JPH06503044A - Process for producing shaped articles by compacting small particles or granules based on polyisocyanate polyaddition products - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

[Detailed description of the invention] For compacting small particles or granules based on polyisocyanate polyaddition products The method of manufacturing molded articles according to the invention is characterized by a pressure of up to 1000 bar and 230°C Small particles based on polyisocyanate polyaddition products are also produced in compression molds at temperatures up to or a method for producing shaped articles by compressing granules.

As mentioned in the introduction, polyisocyanate polyaddition formation under the action of pressure and heat It is known that shaped articles can be produced by extruding particles based on [ EP-A 3 310 896, EP-A-2348760], where this The particles of interest may be produced directly from the reaction mixture to be shaped or produced for this purpose. Either by granulating the material or as it occurs during recycling. Depending on the desired physical properties of the molded article to be created, the material can be obtained in dimensions Granulation is carried out in a range from coarse particles to powder. Mix particles of different dimensions You can also. If necessary, create a molding compound from the granulated material. You can also do that.

Compression (hot pressing, ripening, hot pressing, and especially extrusion can be mentioned) is common The process is carried out in a compression mold made from steel and equipped with a vertical flush surface for sealing. It will be done.

To create a highly homogeneous molded article produced, the material to be compressed is placed in the mold cavity. During compaction, particles or granules must be distributed as evenly as possible within the tee. Press evenly against each other to bring them into direct contact. The nature of this contact is created It primarily determines the properties that can occur in molded articles. For a given material, this property can be influenced by the selection of temperature, pressure and compression time.

It is therefore an object of the present invention to or better coalesce the particles or granules for a given compression time and Improving known methods with the aim of significantly improving the mechanical properties of shaped articles It is in.

The purpose of this is to introduce additional shear stress between individual particles or between individual granules during compression. This can be achieved by making it exist. This shear stress is caused by the characteristic relative motion of particles. can be obtained. However, if a layer of uniform depth is compressed normally, the particles will be compressed only by pressure. receive.

Preferably the shear stress localizes the material to be compressed to one location within the mold cavity. Accumulate and generate.

Surprisingly, a significant improvement in the mechanical properties of the molded articles produced was achieved with this simple method. demonstrated by means. When closing the mold and during the compression process, the material It spreads within the cavity, and relative motion between particles occurs. For large cavities, pressure It goes without saying that the shrinking material may accumulate in several locations. enough Ensure that the flow path and sufficient relative movement of the particles create the desired shear stress. Only that is important.

According to one embodiment of this novel method, shear stress forces particles or granules through an opening. generated by extrusion into the mold cavity.

This means that in the simplest case the mold cavity is open on the side. . However, it is convenient to provide specific openings to obtain the desired flow path.

However, molded articles produced in this way must be trimmed. or extruding particles or granules from a mold cavity into an auxiliary cavity. The same effect can also be achieved by generating shear stress.

According to another particular embodiment of implementing the new method, the shear stress is reduced over the time of compression. or change.

By using this method, it is possible to impart locally variable properties to molded articles. Liisocyanate polyaddition products include, for example, single-stage or multi-stage by law (a) an organic polyisocyanate; (b) having a molecular weight of 1,800 to 12,000 and being anti-isosoameric; Compounds containing at least 2.5 groups on the corresponding statistical average and, if necessary, c) at least two first and/or is a polyamine with a second aromatic bonded amino group and optionally (d) optionally containing ether groups in the molecular weight range of 60-1799; A (cyclo)alkane polyol or (cyclo)alkane polyol having an NCO reactivity of at least 2 b) an alkane polyamine; Further as needed e) 60 to 14 auxiliaries and additives known per se from polyurethane chemistry. used together while maintaining an isocyanate index of 0, and further D) fillers and/or reinforcements It is possible to use those produced by reacting with.

Surprisingly, with the method of the invention the particles or granules adhere better to each other. In addition to these benefits, many other benefits are also obtained that result in improved molded articles. surface, especially the degree of gloss, as well as improved mechanical properties and non-granulated starting material The maintenance of properties is better compared to the properties of quality.

Appropriate auxiliaries and additives used in the production of polyisocyanate polyaddition products Additives (e) include, for example, internal mold release agents, catalysts for polyisocyanate polyaddition reactions, and moisturizers. Lubricants, surface-active additives, foam regulators, pigments, dyes, flame retardants, stabilizers, plasticizers or Does it have antifungal or antibacterial activity? For example, EP-B 0 081 70 No. 1, column 6, lines 40 to 9, line 31.

Suitable auxiliaries and additives which may be used include fillers and/or additives known per se. is a reinforcement material such as barium sulfate, diatomaceous earth, slurried calcium carbonate, cloud matrix, cellulose fibers, lignocellulose fibers, and granulated natural or synthetic fibers. Rubber, synthetic fibers, especially polyamide fibers, LC fibers, aramid fibers, inorganic fibers, Especially glass fibers, glass flakes, glass bulbs or carbon fibers, carbide, gold metal mats made from metal fibers, aluminum, steel or copper; These fillers and/or reinforcements are filled or reinforced polyisocyanate. up to 80211%, preferably up to 50% by weight, based on the total weight of the polyaddition product. Can be used in quantity.

In addition, fibrous fillers can be used in woven fabrics, mats, knitted fabrics, non-woven fabrics, gratings, grids, It can also be present in the form of a mesh or interlock fabric.

Fillers and reinforcements that can be used in producing polyisocyanate polyaddition products (e) are further fillers and reinforcing materials (f) which may be incorporated in the process of the invention. When the fillers and reinforcing materials (f) are incorporated by the method of the invention, the fillers and reinforcing materials (f) The presence of reinforcing agents in the granulated polyisocyanate polyaddition product is a It doesn't really matter.

Crushing and granulation of polyisocyanate polyaddition products can be done from large molded articles to small This is done using a device that is used to create smaller parts. Suitable granulation The methods are, for example, cutting, tearing, shredding or granulating methods and are well known to those skilled in the art. Equipment suitable for zero granulation is commercially available.

For example, the sieves following a granulating device with rotating knives are extremely passable. this species The device is, for example, manufactured by Wyeth Company, D-6430, D-6430, D. It can be obtained from Italy.

Carrying out the method according to the invention, i.e. comminution or granulation by the action of pressure and temperature The processed polyisocyanate addition product can be processed using, for example, compression molds or SMC molds. suitable for this, such as lamps, RIM clamps, calendars or thermoforming compression molds. This can be done using any device that does. However, carrying out the method of the invention If so, the material is known to occur in the strict sense of the term as a "thermoplastic" plastic. does not melt as it does; macroscopic phases of relatively low viscosity liquids do not always occur.

The forming tool to be used in the method of the invention is preferably provided with a vertical flush surface to In addition to facilitating pressure build-up within the mold, it also has cavities or openings. Escaping of material from the actual area of the molded article after closing the tool and applying pressure , thus promoting shear action after the actual pressure build-up.

The method according to the invention is suitable for inserts, cartons, containers of various dimensions and volumes. As a hollow body: dance board, control panel, steering column cover As a cover for things such as wheel guards, airplanes, car body parts, such as doors. A panel, side bars, cloak guard, engine compartment, bonnet The molded article is made as a lining for a boot or boot lid; Allows you to create a camp, seat or seat back. in sheet form The product of the method according to the invention is a desk pad, a desk pad with a magnetic support. As sprayboards, adhesive sheets, protective sheets and covers for a very wide range of purposes. The product of the process according to the invention can also be used for sheets, seat backs, cushions, suitcases and similar containers, structural parts of automobile bodies, shirt shirts – reinforcing members, such as frames, supports, rigid external parts of the car body, etc. e.g. mudguards or bonnets or bootlids, hubcaps etc. Reinforcement of parts, screens, automobile interior door exteriors, doors, tailgates, roofs It can also be used as articles such as members. Furthermore, these materials are made from materials such as wood. It can also be compressed together and then used in automobile interiors. In addition, the leisure field It is also suitable for other items.

Furthermore, the products of the method according to the invention are keyboard components, rigid-elastic seals and Collar, notch grip and handle, small damper member or plain washer Alternatively, use spacing washers, reinforcement of cable ducts and seal lips, etc. A material that can also be used as an unreinforced part or as other small, sturdy articles. Example Plates were made from the following ingredients: NGO reactive components: 83.3 parts: initially 83% by weight propylene oxide and then 17% by weight Converting ethylene oxide to trimethylolpropane with primarily primary hydroxyl groups Triether polyol having an OH number of 28 created by block addition, 4 parts: 1 part carbon black and 4 parts polyether (having an OH number of 35) , first 87% by weight propylene oxide and then 13% by weight ethylene oxide. (prepared by the block addition of trimethylolpropane), 12 parts 80% 1-methyl-2,4-diamino-3,5-diethylbenzene and 20% Mixture of 1-methyl-2,6-diamyto-3,5-diethylbenzene, 0, Part 1: Davgo (registered trademark) 33LV, i.e. Air Products, USA? amine catalyst, 0, Part 1: Homerez (registered trademark) UL2B, i.e. Lightco, USA? The tin catalyst of et al.

NGO ingredients: PU0743, containing 23% NGO and a density of 1.22 g/cm3 Bayer AG, D-5090, Leverkunsen, based on urethane modified MDI Commercial product from Germany.

A ratio of 100 to 39 NCO reactive components to NCO components was used. PUR granules To prepare a 4 mm sieve insert, the plate prepared as above was Cutting of Ballman D-6660, Zwiblinoken, type PS-4-5 It was granulated using a granulator. Impact grinder that grinds materials to <2mm powder Alternatively, a hammer mill can also be used for granulation.

The granulated material was heated in a heating cavity vent set at 180°C for 15 minutes. or preheated and then immediately placed into a sheet mold with a vertical flush surface. This mold closed, then hydraulic brace [Sparchentan, D-1000 Herlin, Germany] The pressure was increased to 200 bar using a model 200T from Turkey.

The actual compression process was continued for 3 minutes at 180"C. Then the plate was heated to a still warm temperature. It was taken out from the mold. The surfaces of these plates exhibit a typical grain structure and are extremely smooth. Met. ASTM tensile test samples were taken from these plates and the tensile strength was 4. ．． 2 MPa and an elongation at break of 8 according to DIN 53504. It was determined to be 8%.

The test was repeated using the same compression conditions but between compression plates with open sides. . In this way, the particles were stressed by shear forces. A program created in this way A plated molded article exhibits clearly visible flow lines and has a It was half the thickness. Tensile strength in ASTM tensile test samples from these plates The test showed a tensile strength of 8.8 MPa and an elongation at break of 310%.

1 injury I Plates were made from the following ingredients: NGO reactive components: 83.3 parts: polyether polyol having an OH number of 35 [87 parts % by weight of propylene oxide and then 13% by weight of ethylene oxide. Created by block addition to trimethylolpropane having an H group], 4 parts: 1 part carbon black and 4 parts polyether with an OH number of 35 ( First 87% by weight propylene oxide and then 13% by weight ethylene oxide (created by block addition of trimethylolpropane), 12.5 parts: 65% 1-methyl-2,4-diamino-3,5-diethylbenze of 1-methyl-2,6-diamitu-3,5-diethylbenzene at 35%. Compound, 0.1 part: Davgo® 33LV, i.e. Air Products, US amine catalyst from A, 0.1 part: Homere (registered trademark) UL28, i.e. from Liteco, USA tin catalyst.

NGO ingredients: PU 0743, i.e. with 23% NCO and a density of 1.22 g/cm3 Bayer AG, D-5090, based on urethane modified II MDI Commercial product from Germany.

The NCO reactive component and NCO component were used in a ratio of 100:39.

The granulation and preparation for the compression process, as well as the compression process itself, are described in Example 1. I did as I said.

Samples from molded articles made using vertical flush-face molds had a pressure of 13.3 MPa. It exhibited tensile strength and elongation at break of 390%. 2 pieces with open sides A sample of the molded article made between compression plates of had a tensile strength of 16.3 MPa. It also showed an elongation at break of 440%.

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Claims (5)

[Claims] 1. In compression molds under the action of pressures up to 1000 bar and temperatures up to 230 °C compacting small particles or granules based on polyisocyanate polyaddition products using In the method of manufacturing shaped articles, additional shear stress is applied to individual particles during compression. A method for producing a molded article, characterized in that the molded article is produced between particles or between individual granules. 2. Accumulates shear stress specifically in the material to be compressed at a predetermined location within the mold cavity The method according to claim 1, characterized in that the method is produced by: 3. The shear stress is applied by forcing the particles or granules through the opening into the mold cavity. A method according to claim 1, characterized in that the method is generated by: 4. The shear stress is applied to push the particles or granules from the mold cavity into the auxiliary cavity. 2. A method according to claim 1, characterized in that the method is generated by emitting a liquid. 5. Claim 1 characterized in that the shear stress is varied over the time of compression. 4. The method according to any one of items 4 to 4.