viscosity of 1.3 (0.5% by weight solution in methylene chloride);</li><li>h) polyether sulfone based on bisphenol A, produced by reacting dichlorodiphenyl sulfone and bisphenol A in diphenyl sulfone by known processes, with a rel. Viscosity of 1,249 (0.5% by weight solution in methylene chloride);</li><li>i) Polyether ketone based on bisphenol-A, produced by reacting difluorobenzophenone and bisphenol A by known processes, for example EP-A 1879), with a relative viscosity of 1,455 (0.5% by weight solution in methylene chloride).</li></ul></li><li>III) Production of the films from substances I) and II) The films were produced from the substances by a known method. For this purpose, the films were extruded in the melt from a die slot in a manner known per se, biaxial stretching being dispensed with. The nozzle slot was adjusted so that the films each had a thickness of approximately 100 μm.</li><li>IV) Examples not according to the invention:<ul id="ul0005" list-style="none"><li>1. example Film Ia) was heated to 180 ° C. for 2 minutes, film IIa) was heated to 140 ° C. for 2 minutes, then both films were pressed for 3 minutes at temperatures of approximately 160 ° C. using a pressure of 200 bar. The films did not adhere very well to one another. They could be pulled apart in a simple manual test.</li><li>2nd example As in Example 1, but after washing the film Ia) with<ul id="ul0006" list-style="none"><li>(i) water,</li><li>(ii) methylene chloride,</li><li>(iii) acetone,</li></ul> with a contact time of about 30 seconds and subsequent wiping of the liquid residues, a composite film was produced. It also did not show good adhesion properties.</li></ul></li><li>V) Examples according to the invention<ul id="ul0007" list-style="none"><li>3rd-5th Example: (comparison to example 1) As in the example not according to the invention, but with additional use of the method according to the invention, the foils Ia) and IIa) were brought together. First, the film Ia) was each with one of the substances<ul id="ul0008" list-style="none"><li>(i) NMC</li><li>(ii) NMP</li><li>(iii) 2-methyltetrahydrofuran</li></ul> Contacted for 45 seconds at 25 ° C, then the surfaces were dried in air at room temperature after having been wiped with a drying cloth and then the composite film according to Example 1 was produced. The composite film adhered excellently.</li><li>Examples 6-13 In accordance with Example 3, but at press temperatures which were in each case 30 ° C. above the glass temperature for the material II) b) -i) used, composite films were produced after pretreatment with NMC, NMP and 2-methyl-tetrahydrofuran (THF) according to Table I:</li></ul></li></ul><tables id="tabl0001" num="0001"><img file="EP0448822A2_D0002.tif" /></tables> Liability was good in all cases.